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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional of U.S. patent application Ser. No. 12/917,925, filed Nov. 2, 2010; the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Technical Field
[0003] The present invention relates generally to apparatus and methods for cleaning elongate tubes. More particularly, the apparatus and methods relate to using a lance to spray high pressure water into elongated tubes. Specifically, the apparatus and methods of the present invention relate to guiding a lance into elongated tubes by opening and closing doors supporting the lance.
[0004] 2. Background Information
[0005] Heat exchangers are used for the transfer of heat from one fluid medium to another. One of the fluids passes through a series of conduits, or elongated tubes, while the other passes on the outside of the tubes. During this process, carbonaceous and other deposits form on the interior of the individual tubes. Debris and other dirt collects on the surface of the individual tubes. To maintain efficient operation, it is necessary to periodically remove the tubes and clean their interior and exterior surfaces.
[0006] One method of cleaning the interior of heat exchanger tubes includes the progressive insertion of a small diameter tube, known as a lance, into the heat exchanger tube and the pumping of high pressure water through the lance to clean the interior of the tube. The water pressure in a lance may easily exceed 10,000 psi with flow rates in excess of 100 gallons per minute. There are problems inherent in using a lance to clean heat exchangers. For example, it is very difficult to keep the lance from buckling and bending while it is being guided into the tube. A more serious problem, however, is jet reaction from the high pressure stream. Since the fluid is forced through the lance at extremely high pressures (in excess of 10,000 psi) the fluid discharge from the lance tip can frequently blow backward and strike the operators guiding the lance.
[0007] One apparatus used to clean heat exchangers supports the rear portion of the lance in an elongated channel member which has an open top. The front end (operating end) of each lance is fed into the tube through a vertical separator plate positioned at the front end of the channel member. The drive means comprises a set of motor-driven friction rollers which engage the lances immediately behind the separator plate. The major portion of the lance is supported in the open channel member behind the drive rollers and the motor. However, in these types of apparatus the lance can be quite long and hard to accurately position as it travels on the channel member. Therefore, improved heat exchanger cleaning technology is desired.
SUMMARY
[0008] The preferred embodiment is an apparatus for cleaning elongated tubes. The apparatus includes a cart, a lance, and a pressure sensing device and a propulsion device. The lance sprays material into elongated tubes to clean the elongated tubes. The cart supports the lance while the cart is moves in a rail in a forward direction and in a reverse direction. The pressure sensing device is located in the cart and detects a pressure exerted on the cart as the cart moves in a forward direction in the rail. The propulsion device, upon the pressure sensing device detecting a pressure crossing a threshold value, propels the cart in the reverse direction for predetermined distance or time before again propelling the first cart in the forward direction.
[0009] Another configuration of the preferred embodiment is a method of cleaning elongated tubes. A cart holding a lance is propelled through a rail in a forward direction. Material is sprayed out of the lance to clean an elongated tube. During this process a pressure may be applied to the cart and this pressure may cross a threshold value. In response to the pressure crossing the threshold, the cart stopped and backed up in backward direction for a distance. This distance may be a predetermined distance or the cart can back up for a time period. After backing the cart up the distance, the cart is again moved in the forward direction to continue cleaning the elongated tube.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] One or more preferred embodiments that illustrate the best mode(s) are set forth in the drawings and in the following description. The appended claims particularly and distinctly point out and set forth the invention.
[0011] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate various example methods, and other example embodiments of various aspects of the invention. It will be appreciated that the illustrated element boundaries (e.g., boxes, groups of boxes or other shapes) in the figures represent one example of the boundaries. One of ordinary skill in the art will appreciate that in some examples one element may be designed as multiple elements or that multiple elements may be designed as one element. In some examples, an element shown as an internal component of another element may be implemented as an external component and vice versa. Furthermore, elements may not be drawn to scale.
[0012] FIG. 1 illustrates an example environment in which a preferred embodiment of an apparatus for cleaning elongated tubes operates.
[0013] FIG. 2 illustrates an example side view of a motorized cart and a lance cart of the preferred embodiment.
[0014] FIG. 3 illustrates an example top view of the motorized cart and the lance cart of the preferred embodiment.
[0015] FIG. 4 illustrates an example front view of the lance cart of the preferred embodiment.
[0016] FIG. 5 illustrates an example bottom view of the motorized cart and the lance cart of the preferred embodiment.
[0017] FIG. 6 illustrates an example perspective view of a rail and two doors of the preferred embodiment.
[0018] FIG. 7 illustrates an example front view of a door of the preferred embodiment in the closed position.
[0019] FIG. 8 illustrates an example side view of a door of the preferred embodiment in the open position.
[0020] FIG. 9 illustrates an example cross-sectional view of the door of the preferred embodiment taken at line 9 in FIG. 8 .
[0021] FIG. 10 illustrates an example internal side of a motorized cart and a lance cart of the preferred embodiment as viewed through the rail.
[0022] FIG. 11 illustrates an example cross-sectional view of the motorized cart of the preferred embodiment taken at line 11 in FIG. 10 .
[0023] FIG. 12 illustrates an example cross-sectional view of the motorized cart of the preferred embodiment taken at line 12 in FIG. 10 .
[0024] FIG. 13 illustrates an example cross-sectional view of the motorized cart of the preferred embodiment taken at line 13 in FIG. 10 .
[0025] FIG. 14 illustrates an example side view of the lance cart of the preferred embodiment as it approaches a door.
[0026] FIG. 15 illustrates an example top view of the lance cart of the preferred embodiment as it approaches the door.
[0027] FIG. 16 illustrates an example top view of the lance cart of the preferred embodiment as it opens the door.
[0028] FIG. 17 illustrates an example top view of the lance cart of the preferred embodiment as it passes through two doors in the open position.
[0029] FIG. 18 illustrates an example side view of the lance cart of the preferred embodiment as it opens the door.
[0030] FIG. 19 illustrates an example top view of the lance cart of the preferred embodiment as it travels in the reverse direction.
[0031] FIG. 20 illustrates an example top view of the lance cart of the preferred embodiment as it closes a door while traveling in the reverse direction.
[0032] FIG. 21 illustrates an example top view of the lance cart of the preferred embodiment after it has closed two doors while traveling in the reverse direction.
[0033] FIG. 22 illustrates an example side view of the apparatus of the preferred embodiment showing the lance traveling in the forward direction while encounter heavy material in the tube.
[0034] FIG. 23 illustrates an example side view of the apparatus of the preferred embodiment showing the lance traveling in the reverse direction after encountering heavy material in the tube.
[0035] FIG. 24 illustrates an example side view of the apparatus of the preferred embodiment showing the lance traveling in the forward direction after traveling in the reverse direction after encountering heavy material in the tube.
[0036] FIG. 25 illustrates an example side view of the lance cart of the preferred embodiment mounted with a dual lance.
[0037] FIG. 26 illustrates an example front view of the lance cart of the preferred embodiment mounted with the dual lance.
[0038] FIG. 27 illustrates configuration of the preferred embodiment as a method of cleaning elongated tubes.
[0039] Similar numbers refer to similar parts throughout the drawings.
DETAILED DESCRIPTION OF THE INVENTION
[0040] FIG. 1 illustrates a tube cleaning apparatus 1 resting on two support structures 2 while cleaning one of the tubes 4 of a heat exchanger 3 . Those of ordinary skill in the art will appreciate that the tube cleaning apparatus 1 can be mounted in a mechanical rack that is sturdy enough to support the apparatus 1 and to provide for the rapid repositioning of the apparatus 1 to other positions to clean other tubes 4 of the heat exchanger 3 . The tube cleaning apparatus 1 includes a rail 17 (e.g., channel) with a front end 6 and a back end 7 , and a tube cleaning cart system 19 . The tube cleaning cart system includes a motorized cart 20 and a lance cart 50 mounted with a lance 51 . The carts 20 , 50 are made out of solid material such as a metal and are best seen in FIGS. 2 , 3 and 5 . The motorized cart 20 includes a left side wall 34 , right side wall 36 , front side wall 35 and a back side wall 37 . Similarly, the lance cart 50 includes a left side 64 , a right side 65 a front side 63 and a back side 62 .
[0041] FIG. 1 also illustrates four door assemblies 13 , 14 , 15 , 16 attached to the rail 17 . In the preferred embodiment, the door assemblies 13 , 14 , 15 , 16 are equally spaced from each other and evenly distributed the length of the rail 17 . One of ordinary skill in the art will appreciate that FIG. 1 illustrates four door assemblies 13 , 14 , 15 , 16 ; however, fewer than four doors or more than four doors can be attached to the rail 17 . As discussed in detail below, the door assemblies 13 , 14 , 15 , 16 support the lance 51 as it travels forward and backward in the rail 17 . Also as discussed in detail below, as the lance cart 50 approaches a door moving in the forward direction toward the back end 7 of the rail, the door is opened. When the lance cart 50 approaches a door moving in the reverse direction toward the front end 6 of the rail, the door is closed.
[0042] A supply of high pressure water 10 and/or high pressure air 9 is connected to the motorized cart 20 and to the lance cart 50 . FIG. 2 illustrates the water line connector 60 and the air line connector 61 on the lance cart 50 . The high pressure water and/or air can be used as a material that is ejected from a tip 52 of the lance 51 at high pressure as a spray 53 to clean unwanted materials from the tubes 4 . The water and/or pneumatic oil can also be used as an energy source to propel the two carts 20 , 50 in the rail 17 so that the lance 51 can be inserted into the tubes 4 and removed from the tubes 4 of the heat exchanger 3 . Water may generally exit the lance tip 52 at 10,000 to 40,000 psi. The water may be connected to a controller 11 of the motorized cart 20 . The controller 11 can regulate the amount of air and/or pneumatic oil received at a cart motor 21 to regulate the speed that the motorized cart 31 that propels the lance cart 50 .
[0043] FIG. 6 illustrates that in the preferred embodiment, a cross-section of the rail 17 is C-shaped with an open top 75 that allows the lance 51 to project out of the open top 75 . The rail 17 is a rectangle shape with a flat bottom wall 70 , a left side wall 71 , a right side 72 and a pair of upper lips 73 and 74 projecting inward from the tops of the sides 71 , 72 . These walls form an inner channel chamber 78 . The left side wall 71 of the rail 17 has a gear rack 76 running generally the length of the rail 17 . As best shown in FIG. 11 , this provides for a drive gear 22 in the motorized cart 20 to engaged the gear rack 76 and, thus, propel the motorized cart 20 and lance cart 50 across the rail 17 . An opening is 26 formed in the right side wall 36 of the motorized cart 20 and the drive gear 22 extends from this opening 26 to engage the gear rack 76 .
[0044] As best seen in FIG. 10 , a variety of wheels mounted on the motorized cart 20 and the lance cart 50 ensure the carts 20 , 50 travel securely within the rail 17 . Lower motorized cart wheels 23 and lower lance cart wheels 54 travel along the bottom 70 of rail 17 . Upper motorized cart wheels 24 and upper lance cart wheels 55 travel along a bottom surface of the upper lips 73 , 74 . Wall motorized cart wheels 25 mounted to the motorized cart 20 with angle bars 27 , 32 travel along the inside surface of the right side 72 . Motorized cart lip wheels 28 and lance cart lip wheels 56 travel along inside edges of the upper lips 72 , 73 of the rail 17 . The motorized cart 20 is held together by bolts 29 and the lance cart 50 is held together by bolts 59 .
[0045] A motor 30 is mounted to the top of the motorized cart 20 . The motor 30 may be a hydraulic or pneumatic motor. A drive shaft 31 ( FIG. 2 ) connects the drive gear 22 with the motor 30 . A coupling 40 connected between the angle bar 32 on the motorized cart 20 and an angle bar 41 on the lance cart 50 connects the carts 20 , 50 together. This connector 40 may be a pressure sensitive connector that monitors the pressure between the two carts and sends a pressure indicator to the controller 11 through a feedback line 42 . In other configurations, a pressure indication can be mechanically feedback directly to the motor 30 (or other motor regulator).
[0046] The lance cart 50 includes a lance mounting bracket 66 ( FIG. 2 ) supporting a lance gear box 77 , a drive assembly 68 , and a lance coupling 69 . The lance gear box 77 is coupled to the drive assembly 68 with a drive belt so that this assembly is configured to mechanically spin the lance 51 . The lance coupling 69 is attached to a lance connector 67 . The lance connector 67 allows the lance 51 to be easily attached and removed from the lance cart 50 . The lance cart 50 also includes a top door pusher 80 and a bottom door pusher 81 . The pushers 80 , 81 are made out of polyurethane material and are attached to a pusher mounting bracket 82 . The pusher mounting bracket 82 is mounted to the top of the lance mounting bracket 66 with one or more fasteners 83 . The bottom door pusher 81 is mounted to the bottom of the pusher mounting bracket 82 while the top door pusher 80 is mounted to the top of the pusher mounting bracket 82 . The pushers 80 , 81 are fastened to the pusher mounting bracket 82 with one or more bolts 84 or other fasteners. The top door pusher 80 may be formed with beveled corners 86 at the two corners used to push close doors of the door assemblies 13 , 14 , 15 , 16 . The bottom door pusher 81 may be formed with beveled corner at the two corners used to push open the doors of the door assemblies 13 , 14 , 15 , 16 .
[0047] In the preferred embodiment, the door assemblies 13 , 14 , 15 , 16 are placed on alternating sides of the rail 17 . For example, door assemblies 13 and 15 can be placed on the of right side wall 72 the rail 17 as shown in FIG. 1 and door assemblies 14 and 16 can be placed on the left side wall 71 . Each door assembly 13 , 14 , 15 , 16 includes a door base 89 and a door 12 . This is best seen in FIGS. 7-8 that illustrate door assembly 14 . The door base 89 is comprised of mounting blocks 92 , 92 attached to a base 90 . The door 12 is pivotally mounted with a pivot rod 85 to the door base 89 . The pivot rod 85 is passes through the mounting blocks 91 , 92 . The base 90 is connected to the rail 17 with one or more fasteners 93 that can be bolts. A stop block 94 with a first leg 120 and a second leg 122 ( FIG. 9 ) is also attached to the pivot rod 85 between the mounting blocks 91 , 92 .
[0048] The door 12 includes a lance support 100 that is sandwiched between two lance brackets 101 . The lance support 100 is a generally rectangular shaped polymer block with a tapered opening 103 cut out from one sided of the block. The tapered opening 130 further includes a lance support opening where a lance 51 is supported when the door 12 is in the closed position. In operation the tapered opening 103 supports the lance 51 until the door 14 is pushed open by the lance cart 50 . The lance brackets 101 are fastened together with fasteners 102 so that the lance support 100 is rigidly attached to the pivot rod. A pusher tab block 104 with a first surface 105 and a second surface 106 is attached to the top of the lance brackets 101 .
[0049] As seen in FIG. 9 , two first magnets 95 are located adjacent one surface of the stop block 94 . Two different second magnets 96 are located adjacent a second surface of the stop block 94 . A filler nut 99 can be inserted opposite the magnets 95 , 96 . Firsts metal pegs 97 are attached at a first location on the rail 17 and second metal pegs 98 are attached at a second location on the rail 17 . The metal pegs 97 , 98 are formed with a metal that the magnets 95 , 96 are attracted to. When the door 14 of FIG. 6 is in the “closed position” the lance support 100 spans across the upper open portion of the rail 17 and the second magnets 96 are adjacent the second metal pegs 98 . When the door 14 of FIG. 6 is in the “open position” the lance support 100 is generally parallel to the left side 72 of the rail 17 and the first magnets 95 are adjacent the first metal pegs 97 . The stop block 94 is formed so that the lance support 100 cannot be rotated beyond 90 degrees between the open position and the closed position. The attractive force of the magnets 95 , 96 and the metal pegs 97 , 98 holds the door 14 in one of the corresponding positions until sufficient force is applied to the door 14 to rotate it toward the other position. Alternative to the metal pegs 97 , 98 magnets with a polarity that attracts them to magnets 95 , 96 can be used in place of the metal pegs 97 , 98 .
[0050] At the start of an elongated tube 4 cleaning operation, the motorized cart 20 and the lance cart 50 are located near the back side 7 of the rail 17 with both carts 20 , 50 between the back side 7 and the first door 13 . All the doors 12 are in the closed position. The cleaning operation is started when air and/or water are feed to the motor 30 and the lance cart 50 . The motor 30 will drive the drive gear 22 which will rotate while engaged with the gear rack 76 to propel the two carts 20 , 50 toward the front end 6 of the rail 71 and the so the lance 51 is inserted into the heat exchanger 3 and high pressure water exiting the lance tip 52 can begin cleaning one of the elongated tubes 4 . The lance gear box 77 will rotationally spin the lance 51 . This spinning assist in stabilizing the lance 51 as it ejects high pressured water.
[0051] As the lance cart 50 progresses toward the front 6 of the rail 17 in the direction of arrow A it will reach the first door assembly 13 as shown in FIG. 15 . As shown in FIGS. 14 and 15 , the lance coupling 67 will make contact with the door 12 of door assembly 13 and begin pushing the door 12 open. As the door continues to open, eventually a beveled surface 87 of the bottom door pusher 81 will make contact with the door 12 to continue to push the door 12 open. This contact will eventually cause the magnetic attraction between the second magnets 96 and the second metal pegs 98 to be overcome and the door will begin to rotate in the direction of arrow B from the closed position toward the open position. As the door 12 is rotated open, eventually the first magnets 95 form an attractive force with the first metal pegs 97 to snap the door 12 of door assembly into the open position and to hold the door 12 in this position. FIG. 17 shows the lance cart 50 as it is passing the second door 14 with both doors assemblies 13 , 14 in the open position. Notice that the second door assembly 14 on the opposite of the rail 17 than first door assembly 13 so that its door 12 will rotate in the direction of arrow C which is the opposite of arrow B. The bottom door pusher 81 continues to open doors in this manner until the lance 51 has been inserted sufficiently far into the elongated tube 4 .
[0052] After the lance 51 has been inserted sufficiently far into the elongated tube 4 , the motor 30 will reverse direction and the two carts 20 , 50 will begin to travel in the direction of Arrow D toward the back end 7 of the rail 17 as the lance 51 is withdrawn from the tube 4 . As the lance cart 50 reaches the door 12 of door assembly 16 as shown in FIGS. 18 and 19 , one of the beveled corners 87 of the top door pusher 80 will make contact with the second surface 106 of the pusher tab block 104 . This contact will cause the magnetic attraction between the first magnets 95 and the first metal pegs 97 to be overcome and the door 12 of door assembly 16 will begin to rotate in the direction of arrow E ( FIG. 20 ) from the open position toward the closed position. As the door 12 is rotated closed, eventually the second magnets 96 form an attractive force with the second metal pegs 98 to snap the door 12 of door assembly 16 into the closed position and continue to hold the door 13 in this position. FIG. 21 shows the lance cart 50 as it is passing door assembly 15 with both door assemblies 15 , 16 in the closed position. The top door pusher 80 continues to close doors in this manner until the lance 51 has been sufficiently removed from the elongated tube 4 .
[0053] In operation, as the lance cart 50 travels in a forward direction as shown by arrow S in FIG. 22 the lance may encounter enough dirt or grime built up inside the tube 4 that is difficult to blast out of the tube 4 by the lance 51 , the pressure in the coupling 40 will cross a threshold level. When this happens, the controller 11 can cause the motorized cart 20 to run in the reverse direction as shown by arrow T in FIG. 23 . Traveling in the reverse direction least partially pulls the lance 51 away from the heat exchanger 3 . After the lance 51 is partial removed, the controller 11 can then signal for the motor 30 to run in the forward direction as shown by arrow U in FIG. 24 to begin re-inserting the lance 51 back into the heat exchanger 3 . These actions can increase the chances of the apparatus 1 removing unwanted material that is tightly attached to the heat exchanger 3 .
[0054] In another configuration of the preferred embodiment, lance cart 50 of the apparatus 1 is mounted with a dual lance 100 as shown in FIGS. 25 and 26 . The dual lance 100 contains a first lance 101 and a second lance 102 . The dual lance connectors 114 , gear box 113 , drive assembly 68 , and some other components of the single lance cart 50 may need to be modified and/or duplicated in the dual lance configuration. The dual lance is support on a dual lance cart 115 that is similar to the single lance cart 50 . In operation, the first lance 101 can be inserted into a first tube 4 and the second lance 102 can be inserted into a second tube 4 to clean two tubes 4 at the same time. In one configuration of the preferred embodiment, the distance between the first lance 101 and the second lance 102 is adjustable so that tubes 4 with different diameters can be cleaned. Of course, in other configurations more than two lances can be mounted onto the lance cart 50 .
[0055] While the present invention has been described in connection with the preferred embodiments of the various figures, it is to be understood that other similar embodiments may be used or modifications and additions may be made to the described embodiment for performing the same function of the present invention without deviating therefrom. Therefore, the present invention should not be limited to any single embodiment, but rather construed in breadth and scope in accordance with the recitation of the appended claims.
[0056] Example methods may be better appreciated with reference to flow diagrams. While for purposes of simplicity of explanation, the illustrated methodologies are shown and described as a series of blocks, it is to be appreciated that the methodologies are not limited by the order of the blocks, as some blocks can occur in different orders and/or concurrently with other blocks from that shown and described. Moreover, less than all the illustrated blocks may be required to implement an example methodology. Blocks may be combined or separated into multiple components. Furthermore, additional and/or alternative methodologies can employ additional, not illustrated blocks.
[0057] FIG. 28 illustrates a configuration of the preferred embodiment as a method 500 of cleaning elongated tubes such as the tubes in a heat exchanger. The method 500 begins by moving a cart, at 502 , in a channel in a forward direction. The cart mounted with a lance sprays water or other material, at 504 , at high pressure to clean grime and other unwanted material from the elongated tubes. The water is sprayed from the lance as the cart moves in the channel.
[0058] A first door is moved from a first closed position to a first open position, at 506 , as the cart approaches the first door. A second door is moved from a second closed position to a second open position, at 508 , as the cart approaches the second door. The second door is moved to the second open position after the first door is moved to the first open position.
[0059] When removing the lance from the tube, the cart is moved in the channel in a reverse direction. The second door is moved from the second open position to the second closed position as the cart approaches the second door in the reverse direction. The first door from the first open position to the second closed position as the cart approaches the first door in the reverse direction. The first door is moved to the first closed position after the second door is moved to the second closed position.
[0060] In the foregoing description, certain terms have been used for brevity, clearness, and understanding. No unnecessary limitations are to be implied therefrom beyond the requirement of the prior art because such terms are used for descriptive purposes and are intended to be broadly construed. Therefore, the invention is not limited to the specific details, the representative embodiments, and illustrative examples shown and described. Thus, this application is intended to embrace alterations, modifications, and variations that fall within the scope of the appended claims.
[0061] Moreover, the description and illustration of the invention is an example and the invention is not limited to the exact details shown or described. References to “the preferred embodiment”, “an embodiment”, “one example”, “an example”, and so on, indicate that the embodiment(s) or example(s) so described may include a particular feature, structure, characteristic, property, element, or limitation, but that not every embodiment or example necessarily includes that particular feature, structure, characteristic, property, element or limitation. Furthermore, repeated use of the phrase “in the preferred embodiment” does not necessarily refer to the same embodiment, though it may. | A system and method for cleaning elongated tubes is presented. An apparatus for cleaning elongated tubes includes a cart, a lance, a pressure sensing device and a propulsion device. The lance sprays material into elongated tubes to clean the elongated tubes. The cart supports the lance while the cart is moves in a rail in a forward direction and in a reverse direction. The pressure sensing device is located in the cart detects a pressure exerted on the cart as the cart moves in a forward direction in the rail. The propulsion device, upon the pressure sensing device detecting a pressure crossing a threshold value, propels the cart in the reverse direction for predetermined distance or time before again propelling the first cart in the forward direction. | 5 |
FIELD OF THE INVENTION
This invention relates to a clamp. In particular, though not exclusively, the invention relates to a clamp used as a base for attaching an item to a surface.
BACKGROUND OF THE INVENTION
Clamps are used for numerous reasons. In some instances, a clamp is used to hold a work piece in place to be worked on. In other instances, a clamp is used to provide a base to mount an item to a surface.
In the case of a table clamp, the clamp can be used as a base for mounting an item on the table. For example, the clamp is fastened to the table; the clamp is adapted to connect to an arm; and an item can be suspended from the arm which is connected to the clamp. Examples of items attached to tables in this manner are task lamps, computer monitors, and various trays for holding items such as office supplies and telephones.
A clamp used for such a purpose is typically designed to accommodate tables of varying thicknesses. Such clamps are often C-clamps which include a screw that can be used to adjust the distance between the opposing clamping surfaces of the C-clamp so the clamp may be tightened against the table and thus held in place. The range of thicknesses of tables to which such a C-clamp can attach is limited by the size of the C-clamp and the length of travel of the screw in the C-clamp. To accommodate a greater range of table thicknesses, typically the size of the C-clamp and the length of the screw needs to be increased.
SUMMARY OF THE INVENTION
In a broad aspect, the invention provides a clamp comprising a frame supporting opposed members having clamping surfaces defining a distance therebetween for receiving and clamping an object; an adjustment mechanism associated with at least one of the members for varying the distance over a continuous range; and a spacer assembly being removably fastenable to at least one of the members for varying the distance by at least one discrete increment.
In some embodiments, the opposed members comprise a first member and a second member and the spacer assembly is associated with the first member.
In some embodiments, the spacer assembly comprises a block having a thickness and the block and the first member define co-operating protrusions and receiving portions for fastening the block to the second member with the distance decreased by the thickness.
In some embodiments, the protrusions comprise the first member having parallel arms which define a channel therebetween and the receiving portions comprise a narrow portion of the block sized to receive the arms.
In some embodiments, the narrow portion comprises a post which connects a first portion of the block to a second portion of the block.
In some embodiments, the first portion of the block has a first thickness and the second portion of the block has a second thickness different from the first thickness and the block can be reversibly fastened in the first member wherein the distance can be decreased by either the first thickness or the second thickness.
In some embodiments, the spacer assembly further comprises at least one block adapter having an adapter thickness wherein the block and the block adapter define co-operating adapter protrusions and receiving portions for fastening the block adapter to the block to further decrease the distance by the adapter thickness.
In some embodiments, the adapter protrusions comprise at least one post projecting from the adapter and sized to fit into a hole on the block.
In some embodiments, the clamp further comprises at least one second adapter having a second adapter thickness wherein the adapter and the at least one second adapter define further co-operating protrusions and receiving portions for fastening the second adapter to the block adapter to further decrease the distance by the second adapter thickness.
In some embodiments, the spacer assembly comprises a rod having spacing elements slidably retained on the rod; a space being movable between the spacing elements by moving the spacing elements on the rod; the first member defining a protrusion for insertion into the space for fastening the spacer assembly to the first member, the distance decreasing by the thickness of the spacing elements inserted into the distance.
In some embodiments, the protrusions comprise the first member having parallel arms which define a channel therebetween for receiving a portion on the rod extending through the space.
In some embodiments, the spacing elements comprise a plurality of rings of different thicknesses.
In some embodiments, the spacing elements further comprise plates fastened on each end of the rod.
In some embodiments, the adjustment mechanism is associated with the second member.
In some embodiments, the adjustment mechanism comprises a threaded opening in the second member and a threaded bolt axially moveable therein in a direction of the distance.
In some embodiments, the bolt comprises an orifice opposite the direction, the orifice being sized to receive a post for mounting the post thereto.
In some embodiments, the post is a post of a table lamp for mounting the table lamp to a table.
In some embodiments, the clamp further comprises a removable sleeve encircling a head of the bolt.
In some embodiments, the adjustment mechanism further comprises a plate mounted to swivel on the end of the bolt for clamping the object.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the invention will now be described with reference to the attached drawings in which:
FIG. 1 is a perspective view of a clamp according to an embodiment of the invention in which a spacer is removed from the clamp;
FIG. 2 is a side view of the embodiment of FIG. 1 in which the spacer is attached to the clamp in a first position;
FIG. 3 is a side view of the embodiment of FIG. 1 in which the spacer is attached to the clamp in a second position;
FIG. 4 is a top view of the embodiment of FIG. 1 ;
FIG. 5 is a front view of the embodiment of FIG. 2 ;
FIG. 6 is a rear view of the embodiment of FIG. 3 ;
FIG. 7 is a side view of a second embodiment of the invention;
FIG. 8A is a side view of a spacer adjustment of the embodiment of FIG. 7 ;
FIG. 8B is a side view of the spacer of the embodiment of FIG. 7 ;
FIG. 8C is a side view of another spacer adjustment of the embodiment of FIG. 7 ;
FIG. 8D is a top view of the spacer of the embodiment of FIG. 7 ;
FIG. 9 is a perspective view of a clamp according to a third embodiment of the invention;
FIG. 10 is a side view of the embodiment of FIG. 9 ;
FIG. 11A is a front view of the spacer of the embodiment of FIG. 9 ;
FIG. 11B is a sectional view of the spacer of FIG. 11A taken along line A-A of FIG. 11A ;
FIG. 12 is a perspective view of a fourth embodiment of the invention in which the spacer is removed from the clamp;
FIG. 13 is an exploded perspective view of the spacer of FIG. 12 ;
FIG. 14 is a side view of the embodiment of FIG. 12 with the spacer attached to the clamp in a first position; and
FIG. 15 is a side view of the embodiment of FIG. 13 with the spacer attached to the clamp in a second position.
DETAILED DESCRIPTION OF THE EMBODIMENTS
FIGS. 1 to 6 show a clamp 10 in three possible configurations. The three possible configurations change the distance between the clamping surfaces. The distance is changed in increments by the presence and orientation of a spacer 12 . The distance can also be varied by the use of an adjustment mechanism at the opposite end of the clamp. The adjustment mechanism includes a bolt or screw 14 connected to a clamping plate 16 . Travel of the screw 14 into and out of the clamp interior will adjust the position of the clamping plate 16 over a continuous range of the travel of the screw 14 and thereby also change the distance between the clamping surfaces.
Turning to the clamp in further detail, the clamp 10 includes a supporting frame or body 18 . The body 18 is made up of two spacer arms 20 connected to two connecting arms 22 which in turn are connected to two head arms 24 . In this embodiment, the arms 20 , 22 and 24 have a square cross-section shape. The head arms 24 in turn connect to a head 26 . As can be seen in the drawings, the embodiment of FIGS. 1 , 2 and 3 is C-clamp. In other words, the arms 20 , 22 and 24 define a squared C-shaped frame. In this embodiment, the spacer arms 20 are parallel to and spaced from the head arms 24 by the length of the connecting arms 22 , with the connecting arms 22 being perpendicular to both the spacer arms 20 and the head arms 24 . The arms 20 , 22 and 24 consist of two parallel arms spaced by a constant gap.
Other orientations of the arms could be utilized with corresponding changes made, if needed, to the spacer 12 and the clamping plate 16 . This invention is also applicable to other styles of clamps which are not C-clamps and could have different configurations for supporting the spacer 12 and the opposing clamping surface, such as the clamping plate 16 of this embodiment.
The head 26 in this embodiment, is connected to the head arms 24 at the opposite end of the head arms 24 from the connecting arms 22 . It would be appreciated, that the head arms 24 can be completely eliminated if the head 26 were of a sufficiently large diameter. The head 26 is internally threaded with complimentary threads to the threads of the screw 14 so that the screw 14 can be screwed to move the clamping plate 16 into and out of the interior of the clamp 10 to shorten or lengthen a distance X 1 between the clamping surfaces.
The clamping plate 16 of this embodiment is generally ring shaped with an extension 32 which is smaller in diameter than the body of the clamping plate 16 and is roughly of the same diameter as the screw 14 . However, such an extension is not essential. The clamping plate 16 is connected to the screw 14 by a smaller screw 30 which extends through a hole in the center of the clamping plate 16 and screws into the screw 14 . The clamping plate 16 also has a depression 34 in the clamping surface. This depression 34 may be tapered or another shape depending on the shape of the head of the connecting screw 30 . This depression ensures that the clamping surface of the clamping plate 16 contacts the surface to be clamped rather than the head of the connector screw 30 . Additionally, when the connector screw 30 is screwed tightly into the clamping plate 16 , the clamping plate 16 can still ride freely on the screw 30 . In other words, the clamping plate 16 can rotate around on the screw 30 .
Other means of securing the clamping plate 16 may also be used. For example, plate 16 may ride on a pin that is snap fit into the screw 14 .
It will be appreciated that the clamping plate 16 and the screw 30 may be totally eliminated. The clamping surface on this side of the clamp would then be provided by the end of the screw 14 . The clamp 10 may have to be held more securely for mounting in this configuration to prevent the contact between the rotating end of the screw 14 and the surface being clamped from causing the clamp 10 to travel along the surface. A protective material may also be used to protect the surface being clamped.
The screw 14 has a screw head 15 . A screw cap 28 can be used to cover the screw head 15 and the upper threads of the screw 14 . In this embodiment, the screw cap 28 is generally cylindrical. However, numerous other shapes may be used which are decorative such as triangular, octagonal or patterned screw caps. The screw cap 28 is a sleeve which covers the head of the screw 14 and it will be appreciated that the screw cap 28 may be completely eliminated. In this embodiment, the screw cap is retained by a press fit onto the screw head 15 . Other retaining means such as a retaining screw through the cap 28 and the head 15 could also be used.
As best seen in FIG. 4 , there is a hole 36 which extends through the screw cap 28 and down into the screw 14 . This hole 36 is a blind hole in this embodiment. In other words, it will typically not extend through the end of the screw 14 . However, it could extend the entire length of screw 14 . The hole 36 is for mounting an item on the clamp. For example, a task lamp may have a cylindrical end that is sized to fit within the hole 36 . The positioning of the hole 36 is also visible in FIGS. 5 and 6 . The hole 36 need not extend through the screw 14 , for example, there may be a block of material mounted above or on the back of the arms 22 and the hole 36 may extend through that block.
Although the hole 36 and a complementary post at the bottom of a lamp could be used to mount a lamp on the clamp, any other fastening means known in the art may be used. For example, the clamp 10 could have a plate with holes on the arm 24 and an item to be fastened could have complementary holes for screwing to the plate. The advantage of the use of the clamp 10 in such a configuration is to avoid the necessity of drilling screw holes in, for example, the table.
As previously explained, the distance between the clamping surfaces may be varied by screwing the screw 14 in the head 26 inwards to the interior of clamp 10 and outwards from the interior of the clamp 10 . In this example, the other way of altering the distance between the clamping surfaces is by use of the spacer 12 . The geometry of the spacer 12 is best seen in the front view in FIG. 5 . The spacer 12 is made up of a thin portion 38 , a thick portion 40 and a narrow portion 42 . In this embodiment, the thin portion 38 and the thick portion 40 are both cylindrical in shape and are connected by the narrow portion 42 . The width of the narrow portion 42 of this embodiment is sized to fit within the width of the distance between the connecting arms 22 by being substantially the same width. Similarly, the space between the thin portion 38 and the thick portion 40 , in other words the height of the narrow portion 42 , is sized to fit around the thickness of the spacer arms 22 by being substantially the same width. With this sizing, the spacer 12 can be press fit onto the spacer arms 22 as shown in FIGS. 2 , 3 , 5 and 6 and thus retained in position. The particular shape of the spacer 12 is not essential. For example, the narrow portion 42 may be narrower and still have a press fit which retains the position. Other means of removably fastening the spacer in position may also be used, including a loose positioning that is secured by the clamping of clamp 10 when used. The spacer 12 may be any shape of block which, with the body 18 , define co-operating protrusions and receiving portions for mounting the spacer block to the body 18 .
As can be seen by comparing the distances X 1 , X 2 , and X 3 in FIGS. 1 , 2 and 3 , the distance X 1 and by extension the thickness of an item which can be clamped, is the maximum of the three distances when the spacer is totally removed as in FIG. 1 . When the spacer 12 is press fit into the clamp with the thin portion 38 inside the clamp as shown in FIG. 2 , the clamping distance is decreased to the distance X 2 by the thickness of the thin portion 38 . When the spacer 12 is press fit into the clamp 10 in the orientation shown in FIG. 3 , the distance is reduced to the distance X 3 by a larger amount namely by the thickness of the thick portion 40 .
It will be appreciated that the use of the spacer 12 allows the distance to be decreased in increments based on the thickness of the portion of the spacer 12 which is added to the interior of clamp 10 inside of the spacer arms 20 . The opposed, in other words the oppositely facing parallel clamping surfaces, are provided by the inner face of the clamping plate 16 and the inner face of the spacing arms 20 in FIG. 1 , the inner face of the thin portion 38 in FIGS. 2 and 5 and the inner face of the thick portion 40 in FIGS. 3 and 6 .
The use of the spacer 12 in conjunction with the screw 14 allows the screw 14 to be of a shorter length than if the spacer assembly was not available. In other words, for the clamp 10 to clamp to a thin item, the screw 14 only needs to be of sufficient length to travel the distance X 3 depicted in FIG. 3 rather than the longer distance X 1 depicted in FIG. 1 . In some embodiments the travel of the screw 14 is ⅜ inches.
Other embodiments of the invention will now be discussed. The further embodiments will be discussed only to the extent that they differ from the embodiments of FIGS. 1 to 6 . Like reference characters will be used for the same parts and the same parts will not be described in detail.
FIG. 7 and FIGS. 8A to 8D show a different spacer assembly which can be used with the clamp body 18 described with respect to FIGS. 1 to 6 . A spacer 44 has the same basic configuration as the spacer 12 . In particular, the spacer 44 has a thin portion 46 connected to a thick portion 48 by a narrow portion 50 . As with spacer 12 , the spacer 44 is sized to be press fit onto the spacer arms 20 of the body 18 of the clamp 10 . The spacer 44 differs from the spacer 12 in that the spacer 44 has a hole 52 defined on the outer flat side of the thin portion 46 and a hole 54 defined on the outer flat side of the thick portion 48 as seen in FIG. 8B . The hole 52 may be square but it also may be other shapes and may not be exactly centered on the surface.
The spacer assembly of FIGS. 7 and 8A to 8 D also includes a thin spacer adapter 56 and a thick spacer adapter 58 . The thin spacer adapter 56 has a protrusion 62 which is sized to fit within either the hole 52 or the hole 54 . Similarly, the thick spacer adapter 58 has a protrusion 60 . The adapters 56 and 58 also have holes 61 and 63 sized to fit the protrusions 60 and 62 . It will be appreciated the spacer adapters 56 and 58 can be press fit onto the spacer 44 by inserting the protrusion 60 or 62 into the hole 52 or 54 . The adapters can therefore be used to vary the thickness of the portion of the spacer assembly which is internal to the clamp 10 and therefore vary the distance between the clamping surfaces by increments other than the thickness of the thin portion 46 or the thick portion 48 . Each of the adapters 56 and 58 may in turn have holes 61 and 60 on the opposite face from the protrusion so that further adapters may be connected to the adapters to allow further spacing increments. It will be appreciated that other co-operation protrusions and receiving portions for connecting the adapters to the spacer may be used. For example, the adapters may be screwed into position or have edge connectors for snapping into position. It will also be appreciated that the adapters need not be circular or of uniform size. Although the upper and lower surfaces of the adapters 56 and 58 and the spacers 12 and 44 are parallel, and the clamping surfaces are parallel, it will be appreciated that other configurations may be used. For example, if the clamp is to be attached to a pipe, the clamping surfaces may be concave.
FIGS. 9 , 10 , 11 a and 11 b depict another embodiment of the invention. The side view in FIG. 10 appears much the same as the embodiment depicted in FIGS. 1 to 8D , however, it will be appreciated from the perspective view in FIG. 9 that a clamp 63 depicted in FIGS. 9 and 10 differs from the clamp 10 depicted in FIGS. 1 to 3 . In particular, the clamp body 64 of the clamp 63 is made up of a single piece rather than two parallel members. Clamp body 64 is made up of a head arm 66 connected to a connecting arm 68 which in turn is connected to a spacer arm 70 in the same manner as arms 20 , 22 and 24 . The screw cap 28 , the head 26 , the screw 14 and the clamping plate 16 of the clamp 63 are the same as the components in FIGS. 1 to 8 .
Because the spacer arm 70 of the clamp 63 is a single piece, a spacer 72 of the clamp 63 differs from the spacer 12 of the clamp 10 . The spacer 72 is made up of a thin portion 74 and a thick portion 76 similar to the thin portion 38 and the thick portion 40 described with respect to spacer 12 . However, the thin portion 74 and the thick portion 76 are connected by a different means. Rather than having a narrow portion 42 which is press fit between two spacer arms 20 , in this embodiment, there are connecting posts 78 on the sides of the spacer 72 . These connecting posts 78 connect the thin portion 74 and the thick portion 76 as shown in FIGS. 11A and 11B . As can be seen from FIG. 9 , the positioning of the connecting posts 78 allow the spacer arm 70 to be inserted between these connecting posts to fasten the spacer 72 in position. In other words, the thickness of the spacer arm 70 substantially equals length of the connecting posts 78 and the width between the connecting posts 78 substantially equals the width of the spacer arm 70 so that the spacer 72 is press fit into position around the spacer arm 70 . A press fit is not essential and other configurations may be used. For example, one connecting post may be eliminated if the remaining connecting post is sufficiently rigid. The connecting posts 78 may be separate components which are attached to the thin portion 74 and the thick portion 78 , for example, by an adhesive. Alternatively, the entire spacer 72 may be machined from a single block of material.
The spacer 72 could also be used with the clamp 10 and fitted to the outside of the spacer arms 22 . The use of adapters as shown in FIGS. 7 to 8D could also be made to the spacer 72 of FIGS. 9 to 11B . The arms 22 and 24 may also be a single arm like arms 64 and 66 .
FIGS. 12 to 15 depict another embodiment of the invention. In particular, these Figures depict a clamp 80 . The basic configuration of the clamp body 81 is the same as described with respect to FIGS. 1 to 6 . In particular the clamp 80 is made up of a body 81 comprising spacer arms 87 connecting arm 83 and head arms 85 . In this embodiment, these arms are depicted as having a tubular rather than square shape. The continuous adjustment assembly is comprised of the head 26 , the screw 14 and the clamping plate 16 as previously described. In FIG. 12 , the screw cap 28 is removed so that the screw head 15 is visible.
This embodiment includes a spacer 84 . The spacer 84 is made up of first spacer end 86 in a second spacer end 88 . The spacer ends 86 and 88 are connected by a rod 90 . On the rod 90 between the spacer ends 86 and 88 are spacer elements which are thin spacer rings 92 and thick spacer rings 94 . The spacer rings 92 and 94 each have a hole through them which is larger than the diameter of the rod 90 . This allows the spacer rings 92 and 94 to move freely along the rod 92 within the limits of travel imposed by the spacer ends 86 and 88 .
The entire rod 90 is not occupied by spacer rings 92 and 94 . It will be appreciated that there will always be a blank area or gap on the rod 90 as shown in FIG. 12 . This area can be repositioned along the spacer 84 by sliding the spacer rings 92 and 94 . For example, FIG. 15 depicts the gap in one position and FIG. 14 depicts the gap in another position. The size of this gap in this embodiment is about the same as the thickness of the spacer arms 20 so that the spacer arms 20 can be press fit between any two successive spacer rings 92 , 94 or between a spacer end 86 or 88 and the next adjoining spacer ring 92 and 94 . This allows for a wide range of incremental spacer thicknesses to be added to the interior of the clamp 80 . For example, in FIG. 14 , the distance has been decreased to a distance X 4 by the cumulative thickness of the spacer end 86 , three thin spacer rings 92 and two thick spacer rings 94 . In contrast, in FIG. 15 the distance has been reduced to a distance X 5 only by the thickness of the spacer end 86 and the thickness of one thin spacer ring 92 and one thin spacer ring 94 .
It will be appreciated that the spacer 84 may have an effective thickness within the clamp 80 equal to the thickness of any successive grouping of spacer rings 92 and the associated spacer end 86 or 88 . The spacer ends 86 and 88 may be smaller and fit within a recess in the end most spacer rings so they do not add to the effective thickness. Any thickness of rings and ends and positioning the spacer rings may be employed. For example, the rod 90 may be telescoping so that no gap is left and the rod is expanded to allow the insertion of the spacer arms 20 into the spacer 84 . Alternatively, there may be multiple gaps. It would also be appreciated that spacer 84 may be configured similar to the spacer 72 of FIGS. 9 to 11B with peripheral rods rather than a central rod.
Although the embodiments depicted show circular spacers, it would be appreciated that other shapes may be employed. The spacers also may be screwed in or slid in from the sides rather than the front. The spacer, rather than the screw can have a hole or other protrusion or receiving portion to which an object can be mounted.
Although the embodiments depicted show the continuous adjustable screw assembly at one end of the clamp and the spacers at the opposite end of the clamp, it will be appreciated that spacers could also be attached to the clamping plate or be used in line in the connecting arms 22 as extensions.
An adjustable assembly other than a screw may be used as the complementary adjustment assembly to the spacer assembly. For example, a cam assembly may be used. The screw 14 may be replaced by a shaft connected to a cam. The cam in turn is connected to a rod. When the cam is in a released position, the shaft would slide freely up and down inside the head. When the rod is rotated to the engaged position, the cam will press against the shaft, holding it in place.
The parallel connecting arms 22 may also be used to facilitate a tracking system. For example, the arms may be extended to a much greater length than depicted in the figures and elements fixed between these parallel tracks or arms.
Numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. | A clamp comprises opposed members having clamping surfaces defining a distance therebetween for receiving and clamping an object. An adjustment mechanism is associated with at least one of the members for varying the distance over a continuous range. A spacer assembly being removably associated with at least one of the members for varying the distance by at least one discrete increment. | 5 |
TECHNICAL FIELD
The present invention refers to a method for forming an air laid fibrous web, wherein an air born fiber stream is laid on a web-shaped forming member, such as a wire, and the air laid fibrous web is bonded together.
BACKGROUND OF THE INVENTION
When air laying a fibrous web there are normally used one or more fiber distributors by means of which the air born fiber stream is distributed over a flat wire, which is under a vacuum, at which a fibrous web is formed. The fibrous web is compacted and bonded by means of moisture or a bonding agent, such as latex or bonding fibers. The bonding agent can either be contained as a component in the fiber stream or be added to the fibrous web after the air laying thereof.
Such dry or air formed materials obtains a high bulk, softness, smoothness and drapability as compared to a corresponding wet laid material and obtains almost textile like properties. Due to the bonding agent a high wet strength is also obtained. The drawback of the air laying process is that it is not possible to run in the high production speeds that are possible in a wet laying process. This involves a considerable higher production cost, which leads to that the method usually is limited to the production of relatively exclusive materials such as dinner napkins, table cloths, washing cloths and the like. The materials are also often used as pail of other hygiene products, like sanitary napkins and panty liners.
The production speed of such air laid fibrous webs is limited, mainly due to the fact that the unbonded web is very sensitive to all kind of mechanical influence which may lead to web breaks at free draughts and cause an uncontrolled rearrangement of the fibers and thus influence the fiber distribution in the web. Besides problems occur with dusting from the open fibrous web.
OBJECT AND MOST IMPORTANT FEATURES OF THE INVENTION
An object of the present invention is to provide a method for forming an air laid fibrous web of the kind mentioned above, and which permits production at considerably higher speeds than in conventional air laying technique on a flat wire and where the above mentioned problems are avoided. This has according to the invention been provided by feeding the air laid fibrous web between two web-shaped forming members and binding the fibrous web either when this is located between the two web-shaped forming members or immediately after one forming member has left the fibrous web.
According to one embodiment the fibrous web is exerted to a mechanical actuation when located between the forming members, in order to provide a more even fiber distribution. By this a very even fiber formation can be obtained by simple means.
According to a further embodiment at least one of the web-shaped forming members has a three-dimensional structure which is shaped into the fibrous web. Preferably a pressure is applied to the forming members in order to press the structure into the fibrous web.
According to one embodiment the air born fibrous stream is applied in a nip between two wires which are brought together immediately after the laying of the fibers. Preferably the wires are brought together over a curved forming element.
According to a further embodiment the air born stream is laid on a first substantially flat forming member, after which a second forming member is brought together with the first forming member with the air laid fibrous web therebetween.
According to a further embodiment the air born fibrous stream is fed between two forming members which are brought together gradually for admitting deaeration of the fibrous web over a relatively large area, at which the first part of the forming takes place over an open zone between forming members and the final part takes place over a closed zone where the forming members have been brought together. The mechanical agitation of the fibrous web takes place either as well in the open as in the closed zone or only in one of them.
The mechanical agitation of the fibrous web is done by a direct actuation thereof and/or by an indirect actuation via at least one of the web-shaped forming members.
Said agitation can be provided by means of vibrations, breaking over one or more rolls, air pulses, alternating vacuum and over pressure and/or by ultrasonic, infra sonic etc.
According to a preferred embodiment bonding of the fibrous web takes place when this is located between the wires.
DESCRIPTION OF DRAWINGS
The invention will in the following be closer described with reference to some embodiments shown in the accompanying drawings.
FIG. 1 is a schematic illustration of an air laying process according to a first embodiment.
FIG. 2 is a schematic illustration of an air laying process according to a second embodiment.
FIG. 3 is a schematic illustration of an air laying process according to a third embodiment.
DESCRIPTION OF EMBODIMENTS
In FIG. 1 there is schematically shown a process for forming a fibrous web according to the twin wire principle, at which a fibre stream is blown into the nip between two wires 11 and 12 , which are brought together over a forming roll 13 . The twin wire principle is commonly used within paper production according to the wet laying technique. The fibers are fed into the nip by means of a headbox 10 adapted for this purpose.
Instead of wires 11 and 12 there may be used other kinds of web-shaped forming means, such as felts, membranes, bands or the like. However at least one of the forming members 11 , 12 has to be air permeable.
The fibers used in an air laying process may be of varying kind, such as cellulosic fibers and natural fibers of different kind, regenerated cellulose and synthetic fibers of different kind and mixtures of these different fiber types. Besides substances in powder or particulate form other than fibers may be contained, for example superabsorbent particles, filling agents, bonding agents and the like.
The forming roll 13 can have a solid or open surface, be under a vacuum or not. The fiber stream which is laid between the wires 11 , 12 forms a fibrous web after deaeration and is kept between the wires during the continued transport through the process. The fibrous web is mechanically actuated during the transport by means of actuating means 14 , at which a redistribution of the fibers as well as a breaking up or possible fiber flocks may occur. This can be done due to the fact that the fibrous web at this stage still is unbonded, and since it is kept between the two wires the fibers can not be redistributed in an uncontrolled way or even be blown off the wires, which would be the case in a conventional air laying process where the fibrous web is fed on top of a flat wire. Besides dusting is avoided. The agitation at this stage does not involve any negative influence on the strength properties of the final product, since the bonding of the fibrous web has not yet taken place.
The mechanical actuation of the fibrous web while held between the wires can be caused in different ways, for example by breaking the wires over one or more rolls 15 , by air pulses, alternating over- and sub pressures, ultrasonic, infrasonic and/or other vibration generating means. According to an embodiment there can already in the forming zone 13 be blowing zones causing an agitation of the fibrous web.
By agitating the fibrous web the formation is improved and a more even basis weight of the final product is obtained. Possible irregularities which may occur during the fiber formation can by this be evened.
Bonding of the air laid fibrous web can be made in a conventional way. One example of a bonding method is that the air laid fibrous web contains a bonding agent which is activated by for example heat, plasma, or corona treatment or by UV-irradiation.
Examples of such bonding agents are thermoplastic fibers or particles, which soften by heat and by that bind the fibers together. The bonding agent may also be a reactive component that is anchored on the fiber surface and which is activated in any of the above mentioned ways. By using this type of bonding method the bonding of the fibrous web can be made while this is still between the wires 11 , 12 . The activation of the bonding agent takes place in a bonding station 16 .
Bonding can also be made by moisture, at which the fibers already from the start can have a certain moisture content, for example at least 30%, or by adding moisture to the laid fibrous web. It is also possible to after laying of the fibrous web add a bonding agent, for example latex, by spraying, coating or the like, said bonding agent can then be activated by heat, irradiation or in some other way.
At least one of the web-shaped forming members 11 , 12 can have a three dimensional structure which is shaped into the fibrous web and be permanented by the bonding. It is also in this case appropriate that bonding of the fibrous web is done while this is still between the forming members /wires, at which the pattern is pressed into the fiber web. It would also be possible to apply a pressure on the forming members/wires in order to reinforce the patterning effect.
As forming means there could also be used for example similar wires that are today used within the so called TAD-technique (through-air-drying) for paper production and for drying wires or forming wires. The material in the wires 11 , 12 should be of a heat resistant, weal resistant material. Polyamide, polyester, PEEK (polyether ether ketone) and aramide can be suitable materials for the wires.
According to that embodiment shown in FIG. 2 the fibrous web is laid on a flat wire 17 with conventional air laying technique by means of a forming head, after which the wire 17 is brought together with a second wire 18 so that the fibrous web is held between the wires 17 , 18 . A mechanical agitation 14 of the fibrous web is done in a corresponding way as disclosed above. Bonding of the fibrous web is then made in a bonding station 16 in any of the ways described above. In this case it is shown that bonding takes place after the second wire 18 has left the fibrous web and this is supported only by the flat wire 17 . With the embodiment shown in FIG. 2 a conventional already existing air laying device can be easily rebuilt.
According to the embodiment of FIG. 3 the air born fiber stream is fed between two wires 19 , 20 which are gradually brought together, at which deaeration of the fibrous web can take place over a larger area. In the initial phase of the forming there is an open zone 21 between the wires and in the final part of the forming a closed zone 22 in which the wires 19 and 20 are brought together. Mechanical agitation 14 of the fibrous web can take place as well in the open zone 21 as in the closed zone 22 or in only any thereof. In the open zone the distance between the wires is determined by the relative positions of the rolls, which may be adjustable. In the closed zone the distance between the wires is primarily determined by the thickness of the fibrous web.
After bonding the fibrous web can be exerted to a conventional after treatment such as calendering, lamination, embossing or the lime before winding and further converting to the final product.
The invention offers an improved process for the production of air laid fibrous materials, which can be run at considerably higher speeds than a conventional air laying process and where it is possible by simple means to provide an even fiber distribution. At the same time all advantages concerning product properties of the air laid fibrous material are obtained. Besides the fibrous web can by simple means be given a three-dimensional structure. | Method for forming an air laid fibrous web, wherein an air born fiber stream is laid on a web shaped forming member, such as a wire, and the air laid fibrous web is bonded together. The air laid fibrous web is fed between two web-shaped forming members and bonding of the fibrous web takes place either when this is located between the two web-shaped forming members or immediately after one forming member has left the fibrous web. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for fabricating semiconductor device, and more particularly, to a method for fabricating an SOI semiconductor device.
2. Description of Related Art
A related art SOI device is disclosed in U.S. Pat. No. 6,110,769 issued to Jeong Hwan Son, titled “SOI (SILICON ON INSULATOR) DEVICE AND METHOD FOR FABRICATING THE SAME”, which is shown in FIGS. 1 A and 1 B- 1 H. Refer to FIG. 1A, which is a cross-sectional view showing a structure of a conventional SOI device.
A buried oxide film 25 is formed on a semiconductor substrate 24 . P and N-type heavily doped polysilicon layers 23 a and 23 b are formed on the buried oxide film 25 and isolated from each other by an isolation oxide film 26 formed on the buried oxide film 25 . Buried oxide films 22 a are formed in the p and N-type heavily doped polysilicon layers 23 a and 23 b to be spaced apart.
A P-type semiconductor layer 20 b and a first active region are formed on the first buried oxide film 22 a, spaced apart from the P-type heavily doped polysilicon layer 23 a. A first oxide film 21 is formed between the P-type semiconductor layer 20 b and the first active region.
An N-type semiconductor layer 20 c and a second active region are formed on the first buried oxide film 22 a, spaced apart from the N-type heavily doped. A first oxide film 21 is formed between the N-type semiconductor layer 20 c and the second active region.
A gate oxide film 29 and a first gate electrode 30 a are successively formed on the first active region on the P-type heavily doped polysilicon layer 23 a. Source/drain regions 34 a / 34 b are formed in the first active region at both sides of the first gate electrode 30 a.
A gate oxide film 29 and a second gate electrode 30 b are successively formed on the second active region on the N-type heavily doped polysilicon layer 23 b. Source/drain region 32 a / 32 b are formed in the second active region at both sides of the second gate electrode 30 b.
Formed is an interlayer insulating film 35 having contact holes on the p and N-type semiconductor layers 20 b and 20 c and the source/drain regions 32 a / 32 b and 34 a / 34 b. Contact pads 36 a and 36 f and line layers 36 b, 36 c, 36 d, and 36 e are formed in the contact holes and on the interlayer insulating layer adjoining to the contact holes.
The first and second active regions are connected to the p and N-type semiconductor layers 20 b and 20 c through the p and N-type polysilicon layers 23 a and 23 b, respectively.
Refer to FIGS. 1B-1H, are cross-sectional views showing conventional process steps of a method for fabricating the SOI device as shown in FIG. 1A First refer to FIG. 1B, a first semiconductor substrate 20 is provided. The first substrate 20 is etched to form a plurality of trenches. An oxide film is deposited on the substrate 20 and the trenches. Subsequently, a CMP process is performed to form a first oxide film 21 filling the trenches.
Next, a first buried oxide film 22 is formed on the first semiconductor substrate 20 by CVD.
A photoresist film is formed on the first buried oxide film 22 and patterned to expose areas of the first buried oxide film 22 . Using the patterned photoresist as a mask, the first buried oxide film 22 is removed to expose the first substrate 20 . Next an undoped polysilicon layer is deposited on the first buried oxide film 22 and the first substrate 20 . The undoped polysilicon layer is then etched-back forming a thick undoped polysilicon layer 23 .
A second semiconductor substrate 24 is provided and a second buried oxide film 25 is deposited on the second substrate 24 . Subsequently, the second buried oxide film 25 on the second substrate 24 and the undoped polysilicon layer 23 on the first substrate 20 are bonded together by undergoing a high temperature process
Refer to FIG. 1 C. The first substrate 20 is polished until the first oxide film 21 using the first oxide film 21 as an etch stop. In order to form a trench isolation region, the semiconductor layer 20 a between the first oxide film 21 , the first buried oxide film 22 , and the undoped polysilicon layer 23 are etched. An oxide film is deposited on the first oxide film 21 , the semiconductor layer 20 a, and the trench isolation region and then planarizing the oxide film to form an isolation oxide film 26 .
Next, a photoresist film 27 covers the first oxide film 21 , the semiconductor layer 20 a and the isolation oxide film 26 . The photoresist film 27 is patterned and removed to expose part of the isolation oxide film 26 . Using the patterned photoresist film 27 as a mask, the undoped polysilicon layer 23 is injected with boron ions to create a P-type heavily doped polysilicon layer 23 a.
Refer to FIG. 1 D. Subsequently, another photoresist film 28 covers the first oxide film 21 , the semiconductor layer 20 a and the isolation oxide film 26 and patterned. The photoresist film 28 is then removed to expose part of the isolation oxide film that was covered by the photoresist film 27 in the previous step. Using the patterned photoresist film 28 as a mask, the undoped polysilicon layer 23 a is injected with phosphorus ions to become an N-type heavily doped polysilicon layer 23 b.
Refer to FIG. 1 E. An oxide film and a silicon layer are deposited and etched. The result is a gate oxide film 29 and a first gate electrode 30 a for an NMOS transistor and a gate oxide film 29 and a second gate electrode 30 b for a PMOS transistor formed on the semiconductor layer 20 a.
Refer to FIG. 1F. A photoresist film 31 is formed and patterned to expose the semiconductor layer 20 a on both sides of the second gate electrode 30 b and where the first gate electrode 30 a is not formed. Using the patterned photoresist film 31 as a mask, the P-type semiconductor layer 20 b is injected with P-type boron ions to form lightly doped source/drain regions 32 a and 32 b.
Refer to FIG. 1G. A photoresist film 33 is formed and patterned to expose the semiconductor layer 20 a on both sides of the first gate electrode 30 a and where the second gate electrode 30 b is not formed. Using the patterned photoresist film 33 as a mask, the N-type semiconductor layer 20 c is injected with N-type As ions to form lightly doped source/drain regions 34 a and 34 b.
Refer to FIG. 1 H. Depositing and removing an insulating film 35 to expose areas of the P-type semiconductor layer 20 b, the N-type semiconductor layer 20 c, the P-type source/drain regions 32 a and 32 b and the N-type source/drain regions 34 a and 34 b and form contact holes. A conductive layer is formed to fill the contact holes. The conductive layer is etched to form contact pads 36 a and 36 f on the P-type and N-type semiconductor layers 20 b and 20 c and line layers 36 b, 36 c, 36 d, 36 e on the n and p source/drain regions 32 a / 32 b and 34 a / 34 b.
The conventional method for fabricating an SOI semiconductor device as described above comprises implanting P-type ions to form regions 20 b, 32 a, and 32 b. Additionally, the conventional method requires implanting N-type ions to form regions 20 c, 34 a, and 34 b. Since photoresist films are used as ion-implantation masks, two lithography mask steps and two ion implantation steps need to be performed, which increases the complexity of the fabrication process and the cost thereof.
SUMMARY OF THE INVENTION
In accordance with the foregoing and other objectives of the present invention, the invention provides a method for fabricating a SOI semiconductor device, which overcomes the drawbacks of the conventional SOI device.
A first semiconductor substrate is etched to form a plurality of trenches. An oxide film is deposited on the substrate and the trenches. A first oxide film is deposited which fills the trenches. A first buried oxide film is formed on the first semiconductor substrate. A photoresist film is formed on the first buried oxide film and patterned to expose areas of the first buried oxide film. Using the patterned photoresist as a mask, the first buried oxide film is removed to expose the first substrate. Next an undoped polysilicon layer is deposited on the first buried oxide film and the first substrate. The undoped polysilicon layer is then etched-back.
A second buried oxide film is deposited on a second substrate. The second buried oxide film on the second substrate and the undoped polysilicon layer on the first substrate are bonded together by undergoing a high temperature process.
The first substrate is polished until the first oxide film is exposed using the first oxide film as an etch stop. In order to form a trench isolation region, the semiconductor layer between the first oxide film, the first buried oxide film, and the undoped polysilicon layer are etched. An oxide film is deposited on the first oxide film, the semiconductor layer, and the trench isolation region and then planarizing the oxide film to form an isolation oxide film.
Next, a photoresist film covers the first oxide film, the semiconductor layer and the isolation oxide film. The photoresist film is patterned and removed to expose part of the isolation oxide film. Using the patterned photoresist film as a mask, the undoped polysilicon layer is injected with, for example, boron ions to create a P-type heavily doped polysilicon layer.
Subsequently, another photoresist film covers the first oxide film, the semiconductor layer and the isolation oxide film and patterned. The photoresist film is then removed to expose part of the isolation oxide film that was covered by the photoresist film in the previous step. Using the patterned photoresist film as a mask, the undoped polysilicon layer is injected with, for example, phosphorus ions to become an N-type heavily doped polysilicon layer.
An oxide film and a silicon layer are deposited and etched. The result is a gate oxide film and a first gate electrode for an NMOS transistor and a gate oxide film and a second gate electrode for a PMOS transistor, formed on the semiconductor layer. A doped dielectric layer, for example, n-doped PSG, is formed over the surface by, for example, CVD.
A photoresist film is formed and patterned over the dielectric layer. An area of the doped dielectric layer is removed to expose the semiconductor layer on both sides of the second gate electrode and where the first gate electrode is not formed. Using the patterned photoresist film as a mask, the P-type semiconductor layer is injected with P-type boron ions to form lightly doped source/drain regions. The photoresist film is then removed.
Next, the n-dopant inside the doped dielectric layer is driven into the N-type semiconductor layer to form lightly doped source/drain regions.
Depositing and removing an insulating film to expose areas of the P-type semiconductor layer, the N-type semiconductor layer, the P-type source/drain regions and the N-type source/drain regions and form contact holes. A conductive layer is formed to fill the contact holes. The conductive layer is etched to form contact pads on the P-type and N-type semiconductor layers and line layers on the n and p source/drain regions.
It is to be understood that both the foregoing general description and the following detailed description are exemplary, and are intended to provide further explanation of the invention as claimed.
BRIEF DESCRIPTION OF DRAWINGS
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. In the drawings,
FIG. 1A, which is a cross-sectional view showing a structure of a conventional SOI device.
FIGS. 1B-1H are cross-sectional views showing conventional process steps of a method for fabricating the SOI device as shown in FIG. 1A;
FIGS. 2A-2L are cross-sectional views showing process steps of a method for fabricating the SOI device according to a preferred embodiment of the present invention; and
FIGS. 3I-3L are cross-sectional views showing an SOI device according to an embodiment of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Refer to FIGS. 2A-2L, which are cross-sectional views showing process steps of a method for fabricating the SOI device according to a preferred embodiment of the present invention.
A first semiconductor substrate 220 is etched to form trenches. A first oxide film 221 is deposited which fills the trenches.
Refer to FIG. 2B, a first buried oxide film 222 is formed on the first semiconductor substrate 220 .
Refer to FIG. 2C, a photoresist film is formed on the first buried oxide film 222 and patterned to expose areas of the first buried oxide film 222 . Using the patterned photoresist as a mask, the first buried oxide film 222 is removed to expose the first substrate 220 . Next an undoped polysilicon layer is deposited on the first buried oxide film 222 and the first substrate 220 . The undoped polysilicon layer is then etched-back to form an undoped polysilicon layer 223 .
A second buried oxide film 225 is deposited on a second substrate 224 .
Refer to FIG. 2 D,the second buried oxide film 225 on the second substrate 224 and the undoped polysilicon layer 223 on the first substrate 220 are bonded together by undergoing a high temperature process.
Refer to FIG. 2E, the first substrate 220 is polished until the first oxide film 221 is exposed using the first oxide film 221 as an etch stop. In order to form a trench isolation region, the semiconductor layer 220 a between the first oxide film 221 , the first buried oxide film 222 , and the undoped polysilicon layer 223 are etched. An oxide film is deposited on the first oxide film 221 , the semiconductor layer 220 a, and the trench isolation region and then planarizing the oxide film to form an isolation oxide film 226 .
Refer to FIG. 2F, a photoresist film 227 covers the first oxide film 221 , the semiconductor layer 220 a and the isolation oxide film 226 . The photoresist film 227 is patterned and removed to expose part of the isolation oxide film 226 . Using the patterned photoresist film 227 as a mask, the undoped polysilicon layer 223 is injected with boron ions to create a P-type heavily doped polysilicon layer 223 a.
Refer to FIG. 2G, another photoresist film 228 covers the first oxide film 221 , the semiconductor layer 220 a and the isolation oxide film 226 and patterned. The photoresist film 228 is then removed to expose part of the isolation oxide film that was covered by the photoresist film 227 in the previous step. Using the patterned photoresist film 228 as a mask, the undoped polysilicon layer 223 a is injected with phosphorus ions to become an N-type heavily doped polysilicon layer 223 b.
Refer to FIG. 2H, an oxide film and a silicon layer are deposited and etched. The result is a gate oxide film 229 and a first gate electrode 230 a for an NMOS transistor and a gate oxide film 229 and a second gate electrode 230 b for a PMOS transistor, formed on the semiconductor layer 220 a.
Refer to FIG. 2I, A doped dielectric layer 250 , for example, n-doped PSG (Phosphosilicate Glass) or n-doped SOG (Spin-On-Glass), is sequentially formed over the surface of the substrate 224 by, for example, chemical vapor deposition (CVD).
Refer to FIG. 2J, a photoresist film 231 is formed and patterned over the doped dielectric layer 250 . An area of the doped dielectric layer 250 is removed to expose the semiconductor layer 220 a on both sides of the second gate electrode 230 b and the semiconductor layer 220 b beside the first gate electrode 230 a, where the first gate electrode 230 a and the semiconductor layer 220 a beside the second gate electrode 230 b are not exposed. Using the patterned photoresist film 231 as a mask, the P-type semiconductor layer 220 b is injected with P-type boron ions to form lightly doped source/drain regions 232 a and 232 b. The photoresist film 231 is then removed.
Refer to FIG. 2K, the N-type dopants inside the doped dielectric layer 250 are driven into the doped N-type semiconductor layer at a high temperature in an environment of inert gas to form n + doped source/drain regions 234 a and 234 b, as well as the n + doped semiconductor layer 220 c as shown in FIG. 2 K.
Refer to FIG. 2L, depositing and removing an insulating film 235 to expose areas of the P-type semiconductor layer 220 b, the N-type semiconductor layer 220 c, the P-type source/drain regions 232 a and 232 b and the N-type source/drain regions 234 a and 234 b and form contact holes. A conductive layer is formed to fill the contact holes. The conductive layer is etched to form contact pads 236 a and 236 f on the P-type and N-type semiconductor layers 220 b and 220 c and line layers 236 b, 236 c, 236 d, 236 e on the n and p source/drain regions 232 a / 232 b and 234 a / 234 b.
Refer to FIGS. 3I-3L, which are cross-sectional views showing process steps of a method for fabricating the SOI device according to another preferred embodiment of the present invention. The embodiment of the present invention comprises similar steps of forming the SOI device as shown in FIGS.2A-2L through forming the gate oxide film 329 and the first gate electrode 330 a for an NMOS transistor and a gate oxide film 329 and a second gate electrode 330 b for a PMOS transistor, formed on the semiconductor layer 320 a, as shown in FIG. 3 I.
Refer to FIG. 3I, a doped dielectric layer 350 , for example, p-doped boronsilicate glass (BSG) or p-doped SOG is formed over the surface of the substrate 324 by, for example, CVD.
Refer to FIG. 3J, a photoresist film 331 is formed and patterned over the doped dielectric layer 350 . An area of the doped dielectric layer 350 is removed to expose the semiconductor layer 320 b on both sides of the second gate electrode 330 a and the semiconductor layer 320 b beside the second gate electrode 330 b, where the first gate electrode 330 b and the semiconductor layer 320 b beside the first gate electrode 330 a is not exposed. Using the patterned photoresist film 331 as a mask, the N-type semiconductor layer 320 a is injected with N-type As ions to form doped source/drain regions 334 a and 334 b. The photoresist film 331 is then removed.
Refer to FIG. 3K, the P-type dopants inside the doped dielectric layer 350 is driven into the P-type semiconductor layer beside the first gate electrode 330 b to form doped source/drain regions 332 a and 332 b.
Refer to FIG. 3L, which is a cross-sectional view showing an SOI device according to an embodiment of the present invention. Depositing and removing an insulating film 335 to expose areas of the N-type semiconductor layer 320 a, the P-type semiconductor layer 320 c, the P-type source/drain regions 332 a and 332 b and the N-type source/drain regions 334 a and 334 bc and form contact holes. A conductive layer is formed to fill the contact holes. The conductive layer is etched to form contact pads 336 a and 336 f on the P-type and N-type semiconductor layers 320 b and 320 c and line layers 336 b, 336 c, 336 d, 336 e on the n and p source/drain regions 332 a / 232 b and 334 a / 334 b.
An advantage of the present invention is that only one lithography mask step is required to form the doped regions instead of the two steps required by the conventional method. Another advantage of the present invention is that the channel regions of NMOS and PMOS transistors are electrically connected to first and second conductivity type semiconductor layers, respectively, having contact pads through first and second conductivity type polysilicon layers, thereby reducing floating body effects and thus improving the operation characteristics.
It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the present invention cover modifications and variations of this invention provided they fall within the scope of the following claims and their equivalents. | A method for fabricating an SOI semiconductor device with reduced floating body effects and a simplified method of fabrication. In the invention, a N-type doped dielectric layer or P-type doped dielectric layer is used to be driven into the semiconductor layer to form source/drain regions of field effect transistors of CMOS and conductive regions. For fabricating a NMOS transistor and a PMOS transistor of the CMOS device, the invention provides a method which an ion implantation process and a photo mask are omitted, by which the method will decrease the complexity of the fabrication process and the cost thereof. | 7 |
TECHNICAL FIELD
The present disclosure relates generally to the field of automotive protective systems. More specifically, the present disclosure relates to mounting assemblies for inflatable curtain airbags and related methods.
BRIEF DESCRIPTION OF THE DRAWINGS
The present embodiments will become more fully apparent from the following description and appended claims, taken in conjunction with the accompanying drawings. Understanding that the accompanying drawings depict only typical embodiments, and are, therefore, not to be considered to be limiting of the disclosure's scope, the embodiments will be described and explained with specificity and detail in reference to the accompanying drawings.
FIG. 1A is a perspective view of one embodiment of an airbag assembly, wherein the airbag assembly comprises a mounting assembly that is coupled to an airbag, and wherein the mounting assembly is coupling the airbag to a vehicle and the airbag is being retained in a packaged configuration.
FIG. 1B is a perspective view of the airbag assembly of FIG. 1A , wherein the airbag is in a deployed configuration.
FIG. 2A is an exploded perspective view of the airbag assembly of FIG. 1A , wherein the airbag has been partially cutaway.
FIG. 2B is a cutaway perspective view of the airbag assembly of FIG. 2A , wherein the mounting assembly has been coupled to the airbag.
FIG. 2C is a cutaway perspective view of the airbag assembly of FIG. 2B , wherein a portion of the mounting assembly has been folded over and re-sewn to the airbag.
FIG. 3 is another cutaway perspective view of the airbag assembly of FIG. 2C .
FIG. 4A is a cross-sectional view of the airbag assembly of FIG. 1A before the mounting assembly has been folded and re-sewn.
FIG. 4B is a cross-sectional view of the airbag assembly of FIG. 4A after the mounting assembly has been folded and re-sewn.
FIG. 5 is another cross-sectional view of the airbag assembly of FIG. 1A .
FIG. 6 is an exploded perspective view of another embodiment of an airbag assembly, wherein the airbag has been partially cutaway.
FIG. 7A is a cross-sectional view of the airbag assembly of FIG. 6 .
FIG. 7B is a cross-sectional view of the airbag assembly of FIG. 7A after a portion of the assembly has been folded and re-sewn to the airbag.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
It will be readily understood that the components of the embodiments as generally described and illustrated in the figures herein could be arranged and designed in a wide variety of different configurations. Thus, the following more detailed description of various embodiments, as represented in the figures, is not intended to limit the scope of the disclosure, as claimed, but is merely representative of various embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The phrases “connected to,” “coupled to” and “in communication with” refer to any form of interaction between two or more entities, including mechanical, electrical, magnetic, electromagnetic, fluid, and thermal interaction. Two components may be coupled to each other even though they are not in direct contact with each other. The term “abutting” refers to items that are in direct physical contact with each other, although the items may not necessarily be attached together.
Inflatable airbag systems are widely used to minimize occupant injury in a collision scenario. Airbag modules have been installed at various locations within a vehicle, including, but not limited to, the steering wheel, the instrument panel, within the side doors or side seats, adjacent to the roof rail of the vehicle, in an overhead position, or at the knee or leg position. In the following disclosure, “airbag” may refer to an inflatable curtain airbag, overhead airbag, front airbag, or any other airbag type.
An inflatable curtain airbag may be used to protect the passengers of a vehicle during a side collision or roll-over collision. Inflatable curtain airbags typically extend longitudinally within the vehicle and are usually coupled to or next to the roof rail of the vehicle. The inflatable curtain airbag may expand in a collision scenario along the side of the vehicle between the vehicle passengers and the side structure of the vehicle. In a deployed state, an inflatable curtain airbag may cover at least a portion of side windows and a B-pillar of the vehicle. In some embodiments, the inflatable curtain airbag may extend from an A-pillar to a C-pillar of the vehicle. In other embodiments, the inflatable curtain airbag may extend from the A-pillar to a D-pillar of the vehicle.
An inflatable curtain airbag is typically installed adjacent the roof rail of a vehicle in an undeployed state, in which the inflatable curtain airbag is rolled or folded or a combination thereof and retained in the folded or rolled configuration by being wrapped at certain points along the airbag. In this state, the airbag may be said to be in a packaged configuration. When deployed, the airbag exits the packaged configuration and assumes an extended shape. The extended and inflated airbag may be said to be in a deployed configuration. Thus, an airbag mounting apparatus typically allows for a secure connection between the vehicle and the airbag, yet allows the airbag to change configurations from the packaged configuration to the deployed configuration.
FIG. 1A depicts airbag assembly 100 from a perspective view, wherein a mounting assembly 120 is coupled to an inflatable curtain airbag 110 that is in a packaged configuration, and is mounted adjacent a roof rail 12 of a vehicle 10 . Airbag assembly 100 may comprise an inflatable curtain airbag 110 , and an airbag mounting assembly 120 . A plurality of mounting assemblies 120 may be employed to couple curtain airbag 110 to a vehicle. Mounting assembly 120 may comprise a mounting member 130 and a connecting member 140 . In FIG. 1A , only a bottom portion of the connecting member is visible. An optional wrapper 170 may also be employed to retain the airbag in the packaged configuration. For clarity, in the depiction of FIG. 1A , wrapper 170 is darkly colored; however, the wrapper need not be colored differently than any other component of the assembly. In some embodiments, the wrapper may be coupled to one or more components of the mounting assembly, and therefore may be considered a component of the mounting assembly. Mounting assembly 120 may be employed to couple inflatable curtain airbag 110 adjacent a vehicle roof rail 12 , or other vehicle structure. Airbag assembly 100 may further comprise an inflator (not shown). In the depicted embodiment, inflatable curtain airbag 110 extends from an A-pillar 14 to a D-pillar 19 . Inflatable curtain airbag 110 also extends past a B-pillar 16 and a C-pillar 18 such that in a deployed configuration, the inflatable curtain airbag at least partially covers the B- and C-pillars, as depicted in FIG. 1B .
FIG. 1B is a perspective view of inflatable curtain airbag assembly 100 , wherein the airbag is depicted in a deployed configuration. Inflatable curtain airbag 110 is configured to become inflated upon activation of one or more inflators such that the airbag transitions from the packaged configuration to the deployed configuration. During deployment, wrapper 170 is configured to rupture such that inflatable curtain airbag 110 can adopt the deployed configuration. In the deployed and in an extended configuration, such as before rolling and/or folding, inflatable curtain airbag 110 may be described as having an upper portion 111 , a lower portion 112 , a first face 113 , and a second face (not visible). The various faces of inflatable curtain airbag 110 define an inflatable void, which is in fluid communication with an inflator (not visible). The inflatable void may be divided into inflation cells 119 via stitching. The various faces of inflatable curtain airbag 110 may comprise panels of a woven nylon fabric that are coupled together at a seam to form the inflatable void.
Upper portion 111 of inflatable curtain airbag 110 is the portion of the airbag that is closest to the headliner of a vehicle when the airbag is in a deployed state. Lower portion 112 is below upper portion 111 when inflatable curtain airbag 110 is in a deployed state, and is closest to a floor of the vehicle. The term “lower portion” is not necessarily limited to the portion of inflatable curtain airbag 110 that is below a horizontal medial plane of the inflatable curtain airbag, but may include less than half, more than half or exactly half of the bottom portion of the inflatable curtain airbag. Likewise, the term “upper portion” is not necessarily limited to the portion of inflatable curtain airbag 110 that is above a horizontal medial plane of the airbag, but may include less than half, more than half or exactly half of the top portion of the airbag.
Upon activation, the inflator rapidly generates and/or releases inflation gas, which rapidly inflates the inflatable curtain airbag 110 . The inflator may be one of several types, such as pyrotechnic, stored gas, or a combination inflator and may comprise a single or multistage inflator. As inflatable curtain airbag 110 becomes inflated, tension is applied to wrapper 170 , which causes the wrapper to rupture, and therefore, cease to retain the airbag in the packaged configuration.
As will be appreciated by those skilled in the art, a variety of types and configurations of inflatable curtain airbags can be utilized without departing from the scope and spirit of the present disclosure. For example, the size, shape, and proportions of the inflatable curtain airbag may vary according to its use in different vehicles or different locations within a vehicle. Also, the inflatable curtain airbag may comprise one or more of any material well known in the art, such as a woven nylon fabric. Additionally, the inflatable curtain airbag may be manufactured using a variety of techniques such as one piece weaving, cut and sew, or a combination of the two techniques. Further, the inflatable curtain airbag may be manufactured using sealed or unsealed seams, wherein the seams are formed by stitching, adhesive, taping, radio frequency welding, heat sealing, or any other suitable technique or combination of techniques.
Collectively, FIGS. 2A-2C , and their associated text, may be said to comprise a method for manufacturing an inflatable curtain airbag assembly, a method for manufacturing a mounting assembly, a method for packing an inflatable curtain airbag, a method for coupling an inflatable curtain airbag to a vehicle, and any combination of the preceding methods. FIGS. 2A-2C depict airbag assembly 100 and mounting assembly 120 from various views.
FIG. 2A depicts airbag assembly 100 from an exploded perspective view in which inflatable curtain airbag 110 is partially cutaway. Mounting assembly 120 may comprise mounting member 130 and Connecting member 140 . Mounting member 130 may comprise a rigid planar member comprising a metal alloy, or in some embodiments, the mounting member may comprise a flexible fabric, such as a woven nylon material. Mounting member 130 has a mounting aperture 132 , a first side 133 , a second side (not visible), a top portion 135 , a bottom portion 136 , and a connecting aperture 137 . Top and bottom portions 135 and 136 refer to an approximate upper half and lower halves, respectively, when mounting member 130 is in the same orientation as depicted in FIG. 2A .
Mounting aperture 132 is located on top portion 135 and is configured to receive a fastener, such as a bolt or a mounting structure coupled to the vehicle that protrudes through the aperture. Connecting aperture 137 comprises an elongated slot and is located on lower portion 137 and is configured to receive connecting member 140 . In some embodiments, mounting member 130 may not comprise a connecting aperture. In such embodiments, the connecting member may be coupled to the mounting member without the use of an aperture in the connecting member.
One skilled in the art will also recognize that a variety of types of materials may be used to form the mounting member without departing from the spirit of this disclosure. For example, in one embodiment, the mounting member comprises a piece of material, such as nylon webbing. Further, the mounting member may comprise a variety of shapes. For example, the mounting member may be square, triangular, round, or pentagonal. Further, the mounting member may comprise more or fewer apertures than described herein. For example, in one embodiment, the mounting member comprises two mounting apertures, and in another embodiment, the mounting member comprises three mounting apertures. Further, the location of the apertures may vary from the depictions of the figures.
Connecting member 140 comprises a flexible fabric, such as a woven nylon. Connecting member 140 comprises a predetermined length and a predetermined width. The length of the connecting member may vary according to use in different vehicles such that the curtain airbag is located in a predetermined position, with reference to its vertical placement. Connecting member 140 comprises a first portion 141 and a second portion 142 . Generally, it may be said that first portion 141 is an upper portion and second portion 142 is a lower portion. Both the first and second portions 141 and 142 comprise two layers of the connecting member.
First portion 141 is that portion of connecting member 140 that is received by connecting aperture 137 of mounting member 130 . In other words, connecting member 140 extends through connecting aperture 137 . Shear-configuration stitching 122 may be employed to attach second portion 142 of connecting member 140 to inflatable curtain airbag 110 . “Shear-configuration” refers to the orientation of the stitching relative to the airbag and a direction of tension that may be placed on the stitching during airbag deployment, such as during a rollover event. In other words, A sheer configuration is any sewn seam that applies a shear load to the sewing thread itself, for example, overlap sew, or folded and overlapped.
In some embodiments, one of the layers of the connecting member does not extend all the way to the end of the other layer, as depicted in FIG. 2A . In such embodiments, additional stitching may be employed to form a loop portion in the first portion of the connecting member and separate stitching may be employed to attach the single layer of the second portion of the connecting member to the inflatable curtain airbag.
In some embodiments, the connecting member may also function as a wrapper, wherein the second portion of the connecting member/wrapper extends well below the point at which the connecting member/wrapper is attached to the inflatable curtain airbag. After the inflatable airbag curtain is rolled, the second portion of the connecting member/wrapper can be wrapped around the airbag and then interact with itself so that the airbag is retained in the rolled configuration. In another embodiment, a separate wrapper is employed, which is threaded through the connecting aperture of the mounting member such that after the airbag is rolled, the wrapper can wrap around the airbag and then interact with itself such that the airbag is retained in the rolled configuration.
Mounting member 130 and connecting member 140 are collectively referred to as a mounting assembly. The mounting member and connecting member may also be called a sub-assembly of an airbag assembly. In some embodiments, a tack stitch may be used to secure the mounting member and the connecting member prior to attachment to an airbag.
For clarity, inflatable curtain airbag 110 is cutaway in FIG. 2A . Curtain airbag 110 has been manipulated into a rolled configuration and oriented such that top portion 111 is turned upward, and first face 113 is facing forward, towards the viewer. In the rolled configuration, airbag 110 has an outer surface, which may be defined by first face 113 of the airbag. Top portion 111 of inflatable curtain airbag 110 may be coupled to mounting assembly 120 at second portion 142 of connecting member 140 . Inflatable curtain airbag 110 may be coupled to the assembly at a non-inflatable portion, such as an area outside of seam 117 . In the depicted embodiment, a tab 115 is formed in the non-inflatable area of the inflatable curtain airbag 110 such that the connecting member can be coupled to the airbag via shear-configuration stitching. In other embodiments, the inflatable curtain airbag may not comprise a tab, such that the connecting member is coupled to the non-inflatable portion that is outside the stitched seam that defines the inflatable void of the airbag. Shear-configuration stitching 122 may extend through four layers of material: the first and second layers of the connecting member and the first and second faces of the inflatable airbag curtain. One skilled in the art will recognize that mounting assembly 120 may be used in conjunction with an inflatable airbag curtain that does not have a tab, but rather, has a non-inflatable portion such as depicted in FIG. 6 .
FIG. 2B is a perspective view of airbag assembly 100 and mounting assembly 120 , as depicted in FIG. 2A after connecting member 140 has been attached to tab 115 . For clarity, inflatable curtain airbag 110 has been partially cutaway in FIG. 2B . Connecting member 140 is coupled to mounting member 130 via a loop of the first portion 141 extending through connecting aperture 137 of the mounting member. In the depiction of FIG. 2B , first side 133 of mounting member 130 is facing the viewer. Rolled airbag 110 may be coupled to mounting member 130 via connecting member 140 at tab 115 . Shear-configuration stitching 122 may be employed to attach connecting member 140 to tab 115 . In the depicted embodiment, connecting member 140 is attached to inflatable curtain airbag 110 on first face 113 of the airbag; however, in other embodiments, the connecting member may be attached on the second face of the airbag. In yet other embodiments, the first layer of the connecting member may be attached on the first face of the airbag and the second layer of the connecting member may be attached on the second face of the airbag.
FIG. 2C depicts airbag assembly from perspective view, wherein inflatable curtain airbag 110 has been partially cutaway. FIG. 2C depicts airbag assembly 100 after connecting member 140 has been folded and re-sewn to cushion 110 . In the depiction of FIG. 2C , cushion 110 is in the same orientation as in FIGS. 2A-2B , wherein upper portion 111 and tab 115 are oriented upwardly, and first face 113 is facing the viewer. FIG. 2C differs from FIG. 2B in that first portion 141 of connecting member 140 has been folded toward front face 113 such that from the viewer's perspective, top portion 135 of mounting member 130 is oriented downward, and bottom portion 136 of the mounting member is oriented upward; also, second side 134 of connecting member 130 is facing the viewer.
After connecting member 140 has been folded toward front face 113 , the connecting member comprises a first loop 143 , which is located at first portion 141 , and a second loop 144 , which is formed at second portion 142 . Second loop 144 may also be described as a fold 145 of connecting member 140 . Connecting member 140 may be retained in the folded configuration by being sewn with peel-configuration stitching 124 , which may protrude through six layers of material: four layers of the connecting member and the first and rear faces of inflatable curtain airbag 110 . “Peel-configuration” refers to the orientation of the stitching relative to the airbag and a direction of tension that may be placed on the stitching during airbag deployment, such as during a rollover event. In other words, peel configuration is any sewn seam that applies a tensile load to the sewing thread itself, for example, perimeter sews with inflatable area on one or both sides. A distance from the mounting aperture of the mounting member to the stitching that couples the inflatable curtain airbag to the connecting member is a parameter that can be tuned to alter deployment characteristics of the airbag.
One skilled in the art will recognize that a variety of sheer and peel configuration stitch types and threads can be employed without departing from the spirit of the present disclosure. Stitch types may be single or double needle lock type stitches Type 301 is most commonly used. Threads with a minimum of 1350 Dtex are used for these types of strength sews, and stitch count can vary from about 30 to about 55 stitches per 100 mm. Thread count may be three twisted yarns that are bonded and lubricated for sewing with compatible fabric. Thread base material may be nylon 6.6 and is compatible with the fabric being sewn. A full or partial back tack can also be used depending on the strength needed in the seam. In some embodiments, partial back tacks may not exceed about 10 mm. In some embodiments, full back tacks may be performed to allow spacing for the needle and thread passing the first sew, which may have about 1 mm offset. The geometry of the seam can be modified for optimal performance, and may comprise a moon shape, or a double row configuration. Seams for attaching modular components, such as mounting tabs or brackets, may extend across the entire length of the modular component. Table 1 provides data regarding threads that may be used in accordance with the present disclosure.
TABLE 1
US
Twisted
Twisted
Tex Size
Decitex
Ticket
Metric
Japan
Nylon
Poly
T-135
1350
BT-
M20
5
420 d × 3
420 d × 3
138/3(RT)
T-210
2100
ST-207/3
M13
4
630 d × 3
630 d × 3
FIG. 3 is another cutaway perspective view of airbag assembly 100 of FIG. 2C , wherein airbag assembly has been rotated 180° vertically compared to FIG. 2C . In the depiction of FIG. 3 , first face 133 of connecting member 130 is facing the viewer and top portion 135 is oriented upward; also, upper portion 111 of inflatable airbag curtain 110 is facing downward, as is second loop 144 of connecting member 140 . Second loop 144 is formed by fold 145 , and if fold 145 is formed tightly, second loop 144 may be compressed. In the depiction of FIG. 3 , airbag 100 may be said to be in a “b-roll” configuration.
The orientation of assembly 100 in FIG. 3 is the same orientation depicted in FIG. 1A . As such, bolt 160 may protrude through the mounting aperture of mounting member 130 and extend into a complementary aperture formed in the roof rail of a vehicle (not shown). For clarity, first face 113 of inflatable curtain airbag 110 , which defines and outer surface of the airbag, is depicted as being located such that tab 115 , as well as shear-configuration stitching 122 and peel-configuration stitching 124 are visible; however, the diameter of the rolled inflatable curtain airbag may be such that when the airbag is in a packaged configuration, the tab and stitching are not visible.
FIGS. 4A and 4B are cross-sectional views of airbag assembly 100 , wherein FIG. 4A depicts the assembly before connecting member 140 has been folded and FIG. 4B depicts the assembly after the connecting member has been folded and re-sewn. In the depiction of FIG. 4A , mounting assembly 120 is attached to tab 115 of inflatable airbag cushion 110 on first face 113 of the airbag. In the depiction of FIG. 4A , first side 133 of mounting member 130 and first face 113 of airbag 110 are facing to the viewer's left and second side 134 and second face 114 are facing to the viewers right. Top portion 135 of mounting member 130 is topmost and includes mounting aperture 132 . Bottom portion 136 includes connecting aperture 137 and is below top portion 135 . First portion 141 of connecting member 140 protrudes through connecting aperture 137 and second portion 142 is attached to tab 115 via shear-configuration stitching 122 , which forms first loop 143 . Shear-configuration stitching 122 protrudes through two layers of the connecting member.
FIG. 4B depicts airbag assembly 100 of FIG. 4A after mounting bracket 130 and first portion 141 of connecting member 140 have been directed downward toward first face 113 of airbag 110 . Folding connecting member 140 at fold 145 forms a second loop 144 , which in the depiction of FIG. 4B is above first loop 143 . First loop 143 is captured by connecting aperture 137 . Connecting member 140 is retained in the folded configuration via peel-configuration stitching 124 , which protrudes through four layers of the connecting member. Shear-configuration stitching 122 protrudes through two layers of connecting member 140 . In the depiction of FIG. 4B , shear-configuration stitching 122 and peel-configuration stitching 124 are in distinct positions and each comprise two rows of stitching. One skilled in the art will recognize that shear-configuration stitching 122 and peel-configuration stitching 124 may not be located in distinct positions, in which case the threads of the stitching may become mingled. Additionally, shear-configuration and peel-configuration stitching 122 and 124 are depicted as each having two rows of stitches; however, one skilled in the art will recognize that the stitching may comprise fewer or more than two rows of stitching.
FIG. 5 depicts assembly 100 of FIG. 4B , wherein the assembly has been rotated 180° vertically and horizontally. The orientation of assembly 100 in FIG. 5 is similar to how the assembly may be mounted in a vehicle if a roof rail were located on the left hand side of the figure, as seen by the viewer. In the depiction of FIG. 5 , top portion 135 of mounting member 130 is above bottom portion 136 and first loop 143 is above second loop 144 and fold 145 . Upper portion 111 and tab 115 of cushion 110 are oriented downward. Upon inflatable curtain airbag 110 deployment, the airbag may change configuration from the packaged state to an extended state.
In the depiction of FIG. 5 , inflatable curtain cushion 110 appears to comprise a single layer of material; however, as described above, cushion 110 may comprise a first and a second panel of material such that the cushion comprises two layers of material. As such, shear configuration stitching 122 protrudes through four layers of material and peel configuration stitching 124 protrudes through six layers of material.
Inflatable curtain airbag deployment trajectory and characteristics are important aspects in the airbag's performance. A b-roll configuration is preferred due to its favorable deployment trajectory and characteristics; however, to be properly oriented within a vehicle, an inflatable curtain airbag is typically coupled to a mounting member via peel-configuration stitching. Peel-configuration stitching typically is not able to withstand a magnitude of tension equal to shear-configuration stitching, which is otherwise identical to the peel-configuration stitching. Airbag deployment and/or impact by an occupant during a rollover event may place a magnitude of tension on the peel-configuration stitching that is greater than their ability to withstand, but which may be withstood by shear-configuration stitching.
During inflatable curtain airbag 110 deployment, or upon being impacted by an occupant, peel-configuration stitching 124 may come under tension such that the stitching ruptures. In such a case, airbag assembly 100 may adopt a configuration similar to that depicted in FIG. 2B and FIG. 4A , wherein inflatable curtain airbag 110 remains anchored to the roof rail of the vehicle via shear-configuration stitching 122 . As such, although peel-configuration stitching 124 may rupture during airbag deployment or when an occupant contacts the inflatable curtain airbag during a rollover event, shear-configuration stitching 122 are configured not to rupture and thereby retain airbag 110 in a predetermined position.
FIG. 6 depicts another embodiment of an airbag assembly 200 from a cutaway perspective view, wherein the airbag assembly comprises a mounting assembly 220 and an inflatable curtain airbag 210 . Assembly 200 may be configured similarly and may function similarly as assembly 100 , described herein. Mounting assembly 220 may comprise a mounting member 230 , a first connecting member 240 , and a second connecting member 250 . Inflatable curtain cushion 210 may be configured similarly and may function similarly as inflatable curtain cushion 110 , except cushion 210 does not have a tab 115 as does cushion 110 . Cushion 210 comprises a perimeter seam 217 and a non-inflatable area 216 that is located outside of perimeter seam 217 . Mounting assembly 220 may be attached to first face 213 of inflatable curtain airbag 210 at non-inflatable area 216 , which is located along top portion 211 of cushion 210 .
Mounting member 230 may be configured similarly and may function similarly as mounting member 130 , described herein. Mounting member 230 comprises a mounting aperture 232 and a connecting aperture 237 . First connecting member 240 may be configured similarly and may function similarly as connecting member 140 , described herein, except first connecting member 240 is not attached to an inflatable curtain airbag; instead, first connecting member 240 is attached to a second connecting member 250 via first shear-configuration stitching 226 . First connecting member 240 may comprise a flexible fabric that can be threaded through connecting aperture 237 such that a first loop 243 is formed when the connecting member is attached to second connecting member 250 . FIG. 6 depicts first connecting member 240 as being attached to second connecting member 250 on a front face; however, as one skilled in the art will recognize, the connecting member may be attached to either face of the second connecting member, including both faces of the second connecting member.
Second connecting member 250 may comprise a flexible piece of fabric, which has a first portion 251 and a second portion 252 , wherein the first and second portions may be considered approximate top and bottom halves of second connecting member 250 . Top portion 251 is attached to first connecting member 240 via first shear-configuration stitching 226 . Bottom portion 252 is attached to inflatable curtain airbag 210 at non-inflatable area 216 via second shear-configuration stitching 222 . In other embodiments, the second connecting member may have an extended bottom portion, which functions as a wrapper.
One skilled in the art will recognize that the various connecting members described herein may be formed from a variety of materials. For example, the connecting members may be formed from one or more layers of Uncoated flat woven nylon fabric of high construction, such as 19×19 yarns per centimeter. Examples of suitable materials include 470 Dtex f 136-144 (19×19 yarns per centimeter) and 700 Dtex f 105-108 (16×16 yarns per centimeter). Additionally, materials having variations in weave and yarn size may be used. Further, the fabrics can be used in multiple layers and/or fused together.
FIGS. 7A and 7B are cross sectional views depicting inflatable curtain airbag assembly 200 , wherein FIG. 7A depicts the assembly before the second connecting member has been folded and FIG. 7B depicts the assembly after the second connecting member has been folded and re-sewn. In both figures, top portion 235 of mounting member 230 is topmost such that connecting aperture 237 is located below the top portion. First connecting member 240 has been captured by connecting aperture 237 and attached to second connecting member 250 via first shear-configuration stitching 226 such that first loop 243 is formed.
FIG. 7A depicts assembly 200 before second connecting member 250 has been folded. Top portion 251 of second connecting member 250 is coupled to first connecting member 240 and bottom portion 252 is attached to top portion 211 of inflatable curtain airbag 210 on front face 213 via first shear-configuration stitching 226 . Assembly 200 as depicted in FIG. 7A can be manipulated into the configuration of FIG. 7B by directing bottom portion 252 of second connecting member 250 upwardly, in a direction that is opposite the side on which inflatable curtain airbag 210 is located.
FIG. 7B depicts assembly 200 after second connecting member 250 has been folded. In a second connecting member-folded configuration, top portion 211 of cushion 210 is directed away from top portion 235 of mounting member 230 . The second connecting member-folded configuration may also be defined by a second loop 254 that is formed by a fold 255 in lower portion 252 of second connecting member 250 . Second loop 254 may comprise a fold of second connecting member 250 , wherein the fold, or an aperture of second loop 254 , is oriented approximately parallel with a long axis of rolled inflatable airbag curtain 210 . After second loop 254 has been formed, assembly 200 may be retained in the second connecting member-folded configuration via another peel-configuration stitching 224 .
Assembly 200 may be mounted in a configuration similar to that depicted in FIG. 7B , and during inflatable curtain airbag 210 deployment, the airbag may unroll and assume an extended configuration. As described above for assembly 100 , during inflatable curtain airbag 210 deployment or upon the airbag being impacted by an object during a rollover event, peel-configuration stitching 224 may fail. In such an event, the inflatable curtain airbag may be retained in position via second shear-configuration stitching 222 , which may resemble the configuration depicted in FIG. 7A , except inflatable curtain cushion 210 would be in an extended configuration rather than a rolled configuration, as depicted in the figure.
In one example, a single mounting assembly attached to a portion of an inflatable airbag assembly was tested in a dynamic load drop testing fixture. The tested mounting assembly and airbag portion were configured as depicted in FIGS. 6-7B . The dynamic load drop testing fixture may be of any type well known in the art and comprises a mass, an anchor, a sample coupling mechanism, a load sensor, and a data acquisition system. To test what magnitude of force is required to rupture the peel and/or shear configuration stitching, as described herein, the mounting member or the first connecting member is coupled to an anchor portion via the sample coupling mechanism. The airbag portion can be coupled to the mass via another sample coupling mechanism such that the mounting member and airbag sample couples the anchored portion of the testing fixture and the mass such that force can be applied to the sample by dropping the mass. The magnitude of force can be measured by coupling a load sensor, or load cell, by coupling the load sensor to the sample somewhere between the mass and the anchor. The magnitude of the mass and the distance the mass is dropped can be tuned to alter the force applied to the sample. The magnitude of the force applied to the sample can be increased until the sample fails.
In the instant example, a double-sewn mounting assembly was tested in a dynamic load drop testing fixture. A magnitude of force was applied to the sample that was sufficient to rupture the peel configuration stitching and the shear configuration stitching. The peel configuration stitching failed when a force of about 1200 Newton was applied, and the shear configuration stitching failed when a force of about 2500 Newton was applied.
Any methods disclosed herein comprise one or more steps or actions for performing the described method. The method steps and/or actions may be interchanged with one another. In other words, unless a specific order of steps or actions is required for proper operation of the embodiment, the order and/or use of specific steps and/or actions may be modified.
Reference throughout this specification to “an embodiment” or “the embodiment” means that a particular feature, structure or characteristic described in connection with that embodiment is included in at least one embodiment. Thus, the quoted phrases, or variations thereof, as recited throughout this specification are not necessarily all referring to the same embodiment.
Similarly, it should be appreciated that in the above description of embodiments, various features are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure. This method of disclosure, however, is not to be interpreted as reflecting an intention that any claim require more features than those expressly recited in that claim. Rather, as the following claims reflect, inventive aspects lie in a combination of fewer than all features of any single foregoing disclosed embodiment. Thus, the claims following this Detailed Description are hereby expressly incorporated into this Detailed Description, with each claim standing on its own as a separate embodiment. This disclosure includes all permutations of the independent claims with their dependent claims.
Recitation in the claims of the term “first” with respect to a feature or element does not necessarily imply the existence of a second or additional such feature or element. Elements recited in means-plus-function format are intended to be construed in accordance with 35 U.S.C. §112 ¶ 6. It will be apparent to those having skill in the art that changes may be made to the details of the above-described embodiments without departing from the underlying principles of the invention. Embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows. | Mounting assemblies can be used to attach an inflatable curtain airbag to a vehicle structure. Mounting assemblies can include a mounting member, a connecting member, and an optional wrapper. The connecting member is attached to the mounting member and the airbag via stitching, which can be categorized according to the primary direction of stress that may be placed on the stitching during airbag deployment. Stitching in shear is stronger than otherwise identical stitching in peel; however, a preferred method of packaging a curtain airbag results in a b-rolled airbag that can not be attached to the connecting member with shear stitching alone. Peel stitching alone may not be strong enough to retain an occupant within the vehicle during a rollover event. As such, a combination of a folded connecting member, shear stitching, and peel stitching allows a b-roll airbag to meet occupant ejection mitigation requirements. | 1 |
FIELD OF THE INVENTION
The invention pertains to electric motors having a plurality of magnetic poles wherein the poles are alternately polarized and neutralized to produce rotation of a motor rotor.
STATE OF RELATED ART
It is commonly known that a magnet pole or a ferrite pole with an energized direct current (DC) coil around it will only allow flux which is in-phase (with the same magnetic orientation) to travel through the pole. Flux which has an opposite magnetic orientation will be rejected unless it is strong enough to overpower and reverse the permanent magnet pole's orientation or to “capture” and reorient the ferrite pole and align it against the DC coil. According to traditional magnetic theory, each magnet or DC electromagnet will only pass flux in one direction, from the south pole through to the north pole. A magnet or DC electromagnet will not allow flux to pass from the north pole through to the south pole.
Further, it is also known that if two coils of equal turns with equal amperage flowing in their turns (equal ampere-turns) are on the same ferrite pole, but with opposite magnetic orientation, that the net magnetic flux coming from that ferrite pole will be zero (0) as the two coils will cancel each other. Because the net magnetizing force is zero (0), the domains of the ferrite pole are not aligned in any one direction and thus remain random under these conditions. The equal and opposite electromotive forces of the two coils cancel each other's magnetomotive force in the ferrite pole, equaling zero (0) magneto-mechanical force between the end of the pole and the ferrite rotor as no flux is manifested from the pole end.
Further, it is known that if two coils of equal turns with equal amperage flowing in their turns are on the same ferrite pole, and they have the same magnetic orientation, the flux from both coils will series in the pole and will cause a magnetomotive force on the ferrite pole much greater than that of each coil independently and that the net flux concentration and manifestation, all other things being equal, will be much greater at the pole end than if only one coil is activated.
OBJECTS OF THE INVENTION
It is an object of the invention to provide an electric motor having poles energized by coils wherein each pole is energized by two separate coils and the coils are so energized as to cause a given pole to have a momentary maximum polarity effect and a momentary neutralized effect to create an effective motor rotor rotation.
Another object of the invention is to provide an electric motor having a plurality of poles wherein magnetic polarity in the poles is produced by coils or windings and where each coil is under the influence of separate coils so synchronized as to alternately produce a predetermined polarity in the pole and a neutral polarity wherein motor rotation is produced
A further object of the invention is to produce a split-pole electric motor which requires only a single phase system and yet provides results similar to multi-phase systems resulting in a less expensive controller than previously known.
An additional object of the invention is to provide an electric motor having a plurality of adjacent poles, each pole being wound by two separate coils, one of the coils utilizing direct current while the other coil utilizes alternating current, and the direct current is controlled by the cycling of the alternating current coils to alternately produce an amplified polarity and a neutral or zero (0) polarity in a given pole.
SUMMARY OF THE INVENTION
In this disclosure, the effect of the invention will be called the Field-Match effect. The reason for the use of the word “match” is that it has two near opposite meanings: one which means “to agree, to be alike” (which we will designate “match 1 ”) and another meaning which means “to oppose”, as in a “football match” (which we will designate “match 2 ”). The torque produced by the stator on the rotor of the Split-Pole Field-Match Motor is caused by a unique design in which two coil fields of near equal value are matched on a single stator pole, alternately, in both senses of the word “match”.
First, they are “matched 1 ” in one part of the electrical phase as like-fields on the same pole which series and causes the pole to exert a magnetomechanical force on a laminated, ferrite, salient poled rotor, then the coils are “matched 2 ” as opposing fields on the same pole in the opposite part of the electrical phase and the opposing magnetomotive forces exerted on the pole cause there to be no magnetomechanical force exerted on the ferrite rotor, as no flux is manifested from the pole.
The Split-Pole Field-Match Motor uses this concept to integrate all the active magnetic components of a motor into the stator which interacts with a laminated salient pole rotor in a smooth and efficient way which makes it unnecessary to use an induction rotor. This makes the stator-rotor configuration look much like that of a variable reluctance motor However, the split-pole field-match system used in the stator of this motor to cause torque on the rotor creates the torque in a very different manner from that of any variable reluctance motor now in use, and this distinction will be easily appreciated from the following description. The Split-Pole Field-Match motor integrates direct current (DC) coils and alternating current (AC) coils on the stator in an overlap configuration to create field concentrations on alternate sets of half-poles on the stator.
With the method of the invention, the split-pole field-match system can produce motors whose operation requires only a single-phase system and produces competitive results equal to motors which require the controller to provide multi-phase operation, thus making the use of less expensive controllers for the same result possible.
It is anticipated that one of the major embodiments of this motor system will provide a new alternative for applications which now use brushless DC motors with the advantage being cost and a wider RPM range due to the inherent safety and durability of the salient pole ferrite rotor which requires no induction coils or casings or no magnets which require lower top RPM to remain within a safe range.
In the disclosed embodiment of the invention, an even number of poles are defined upon the electric motor stator, and two adjacent poles are defined as a set A second set of a pair of poles constitute one of the poles of the first set and the adjacent pole not of the first set. Accordingly, first and second sets of poles will be adjacent and include a common pole. The first set of poles is wound with a direct current coil, and a second set of poles is wound with an alternating current coil. This arrangement causes the first pole set to have a complete DC coil wound thereabout and two one-half alternating current coils disposed thereon. The second set of poles will include a full AC coil and two one-half DC coils. The DC coils are energized through a rectifier to rectify the AC quasi-sine wave from an inverter circuit, or the AC from traditional wall current, connected to the AC coils. The AC coils are all connected into series with each other, and likewise, the DC coils are all connected into series with each other. Thereby, the AC current within the AC coils will be perfectly in synchronization with the rectified DC pulses in the DC coils, and the result is that one of the poles of the first pole set alternately is polarized with a predetermined polarity which is intensified by the effects of the two coils influencing the pole, and the other pole of the set will be neutralized due to the opposite polarity effect of the coils while the first pole is being polarized. In the second set of poles, the non-common pole will be alternately polarized oppositely with effect to the polarized first pole set and alternately neutralized This inter-connection and energization of poles results in alternate poles being oppositely polarized while having a neutralized pole in between This polarity arrangement will cause rotation of the rotor due to the attraction of the rotor poles to opposite polarity stator poles.
BRIEF DESCRIPTION OF THE DRAWINGS
The aforementioned objects and advantages of the invention will be appreciated from the following description and accompanying drawings wherein:
FIG. 1 is a partial schematic view of a motor stator in accord with the invention illustrating the direct current coils, only, being wound upon adjacent sets;
FIG. 2 is a partial schematic view similar to FIG. 1 illustrating the alternating current coils wound upon the appropriate poles of the stator;
FIG. 3 is similar to FIG. 2 and illustrates the polarity and neutrality of adjacent poles and sets;
FIG. 4 is similar to FIG. 3 illustrating the polarity and neutrality of adjacent poles during the opposite cycle with respect to FIG. 3 ;
FIG. 5 is similar to FIG. 3 illustrating the polarity and neutrality of adjacent poles after the cycle illustrated in FIG. 4 ;
FIG. 6 is a schematic depiction of the field flow in adjacent poles only due to the direct current coils;
FIGS. 7 and 8 illustrate how the fields of the DC coils interact with the fields of the AC coils, wherein FIG. 7 illustrates the positive electrical half phase, and FIG. 8 illustrates the negative electrical half phase;
FIG. 9 illustrates a rotor of the type as would be utilized with the stator shown in FIGS. 1-8 ;
FIG. 10 is a schematic illustration utilizing the principles of the invention wherein rotor poles are wound in a manner equivalent to the stator poles;
FIG. 11 is a schematic illustration showing the AC and DC coils located upon rotor poles in a manner equivalent to FIGS. 2-5 and 7 ;
FIG. 12 is a schematic illustration of a transverse cross-section between an assembled motor rotor and stator wherein the rotor poles are wound as shown in FIG. 11 ;
FIG. 13 illustrates the basic circuit used to control the motor of the invention if the AC coils are replaced by bifilar windings. The two resulting coils are connected oppositely to the DC switching and are triggered alternately so that they alternately induce the opposite flux field into the poles around which they are wrapped. This arrangement makes it possible to use a simpler DC circuit which lowers costs; and
FIG. 14 illustrates the basic circuit design to control the motor of the invention if the AC coils are retained and used. In such instance, the circuit creates alternating voltage and current as desired and applies it to the AC coils and the DC coils. The DC coils, as shown, are connected through a full-wave bridge, and therefore, have DC pulses which are in phase with the AC pulses in the AC coils.
DESCRIPTION OF THE INVENTION
FIG. 1 is a diagrammatic view of a portion of the Split-Pole Field-Match Motor stator 100 , which, in its entirety, would be an eight (8) pole stator, in which only the DC stator coils 104 , 105 , 106 , 107 are shown wrapped around the split-poles 101 and 102 (fully shown) and 103 and 108 (partially shown). As illustrated, split-pole 101 is designated as magnetic-pole # 1 and will always have a north field being induced into both halves of the pole by the DC coil 104 . This means that the two salient protrusions which make up the two halves of split-pole 101 form a single magnetic pole which will always have a north field on the face of one of its halves. Split-pole 102 is designated as magnetic-pole # 2 and always has a south field being induced into both halves of the pole by the DC coil 105 . This means that the two salient protrusions which make up the two halves of split-pole 102 form a single magnetic pole which will always have a south field on the face of one of its halves. The description for split-pole 103 , which is designated magnetic-pole # 3 , is otherwise the same as that for split-pole 101 except that its DC field is obviously induced by DC coil 106 . This pattern of north, south, north, south magnetic split-poles continues all around the inside circumference of the stator until it completes the stator split-poles at split-pole 108 , which is next to split-pole 101 and is designated as magnetic pole # 8 , which always has a south field on one of its halves. It can also be observed from FIG. 1 that the halves of each split-pole are spaced apart so that the space used to split the various poles is equal to the space between each of the magnetic poles 1 , 2 , 3 , etc. Thus, all half-poles are the same distance from its other half as it is from the nearest half of any split-pole adjacent to it around the inner circumference of the stator.
In FIG. 2 , the AC coils of the stator are shown added to the same portion of the stator as in FIG. 1 . As is illustrated, the AC stator coils 109 , 110 , 111 , 112 , and 113 are shown wrapped through the split of two different poles so that the AC coils are wrapped on a right half-pole and a left half-pole of two adjacent split-poles which, together, will make up that AC coil's ferrite core. Thus, AC stator coil 109 is wrapped around the right half-pole of split-pole 108 and the left half-pole split-pole 101 , and AC stator coil 110 is wrapped around the right half-pole of split-pole 101 and the left half-pole of split-pole 102 , etc. This means that each AC coil is wrapped so that its ferrite core is made up of two half-poles from two different split-poles which have two different DC fields being induced into them and thus, one of the half-poles of its core has a south field induced into it from its DC coil, and the other adjacent half-pole has a north field induced into it from its DC coil.
Thus, it can be understood that as the AC coils alternate between the positive and negative portions of the electrical phase, it will always match one of the half-poles magnetically as defined by “matched 1 ” earlier in this disclosure and match the other half-pole magnetically as defined by “matched 2 ” earlier in this disclosure. Thus, in each half of the electrical phase, it will always magnetically series with the DC coil on one of the split-poles causing magnetic flux to be induced into that half-pole which will cause a magnetomechanical force to be set up between that half-pole and a ferrite pole of the rotor and it will, at the same time, magnetically oppose the DC coil on the other adjacent half-pole which makes up its core, thus inducing an equal and opposing magnetomotive force in that half-pole and causing it to manifest no flux and thus not cause a magnetomechanical force to be set up between that half-pole and a ferrite pole of the rotor. In the next electrical half-phase, the AC coils will reverse their field, and the opposite effect will occur where they will now series with the half-pole and DC coil it formerly opposed and will also oppose the other half-pole and DC coil with which it formerly went into series.
The AC coils are alternately wrapped so that each AC coil produces the opposite magnetic field from the AC coil either to the right or left of it. This will ensure that a magnetic pattern of flux will be created in which, for one electrical half-phase, every other half-pole, one in each split-pole (e.g., the ones on the left) will manifest magnetomechanical force on the rotor while the other set, i.e., the ones on the right, will not. In the next opposite electrical half-phase, the half-poles on the right will manifest magnetomechanical force on the rotor while the former set of half-poles, the ones on the left, will not. This is illustrated in FIGS. 3 and 4 .
In FIG. 3 , an “X” is placed below each right-hand half-pole of split-poles 101 , 102 , 103 and 108 . This is to indicate that there is no field being produced in these half-poles because the AC coils on those half-poles are out of phase with the DC coils on those half-poles during the electrical half-phase. Thus, no field is manifested. At the same time, the left-hand half of each split-pole 101 , 102 , 103 , and 108 shows either a north or a south below it indicating that a field is being induced by the AC coils into those half-poles which is in phase with the DC coils of those split-poles; thus, field is manifested. In FIG. 4 , the next opposite electrical half-phase is shown, and the left-hand half-poles of each split-pole now has an “X” to indicate that the AC coils have reversed their field and are now out-of-phase with the DC coils on those left-hand half-poles. At the same time, the right-hand half of each split-pole 101 , 102 , 103 , and 108 shows either a north or a south below it indicating that a field is being induced by the AC coils into those half-poles which is in-phase with the DC coils of those split-poles. Thus, field is manifested. FIG. 5 illustrates a return of the AC coils to the first electrical half-phase as in FIG. 3 , and the result is that the magnetic pattern returns to the same as in FIG. 3 , thus causing an alternating, repeating pattern of field manifestation from the half-poles of each split-pole.
FIG. 6 , is a diagrammatic depiction of the field flow in the stator due only to the DC coils. As can be seen, this creates north and south domains in the stator which will always be north or south unless opposed by the field of an AC coil. FIGS. 7 and 8 show how the fields of the DC coils interact with the AC coils, with FIG. 7 being the positive electrical half-phase and FIG. 8 being the negative electrical half-phase.
The laminated, salient pole rotor that is used with the Split-Pole Field-Match stator has salient poles which match the number of magnetic poles on the stator (in the case of the embodiment illustrated above, eight poles), and each salient pole is sized and spaced so that it matches the face of a half-pole of each split-pole. Thus, there is a rotor pole to interact with every other half-pole alternately as the rotor rotates. Such a rotor is illustrated in FIG. 9 , where laminated ferrite rotor 119 is shown with salient poles 120 , which are eight (8) in number. Power take-off shaft center hole 121 is provided so the rotor 119 can be press fitted to a power take-off shaft.
The current to the motor can be supplied in different ways. In the preferred embodiment illustrated above, it is supplied by a single-phase inverter circuit which produces rectangular current waveforms with continuously variable frequency controlled by the speed of the motor by means of simple position sensors.
In the embodiment above, the AC coils are all connected into series with each other. The DC coils are all connected into series with each other. The DC coils are all connected into series with each other and use a bridge circuit to rectify the quasi-sine wave from the inverter circuit into DC pulses which power the DC coils. These DC pulses are perfectly in synchronization with the AC pulses to the AC coils because they are from the same source and are simply bridge-rectified. A constant DC from an alternate power source can be used or a capacitor placed into the bridge circuit to make the pulse DC constant This gives a different kind of motor response which can be “tuned” by adjusting the DC current for the desired performance. However, the pulse DC matches the AC stator coils almost automatically if the AC and DC coils have been properly matched which is usually that they have the same number of turns per coil and wound from the same size magnetic winding wire.
In FIGS. 10-12 , the concepts of the invention are shown wherein the rotor poles, rather than the stator poles, are coil wound in the manner previously described. The inventive concepts and principles of motor operation are identical in the embodiments of FIGS. 10-12 as in the previously described embodiments. FIG. 10 illustrates the rotor at 200 , and the rotor includes pairs of adjacent poles 201 - 208 . In FIG. 10 , these poles are wound in pairs of sets of coils 209 - 216 . The coils 209 - 216 constitute bifilar wound DC coils, and the identical coils are oppositely connected to a DC circuit which alternately switches them so that they alternately induce oppositely oriented flux in their poles. The original single set (non-bifilar wound) DC coils are either put in parallel with these bipolar coils or series. The circuit which is used to control these configurations is shown in FIG. 13 .
In FIG. 11 , the coils 209 - 216 constitute AC coils, while the coils 217 - 224 are DC coils. The embodiment shown in FIG. 11 operates in the manner described in FIGS. 1-9 . The rotor 200 includes the central hole 225 for receiving the shaft, and as shown in FIG. 12 , the stator 300 includes eight poles for accommodating the sixteen-hole rotor having eight sets of poles. The embodiment of FIG. 11 operates in the same manner as the embodiments of FIGS. 1-9 .
The circuit shown in FIG. 13 is used to control the pole wound configuration shown in FIG. 10 . The various components of the circuit are illustrated by applied legends.
In FIG. 14 , the circuit illustrated is that used to control the motor of FIGS. 1-9 and FIG. 11 , wherein one set of DC coils and one set of AC coils are used with pairs of poles. The motor of the invention can run without a circuit from normal 120 volt alternating current When the number of pole divisions are high in the stator and the pole widths are small, the motor of the invention will start itself under load without the need of circuit or starting coil. When the number of pole divisions is smaller and thus the pole widths are larger, a circuit or starting coil is used for poles to come into synchronization.
It is appreciated that various modifications to the inventive concepts may be apparent to those skilled in the art without departing from the spirit and scope of the invention. | An electric motor having a plurality of rotor and stator poles, the poles of one element being alternately polarized and neutralized due to the use of direct current and alternating current windings on each pole. The poles of like current are connected in series, and the direct current poles are energized in synchronization with the alternating current poles. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to financial systems and, in particular, to an international data processing network which provides accessibility, speed, and flexibility in effecting payments 24 hours a day in and among multiple national currencies, such as, but not limited to, U.S. Dollars, Japanese Yen, and British Pounds Sterling. This invention is also directed to a set of mutual fund portfolios used to effect currency payment transactions to settle transactions which require such currency payments as fulfillment of an obligation. This invention is further directed to a set of mutual fund portfolios used to initiate and settle transactions which exchange value between national currencies, similar to foreign exchange.
In general, investors purchasing shares in a typical mutual fund transfer assets, such as cash, to the account of the mutual fund at a custodial institution (custodian). If the mutual fund is closed-ended, there is a limit to the number of shares which the mutual fund may issue. Conversely, if the mutual fund is open-ended, there is no limit to the number of shares which the mutual fund may issue. The mutual fund's investment advisor uses those assets transferred to it by an investor to invest in securities or other approved investments as allowed by the mutual fund's prospectus, although typically a fund will maintain a portion of its assets in cash and cash equivalents. The mutual fund's transfer agent issues to the investor the number of shares equivalent to the value of the assets transferred to the fund by said investor divided by the price of a share in the mutual fund. At this point, the investor becomes a shareholder. The price of the share is determined by the aggregate of the current market value of the mutual fund's assets and the income earned by these investments, less accrued management fees and expenses. Most mutual funds instruct their fund accountants to calculate this share price which is called a net asset value calculation, once a day. This is done by obtaining current market prices for each investment held by the fund. Investors may only purchase shares or redeem shares at a share pricing. When a shareholder redeems some number of shares, to the extent that the fund does not have cash on hand, the investment advisor sells a portion of the mutual funds assets in order to pay said shareholder the value of his shares as determined by the fund price.
There exists a multitude of mutual fund arrangements which allow shareholders to purchase and redeem open-ended shares together with limited rights of third-party purchase, also called share transfer (that is the change of ownership of a share in a portfolio from one owner of record to another), and limited rights of exchange (that is the movement of wealth from one portfolio to another by the same shareholder). Such mutual funds generally exist either as a single, or a group, of portfolio(s) denominated in one national currency, such as U.S. Dollars. For example, in a group of mutual fund portfolios, one portfolio may be invested in technology companies whereas another portfolio may be invested in energy companies. Thus, typical mutual funds earn profits and have losses based on this national currency. Furthermore, there are still other mutual funds which hold assets denominated in more than one national currency. These mutual funds earn profits and experience losses based on each currency in which its investments are denominated.
The art is replete with various concepts involving the use of mutual funds for purposes of cash money management. Additionally, these systems use the same data processing system associated with the mutual fund to provide ancillary services such as brokerage accounts, credit card services and the like. Reference is made to U.S. Pat. No. 4,346,442, which describes a cash money management scheme that is constructed around the architecture of a short term money market fund that invests free cash and uses funds in the money market for purposes of payment of charge card transactions and the like. The fund relates to only one national currency.
Reference is made to descriptions in the literature which describe alternative uses of mutual fund shares including: Gorton, Gary and George Pennacchi ("Financial Intermediation and Liquidity Creation", Journal of Finance, volume 45 number 1, March 1990) and Jacklin, Charles. J. (Working Paper, Stanford University, "Demand Equity and Deposit Insurance", April 1990).
However, mutual fund shares are not currently used through effecting share transfers for purposes of paying for goods, services, and other financial obligations such as meeting collateral requirements common for good faith deposits, securities trades, and other credit requirements. Mutual fund shares are also not used today for settling foreign exchange transactions.
The international financial community today operates using numerous national currencies and with them, distinct systems, rules, procedures and laws for currency payments for settlements of obligations within the country issuing that currency. Most rely on the country s central bank, such as the Federal Reserve in the United States, to guarantee that once a payment is made, it is irreversible. The timing of this guarantee which is called finality of payment, varies by country and by system and may be immediate, at the close of the business day, sometime the following business day, or later. This guarantee, and the execution of transactions, is dependent upon the operating hours of the central bank and the wire system. Thus, there exist within the financial community acute problems and risks when making payments in a particular country when the transfer of the underlying currency of the transaction is not supported by that country's financial system and its central bank.
Furthermore, this fragmentation of financial systems hinders the ability to change the value of the wealth held in one national currency into another national currency. The foreign exchange market is used for this purpose, but carries with it certain costs, delays in money availability and risk. In addition, there are similar problems when moving money within a national currency such as moving U.S. Dollars through the Federal Reserve Bank's Fedwire system, an internal mechanism within the Federal Reserve system to transfer currency which provides immediate finality of payment. Fedwire encompasses several Federal Reserve Bank districts, based on geographical area of the country, each with operational jurisdiction over its node of the Fedwire system. Moving money from one Federal Reserve district to another Federal Reserve district utilizing Fedwire may be subject to delay because it must pass through several nodes. Moreover, the transactions are conducted via the Federal Reserve wire which has at critical times failed. A noteworthy example of a failure(s) of the Federal Reserve wire occurred during the October 1987 stock market collapse.
This shortcoming is not limited to the United States. Other networks exist, not necessarily Government sponsored, for foreign currencies such as CHAPS for Pound Sterling and the Bank of Japan for Yen.
To date, there are no systems in effect or proposed which employ the mutual fund architecture such that issued shares can be used as currency equivalents to alleviate these problems of currency infungibility and the dependence on the central bank for payment movement and payment finality.
Within the business community there is an acute requirement for immediate currency availability to clear and settle transactions, such as in, but not limited to, the field of futures contracts. Futures trading is predicated on deposit and payment of required margins. These include an initial margin payment as a good faith deposit, set as a proportion of the value of a futures contract. Each counterparty (side) to a futures trade pays this initial margin to a clearing house through a clearing member on the day following the trade day. This initial margin is held throughout the life of the contract. The price of the contract fluctuates throughout its life.
These fluctuations in contract price give rise to a requirement for a variation margin, which is required once or twice a day by the counterparty against whom the price has moved. This "losing" party must deposit increased collateral with the clearing house to maintain the contract. This collateral is then transferred immediately to the party in whose favor the price has moved.
As an example, at the Chicago Mercantile Exchange, initial margins are called for at 6:40 a.m. CST on the day following the trade date. Variation margins are also called for at 6:40 a.m. CST and at 3:00 p.m. CST every day throughout the life of the contract, every day starting the day following the trade. Payment for initial margin requirements is generally based on deposit of interest bearing treasury securities, letters of credit or cash. Requirements for variation margin are always paid in cash. There is a time lag between the time this requirement is known until the time the payments can be made, because the United States payment systems are closed at 6:40 a.m. CST. Additionally, these payments are subject to the operating procedures of each bank involved in the process. Which may delay availability of funds and introduce additional costs. These two situations cause the execution of margin payments to occur three to four hours later than is optimal from the clearing house s perspective.
Furthermore, there is no way to pay for margin during U.S. business hours in a currency other than the U.S. Dollar. Because U.S. clearing houses prefer to be paid in the same currency as that in which the price of the futures contract is expressed, the inability to move national currencies other than the U.S. Dollar with immediate finality of payment within the U.S. business day has been a hindrance to the development of such non-dollar denominated contracts. In addition, there is no payment/wire system or network in which clearing houses, and trading firms can make U.S. Dollar payments to each other without using a bank for access to the system.
Yet another example of delays and costs associated with currency transactions is a simple foreign exchange transaction, such as from U.S. Dollars to Japanese Yen. An institution typically wishing to make such an exchange currently requires the intervention of at least two banks, a bank in the United States to initiate the transfer in dollars and a receiving bank in Japan to receive and transfer the converted funds to the Yen account. Multi-day delays for fund availability are common even in the case of wire transfers. The requirement that multiple banks be used increases fees.
Furthermore, since the two sides of the transaction are not effected within the same financial system, there is an opportunity for loss, whereby the Yen transaction is accomplished but the companion U.S. Dollar transaction is not. Thus, there exists a need within the financial community for a vehicle by which currency transactions and exchanges can be made on a timely, reliable and synchronous basis.
In the evolving global economy, a variety of problems continue to exist associated with the use of multiple national currencies. These problems can range from the extreme of currencies which are not convertible, such as the ruble in the U.S.S.R., to merely issues of inconvenience.
SUMMARY OF THE INVENTION
Given these problems with existing financial systems, it is an object of this invention to provide a network which allows for the use of mutual fund shares as currency equivalents in the clearing and settling of commercial transactions.
Yet another object of this invention is to provide a financial transfer network that permits the purchase and transfer of mutual fund shares based on one or more currency portfolios managed in a common fund.
A further object of this invention is to define an international financial transaction network which permits foreign exchange transactions to be predicated on an exchange of mutual fund shares which exist in parallel portfolios each based on a different currency irrespective of the issuer of the currency.
An important object of this invention is to provide a financial exchange network which substitutes mutual fund shares for currency which guarantees collateral and permits more immediate finality of settlement of obligations in financial markets, such as, but not limited to, futures, options and the like.
A further object of this invention is to define a network mechanism which allows shareholders to negotiate share exchanges outside the fund yet use the vehicle of the fund for transfers of shares.
Still another object of the invention to is provide a financial network that maintains records on the network data base managed centrally by the mutual fund in which relationships among accounts may be maintained.
An object of this invention is to establish a financial network that provides a medium of exchange for otherwise non-convertible currencies.
These and other objects of this invention are achieved by means of a financial transaction network that employs one or a number of single currency portfolios tied together in one or more mutual funds which operate using substantially a 24 hour system. Country of registration of the fund(s) does not relate to the performance of the invention. Independent currency portfolios are maintained and managed, generally in the country which issues that currency. The independent portfolios are tied together by a 24 hour host processor providing client service and administration together with a transfer agent in charge of maintaining record ownership and a fund accountant in charge of calculating net asset value. Portfolios are priced at intervals approaching continuous pricing, such as every two hours, which is more frequently than any other money market mutual fund. With this frequent pricing structure the investor may purchase and redeem shares more frequently than he can in a typical mutual fund. However, share transfers may occur at any time. With this pricing mechanism, the mutual fund is tied closely to its custodian(s) for the purposes of notification of incoming funds. Once a day, each portfolio distributes its earnings pro rata to its shareholders in the form of share dividends. In this way, the price of the share is maintained at a constant net asset value.
Given this basic architecture, a shareholder may buy shares in any of the currency portfolios maintained by the network. That is, in the example of U.S. Dollars. Japanese Yen and British Pounds, a shareholder may purchase and redeem shares in any available portfolio with the currency of that portfolio. Transactions between shareholders can take multiple paths in the network. Within any single currency portfolio, shares can be transferred from an account of one shareholder to that of another shareholder. This is called a third party purchase, or a share transfer. Thus, by transferring shares within the U.S. Dollar portfolio, U.S. Dollar equivalent payments are made without the requirement of a bank. This feature is particularly useful in the settlement of financial market contract settlement obligations, such as those in the futures markets, which require payments when banks are not open.
Another transfer mechanism is one which allows for private currency exchanges to be made between two shareholders utilizing the vehicle of fund shares as the transfer mechanism. For example, one shareholder has U.S. Dollar shares and another shareholder has Yen shares. They decide to "swap" or trade their holdings, and both parties notify the mutual fund of their intentions. The mutual fund effects this by transferring a specified number of the first shareholder's U.S. Dollar shares to the other shareholder while simultaneously transferring a specified number of Yen shares from the other to the first shareholder. This share transfer mechanism is also useful for the transfer of value as represented by otherwise non-convertible currencies.
Within the mechanism a shareholder may also move funds from one portfolio to another by redeeming shares in one portfolio and using the proceeds to fund a traditional foreign exchange transaction in which he obtains the currency of the second portfolio, and then, using the second currency purchases shares in the second portfolio.
Access to the financial network would be, generally, a workstation with dedicated software to provide access into a client service and administration system. The financial network also includes a bulletin board feature whereby shareholders can list expressions of interest to "swap" shares with other shareholders. If the two shareholders agree to a swap, they each instruct the client service and administration host processor of the settlement information for the swap. The financial network also includes multilevel directories to provide accounting data at various levels (portfolio, house, customer, etc.). A centralized transfer agent system operates in conjunction with the client service and administration system for purposes of facilitating transfers of shares in all of the portfolios.
Consequently, this financial network acts like a demand deposit account permitting deposits in the form of purchases and withdrawals in the form of redemptions. The portfolios pay dividends in the form of interest to share holders. The financial network permits movement within a currency in the form of share transfers which are equivalent to money transfers within a denominated currency and additionally, movement between currencies by portfolio exchange and by matched transfers. The latter is equivalent to a foreign exchange transaction.
This invention will be described in greater detail by referring to the attached drawing and the description of the preferred embodiment that follows.
BRIEF-DESCRIPTION OF THE DRAWING
FIGS. 1A and 1B are flow charts illustrating the system components of the financial transaction network in accordance with this invention;
FIG. 2 is a flow chart illustrating the transaction flow for a share purchase;
FIG. 3 is a flow chart indicating the transaction flow for a share purchase and transfer:
FIG. 4 is a flow chart illustrating the transactional flow for a matched share transfer:
FIG. 5 is a flow chart illustrating the transactional sequence for a share receive and redeem transaction: and
FIGS. 6A-6E illustrate sample menus and screens used in accordance with this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIGS. 1A and 1B, the basic architectural aspects and relationships of this financial network are depicted. Access to the financial network is achieved through a user workstation 100 located at each customer site. Dedicated software featuring a menu driven system with multiple levels of security, formatted screens for data input, and local editing capability is provided for the workstation 100. The ability to format and transmit instructions, receive confirmations from the host system, and make inquiries to a customer mailbox is provided from the user workstation 100. Thus, the workstations are used by shareholders for data entry, to receive confirmations and to make inquiries regarding transaction status to the financial transaction network.
Communication with the financial transaction network is established from the remote user workstation 100 to a Client Service and Administration (CSA) system 110. This system, which is the hub of the financial network, invokes security routines to insure authorized access to the system and acts to validate, accept or reject, and route all transactions to their appropriate destinations. Additionally, account information, confirmations and status messages are sent to shareholder mailboxes which are maintained by the CSA system 110. It performs administrative tasks, such as assigning transaction numbers to instructions, holding transactions in a pending queue awaiting acknowledgement of further information to complete the transaction and performing additional functions within the financial network. The CSA system may use fault tolerant computer technology. It will be appreciated that a variety of computer technologies are feasible. The invention will be defined in detail by referring to specific transactions.
A communication link is established between the Client Service and Administrative system 110 and a Transfer Agent system 114. The Transfer Agent system executes all transactions and acts within the financial network for purposes of updating shareholder records, applying dividends to fund shares and transmitting netted purchase and redemption information to the Fund Accountant. Additionally, the Transfer Agent provides account balance information and transmits transaction statements and a hard copy of transaction confirmations to the shareholder, as required by law. Thus, the Transfer Agent system 114 performs shareholder recordkeeping and acts in an informational capacity by maintaining and dynamically transmitting updated shareholder record information such as account balance to update the CSA database 112. The database 112 is subject to inquiry by client service and administrative system 110. As illustrated in FIG. 1A thus functionality is limited to inquiry, that is, the data base 112 cannot be altered in any way by the Client Service and Administration system. Shareholder accounts maintained in the data base 112 are updated only by the Transfer Agent system 114.
This invention further employs Custodians 116 located at different international locations. It will be understood that an alternative is a central global custodian and plural sub-custodians. The Custodian(s) maintains custody of the mutual fund's assets including those located outside the United States. The Custodian(s) 116 receives shareholder assets for the purchase of shares, and disburses assets to the shareholder for redemptions. The Custodian(s) also accepts instructions from the CSA to await receipt of good funds from purchasing shareholders. There are (n) custodians, one located in each country as caveated above. While three funds are illustrated, the invention is not so limited. Any number (n) may be used including funds investing in synthetic currencies such as ECU's. The mutual fund may also establish its own synthetic currency or currencies based upon composition of the mutual fund portfolios under management.
The Fund Accountant 120 is responsible for maintaining the mutual fund portfolio records together with its accounting records, such as general ledger and the like. Its responsibilities include valuation of each of the portfolios, calculating the net asset value and income distribution for daily dividends. The Fund Accountant 120 communicates with the Investment Advisors 118 for purposes of providing net investment information. As illustrated in FIG. 1A, the Fund Accountant receives transaction data from the Transfer Agent 114.
The financial network, in accordance with this invention, employs Investment Advisors located internationally. In the example of three currency portfolios maintained in U.S. Dollars, Pounds Sterling, and Yen, three individual Investment Advisors will be employed by the financial network. Each Investment Advisor will have a corresponding banking relationship with the Custodians, that is the banks associated with each currency portfolio that is maintained. The functions of these components in the system will be explained in greater detail by considering basic transactions demonstrating operation of the financial network.
The basic types of transactions that are allowed in the financial network and each of their flows throughout the system will be discussed in more detail. Generally, they are as follows. Purchase transactions involve the purchase of shares with cash or in kind with eligible securities approved and valued by the Investment Advisor.
Redemptions redeem shares for cash or in kind with eligible securities approved and valued by the Investment Advisor. Transfers involve moving shares in one portfolio from one shareholder to another.
Matched transfers are effected when two shareholders come to an agreement outside of the system to exchange shares in two different portfolios. They both submit a matched transfer instruction to effect simultaneous transfers of the agreed upon number of shares between accounts in two different portfolios. For example, shareholder A moves U.S. Dollar shares to shareholder B's U.S. Dollar account while shareholder B moves Yen shares to shareholder A's Yen account.
Expedited transactions will extend the cutoff times for submitting instructions for normal payout for a specified fee. And, finally, contingent transactions link two transactions so that after the first part of the transaction is completed, the second part will be processed immediately. Transactions are processed in the system in the following frequency:
Transfers (on a continuous basis as received)
Purchases (every portfolio pricing)
Redemptions (every portfolio pricing)
To the extent that pricing is considered to be continuous, purchases and redemptions would be processed continuously.
Within each category, transactions are processed on a first-in basis and time-stamped at each stage of processing.
Certain elements of each flow are common to all types of transactions. The shareholder will access the financial network through a workstation 100, located at the customer site, and enter appropriate passwords that denote an authorized subscriber. Instructions will be entered and edited via the menu driven software provided for the workstation. A communications link is established with the Client Services and Administration system in order to transmit those instructions.
At the workstation 100, the shareholder utilizes the workstation menu, illustrated in FIG. 6A, to select a particular transaction type. A data entry screen will prompt the shareholder for required data and the shareholder will enter the appropriate information. For the purposes of his own tracking, the shareholder will also assign a unique client reference number which remains with the transaction throughout the flow. The shareholder at workstation 100 reviews his information, then utilizes a communications link with the Client Service and Administration (CSA) system 110 and transmits the instruction. For all transactions, the CSA will review the instruction received from the shareholder 100 and check for syntax error and content validity. For some transactions, the CSA system 110 will also check for a sufficient share balance by inquiry to the database 112 or to determine whether the transaction is timely, as in the case of expedited transactions. If for any reason the instruction is not valid, it will be rejected and the CSA 110 will issue an appropriate error message to the shareholder workstation. An audit trail of all rejected messages will be sent to the electronic mailbox for each shareholder who was party to the transaction.
Once an instruction has been received and validated, the CSA 110 will assign a transaction number to that instruction. This transaction number generated by the system is separate from the client reference number. The instruction will then be time-stamped and tagged that it has been accepted. Validation of an accepted instruction will be sent to the shareholder workstation 100, thus indicating to the subscriber that the transaction has been accepted for entry into the system. Once approved by the CSA, the transaction will be time-stamped and tagged, then either transmitted to the Transfer Agent system 114 as in the case of transfers, or put in a pending queue, as in the case of purchases and redemptions.
At the same time, a communication link is utilized between the CSA 110 and the appropriate Custodian 116 for purposes of providing instructions to the Custodian to receive funds or securities, in the case of purchase transactions.
Transactions that are put into a pending queue, i.e. those that are dependent on receipt of information from other shareholders or receipt of good money, for example, are checked periodically to see if they meet the criteria for transmission to the Transfer Agent system. With regard to certain transactions, as will be described, the shareholder is notified at the end of a specified period that required events have not occurred, and after a further specified period the transaction will be deleted if said events still have not occurred and an ensuing message will be sent to the shareholder mailbox to indicate same.
When these transactions are approved, they are time-stamped and tagged by the CSA system 110 which releases approved transactions for purchase and redemption to the Transfer Agent 114 on a periodic basis during the business day, generally to coincide with the next determined Net Asset Value calculation of the portfolio.
When the Transfer Agent 114 receives approved transactions from the CSA system 110, it provides the functions of updating shareholder records to complete the transaction request and then time-stamps and tags those transactions as completed. Next, the Transfer Agent 114 system dynamically provides updated transactional information to the data base 112 and provides investment information at a portfolio level to the Fund Accountant 120. Finally, the Transfer Agent 114 provides a communication function back to the CSA system 110 to acknowledge completed transactions, then sends identical confirmation to generate the UCC required hard copy for the shareholder. Thus, the above characteristics are generic to transaction flows.
Referring now to FIG. 2 and the menu illustrated in FIG. 6B, the transactional flow for a purchase of shares is depicted. Shares of the mutual fund, which operates with parallel currency portfolios, may be purchased from the mutual fund by payment of the purchase price in the selected portfolio's designated currency. Thus, U.S. Dollar shares are paid for in U.S. Dollars, pound shares in British Pounds and the like. All purchases of a portfolio's shares for a national currency must be paid by a recognized electronic inter-bank payment system, or book entry on the books of the Custodian, or other designated depository institution in the Portfolio's designated currency directed to the mutual fund's account. Payments will not be deemed to be received by the mutual fund until the Custodian is deemed to have disbursable funds.
In FIG. 2, at processing block 1 the user accessing the workstation 100 will enter purchase information as prompted by the selected data input screen (see FIG. 6B). Thus, utilizing the menu driven system, the user will, once passing security, enter information to effect a purchase instruction. When selected, the screen will automatically reflect the name and account number of the shareholder who has signed on. The shareholder then selects the desired currency portfolio, any one of the portfolios currently managed by the mutual fund. By way of example, this could be U.S. Dollars. British Pounds or Japanese Yen. The number of shares to be purchased is entered using the screen of FIG. 6B. The shareholder then will enter the name of the bank from which the designated currency for payment will be transmitted, and other relevant identifying information and assigns his own unique client reference number. Once reviewed, the shareholder establishes a communications link with the CSA system 110 after passing through the CSA system security checks, transmits the purchase instruction to the mutual fund.
Decision block 2 validates the incoming purchase request against a customer file to insure authorized customer name and account number and for syntax and content validity. If the instruction does not pass the checks, it is rejected and an appropriate error message is sent to the shareholder at workstation 100 along with an audit trail to the shareholder mailbox residing on the CSA 110. If the instruction passes the checks, then it is timestamped at functional block 3 and assigned a transaction number. The transaction number is electronically sent to the shareholder as confirmation that the instruction has been accepted and for tracking purposes.
The accepted purchase instruction is moved to the pending queue shown in functional block 4. The instruction is held here pending acknowledgement of receipt of good funds by the Custodian. It is a unique feature of this financial network that no mutual fund shares will be issued to a subscriber until both a valid instruction and the corresponding disbursable funds arrive. The pending queue is checked on a first-in basis by the CSA who notifies the Custodian shown at functional block 5 to await good funds. Decision block 6 is a check to see if sufficient funds have been received periodically, the on-line connection to the Custodian is checked to verify that funds have been received. If the test proves "No". (block 7) and if funds are not received by a specified period of time, a message is automatically sent to the customer mailbox indicating non-receipt of funds. If money is not received within a further specified period of time from receipt of the instruction, it is automatically deleted and a message is sent to the customer mailbox indicating the action.
If sufficient funds have been received, the flow passes to functional block 8. The Purchase transaction is tagged by the system as approved and time-stamped. Approved transactions are released to the Transfer Agent system 114 work queue at the next scheduled pricing period. At functional block 9, the Transfer Agent system accesses the next approved transaction on a first-in basis, issues the appropriate number of shares based on the current pricing and posts information to the shareholder's account.
At functional blocks 10, and 12, the confirmation trail of the purchase is completed. Once the shareholder records have been updated. (functional block 10) the Transfer Agent system tags the Purchase transaction as completed and time-stamps the transaction. Executed transaction updates are then transmitted to the CSA system. That is, the Transfer Agent system will update the CSA system data base 112 with the most recent transactional information. In turn, the CSA system will transmit electronic confirmation to the shareholder's mailbox which can be accessed from workstation 100. The Transfer Agent 114 will send an identical confirmation to generate the UCC required hard copy, thereby providing the shareholder a paper trail of the purchase.
At functional block 13, the Transfer Agent system compiles the total amount of purchases by portfolio, nets that amount with redemptions and sends netted purchase and redemption information to Fund Accountant 120.
Referring now to FIG. 3, a two-step transaction involving purchase of shares and their immediate transfer, herein called a Purchase and Transfer, is depicted.
At functional block 14, the shareholder utilizing the workstation 100 will enter the same data as required for a purchase instruction and additionally specify the number of shares and the account to which the shares will be transferred once purchased. This transaction, a purchase and transfer of shares, will be used typically for purposes of settling commercial or financial obligations. It allows the shareholder at a remote workstation 100 to execute in a single instruction a two-step process of purchasing shares and transferring them immediately upon issue to the designated account. This technique thus frees the shareholder from having to periodically check his mailbox for confirmation of a purchase before he can initiate a transfer of shares to another party.
As in the case of a purchase transaction, the CSA performs the same steps at blocks 16, 17 and 18 as in the case of the purchase (blocks 3, 4 and 5). The Custodian at block 19, looks to see if sufficient funds have been received. Periodically, the on-line connection to the Custodian is checked to verify that funds have been received. If the test proves "No" (block 20), and if funds are not received by a specified period, a message is automatically sent to the customer mailbox indicating non-receipt of funds. If money is not received within a further specified period from receipt of the instruction, it is automatically deleted and a message is sent to the customer mailbox indicating the action.
If sufficient funds are received by the Custodian, the approved transactions are released to the Transfer Agent, (block 21). Then, the Transfer Agent will issue the shares to the shareholder account at block 22. Block 23 in FIG. 3 is the transfer function. In the case of this instruction, the Transfer Agent, having issued the appropriate number of shares, will then transfer the requested shares to the account of the designated recipient. Information will be posted to the account of the shareholder who initiated the purchase and transfer transaction as well as updating the account of the designated recipient of the transfer. Thus, at block 24, executed transaction updates are transmitted to the CSA system. This updated information sent to the CSA reflects both the purchase and the transfer of shares. At block 25, confirmation is sent to both shareholders the purchase and transfer shareholder and the recipient of transferred shares. Block 26 completes the paper audit trail as in FIG. 2 block 12, thus the Transfer Agent system sends an identical confirmations to generate the UCC required hard copy, thereby providing the shareholders a paper trail of the transaction. Functional block 27 shows that the Transfer Agent system compiles the total amount of purchases by portfolio, nets that amount with redemptions and sends net investment information to Fund Accountant.
Another important aspect of this financial transaction network is the use of the matched transfer transaction. FIG. 4 depicts the flow of this transaction and the data entry screen is illustrated in FIG. 6C.
Matched transfers are effected when two shareholders come to an agreement outside of the financial network to exchange shares in two different portfolios. They both submit a matched transfer instruction to effect simultaneous transfers of the agreed upon number of shares between accounts in two different portfolios. For example, shareholder A moves U.S. Dollar shares to shareholder B's U.S. Dollar account while shareholder B simultaneously moves Yen shares to shareholder A's Yen account.
Shareholders wishing to effect a matched transfer can post information with respect to desired exchanges utilizing the electronic bulletin board 124 which is maintained 24 hours a day. A shareholder at workstation 100 can scan the bulletin board 124 to determine whether there are potential buyers or sellers in the portfolios of interest. Upon finding a potential counterparty (another shareholder to exchange with), the shareholders negotiate the terms of the transaction outside of the financial network by phone, facsimile transmission or other external means.
Once the terms of the matched transfer are agreed upon, both parties must select a matched transfer instruction from the main menu at workstation 100, enter required account information, the party with whom they will do a transfer (the counterparty), the desired portfolios, and the agreed upon number of shares to be transferred in each portfolio.
The two parties will agree on a unique client reference number which will be entered on both screens. Once checked by the shareholders these two instructions will be sent to the CSA system 110.
The instruction from the transferring party is checked at blocks 29 and 30. First the instruction is checked against a customer file to insure authorized customer name and account number and for syntax and content validity. If the instruction does not pass the checks, it is rejected and an appropriate error message is sent to the customer.
As in the case of other transaction types, if the instruction is valid it is assigned a transaction number by the CSA at block 31. The accepted Matched Transfer instruction is moved to the pending queue shown in functional block 32. The instruction is held here pending arrival of a matching transaction. Thus, the authority to initiate the transfer is held by the CSA processor which checks the queue periodically to determine whether a matching instruction is received.
At block 33, the pending queue is searched for a matching transaction identified by the same unique client reference number. If a matching transaction is not found within a specified period of time, the Matched Transfer request is rejected and a message is automatically sent to the shareholder mailbox.
Once a matching transaction has been found, both requests are put through another check against the data base (block 36) to see that each shareholder has sufficient share balance needed for transfer. If one or both parties do not have sufficient shares available, both sides of the Matched Transfer (functional block 37) are rejected and a message is automatically sent to each shareholder's mailbox.
If sufficient available shares have been verified at block 38, the CSA system tags each transaction as approved, time-stamps each transaction and releases approved transactions to the Transfer Agent system 114. The Transfer Agent, as shown in functional block 39, transfers the requested number of shares in the desired portfolios between the designated parties and posts information to the shareholders accounts. Once the shareholder records have been updated, (functional block 40) the Transfer Agent system tags the Matched Transfer transaction as completed and time-stamps the transaction. Executed transaction updates are then transmitted to the CSA system. Functional block 41 shows that the CSA system sends an electronic confirmation to each shareholder mailbox. As required, the Transfer Agent 114 will send and identical confirmation in the form of hard copy to each shareholder.
As can be appreciated, by utilizing this transaction type shareholders can arrange for currency exchanges by swapping, at agreed upon rates, shares within their respective currency portfolios. Such a currency exchange by swapping shares is effectuated without the use of intermediary banks. The result is a more expeditious access to funds without the imposition of interbank transfer fees, the inherent delays and risks in the interbank settlement system and the like. This financial transaction network thus provides for electronic transfers of currency shares utilizing the flexibility of multiple mutual fund portfolios in discrete currencies.
FIG. 5 illustrates another two-step transaction utilizing the financial network of this invention, an instruction to receive and redeem shares. It is used when a shareholder wishes to redeem shares of a portfolio, but is waiting to receive a transfer from another shareholder. Thus, the shareholder expects to receive shares from another source and then redeem a specified number of those received shares.
At functional block 43, the shareholder at workstation 100 will enter the system passing security checks and the like. Utilizing a screen such as the one illustrated in FIG. 6D, the shareholder selects the desired currency portfolio and indicates the number of shares to be redeemed. The shareholder also indicates the bank, and other identifying information, into which the designated currency will be transmitted once redeemed. A unique client reference number is then given to this instruction. Once reviewed and approved the shareholder transmits the instruction to the financial network.
As in the case of other transactions, the instruction is checked to determine whether it is valid. If rejected due to incorrect syntax or content validity, an error messages is sent to the shareholder. If accepted, the CSA 110 assigns a transaction number and transmits such to the shareholder indicating that the instruction is valid. The instruction is then held in the pending queue at block 46 pending receipt of shares. The queue is accessed periodically at decision block 47: that is, the data base 112 is accessed to see whether it has been updated to indicate that the expected number of shares has been received and credited to the shareholder's account. Thus, a check of the database 112 is made to determine if the required number of shares have been received and are available for redemption. At the end of a predetermined time, if insufficient shares are in the shareholder's account, the transaction is cancelled. That is, the queue is refreshed by purging expired instructions, and the shareholder is notified with an ensuing message to the shareholder mailbox.
If sufficient shares are received within the specified period, the CSA 110 will tag the receive and redeem transaction as approved, time stamp the transaction and release approved transactions to the Transfer Agent system 114 at the next pricing period. The Transfer Agent system at block 51 will redeem the shares now in the shareholder's account and post that information to the shareholder account by updating the database 112. The CSA system also receives an indication that the transaction has been executed, and the shareholder receives both electronic confirmation sent to his mailbox and identical hardcopy generated by the Transfer Agent system. The Transfer Agent system completes the chain by netting purchases with redemptions and sending net investment information to the Fund Accountant.
As is therefore apparent, by utilizing the receive and redeem instruction, a shareholder can use the financial network for purposes of effectuating near real-time use of redeemed shares. That is, without the requirement of intermediary banks and intra-bank transfers, mutual fund shares can be received from third party sources and promptly redeemed into the currency used by that portfolio. The time based availability of funds is therefore expedited and traditional passing fees minimized.
The preceding description of four typical transactions is illustrative of basic operations of this system. It is apparent that other types of transactions are within the scope of this invention. For example, in addition to a regular purchase of shares, a purchase-in-kind can also be effected. This would be a purchase of shares in a particular portfolio for which the consideration would not be cash but rather securities which are deemed to be permissible investments by the investment advisor for that portfolio. Analagously, redemptions-in-kind are also a recognized transaction type. Also, while a description of a matched transfer is discussed as an example, it is apparent that a regular exchange, that is a currency conversion from an investment of shares of one portfolio into shares of another portfolio is within the scope of this invention. FIG. 1B illustrates such an "exchange" whereby shares are redeemed from one portfolio, the redemption proceeds converted through foreign currency exchange procedures into the designated currency of another portfolio, then shares are purchased with the proceeds of the currency conversion.
Yet another example of the flexibility of this system is the use of the invention for purposes of two-step transactions. In addition to the purchase and transfer transaction and the receive and redeem transaction, a receive and transfer transaction can also be effectuated. This occurs when a shareholder wishes to transfer shares of a portfolio, but is waiting to receive a shares from another shareholder. The transaction is a two step process whereby the system awaits receipt of the transferred shares, then permits the receiving shareholders to transfer those shares as specified.
The system also allows for expedited transactions as in the cases of an expedited redemption and expedited exchange. Expedited redemptions may be accepted only during specified hours depending on the requirements of a particular portfolio and will result in the redemption of shares in a shorter timeframe than in the normal course of a redemption as specified in the prospectus. These transactions are subject to a fee for expedited transactions.
Another important aspect of this invention is the improved access to data for purposes of inquiry and reporting. The shareholders utilizing the workstations 100 can make inquiries into the status of their account by a network inquiry. FIG. 6E illustrates a typical menu for database inquiry at the shareholder level. Also, real-time queuing of instructions is maintained through the system such that a shareholder can at any time know the status of transactions in terms of their status in the system.
Flexibility is also obtained by allowing a shareholder to distribute dividends directly to beneficial owners for whom the shareholder is acting. That is, for example, when a clearing house holds shares which have been put up as collateral by a clearing member, the clearing house can distribute dividends on that collateral back to the clearing member.
Additionally, by reviewing a bulletin board maintained by the mutual fund, shareholders obtain information relative to the requests of other shareholders with respect to secondary market transactions. It will be appreciated that this is operated 24 hours a day, it can be utilized internationally with great flexibility by all shareholders to the system.
At the host system, the Client Service and Administrative functions allow access for purposes of reading and updating transaction queues. Inquiries regarding transaction records are fulfilled on a real-time basis. The Transfer Agent is responsible for its own shareholder record keeping and dynamically updating the CSA data base. Importantly, however, the Fund Accountant does not have access to shareholder records. That is, the Fund Accountant 120 is locked out of the data base 112. This security protection insures independence of the Fund Accountant by having its activities pass directly to the Transfer Agent for purposes of accounting details and verification.
With this invention the improved reporting is also effectuated. At the shareholder level both electronic confirms to shareholder mailboxes and confirmations required by the Uniform Commercial Code are provided. The shareholder also receives periodic statements listing transactional and account information. Management reports regarding financial network performance provide fund data on a portfolio-by-portfolio basis along with data concerning shareholder activity. Tax and regulatory reporting is provided as well. It can thus be appreciated that given this system architecture, important advantages accrue to shareholders. Other uses will be apparent to those skilled in the art.
The transactions thus described are illustrative of this invention. Transactions such as purchases or redemptions are conducted using a fund comprised of a single currency. The invention thus permits the use of mutual fund shares in a single currency to effectuate the settlement of commercial transactions in that currency.
In practicing this invention, the assets of a portfolio are unrelated to the functioning of the financial network. Country of registration of the funds is not germane to the operation of the fund. While described in the context of multiple portfolios, the invention is applicable to multiple funds.
Modifications of this invention may be practiced without departing from the scope thereof.
Use of the fund's portfolios as currency equivalents is not diminished by any discounts applied by regulatory or by designated self-regulatory entities.
For example, this invention can also be used to facilitate the exchange of those currencies (national or otherwise), which are currently inhibited from being exchanged by practice, economics or statute, by providing securitization of the currency as a mutual fund share. Securitization is obtained by equating a unit share of a portfolio to the unit, or fraction or multiple, of the associated currency to be securitized. This will allow currencies to be exchanged via their securitized representation without violating existing statutes concerned with the actual transfer of currency itself (such as the Johnson Debt Default Act in the case of rubles), and will potentially circumvent issues of practice or economics associated with the currency by allowing the market to set the exchange rate on the securitized version of the currency via the bulletin board of this invention.
This invention can be used as a supplement or replacement for many of the current bank practices concerned with the exchange of currencies through the mechanism of foreign exchange. It can also be used to effect the transfer of different currencies between shareholders of this financial transaction network via the matched transfer transaction, thereby eliminating the possibility of outright loss in foreign exchange settlement (known as the "Herstadt effect"). This invention can also be used as a multi-currency guarantee fund for those foreign exchange netting systems engaging in bilateral or multilateral netting by novation which maintain a guarantee fund to assist in insuring settlement in case of member default.
This invention can further be used as a collateral type for pledging to or depositing in guarantee funds in general. This would include, but not be limited to, private and central bank collateral pools used as a basis for determining the creditworthiness of a participant, or size or number of payments a participant is allowed to effect.
It will be appreciated that this invention can also be used by shareholders as a settlement tool in a mode known as "delivery versus payment" to insure the safe and orderly settlement of any asset permitted in any portfolio. Such settlement would be effectuated through transactions known as receipt-in-kind and delivery-in-kind.
These additional uses are indicative of the scope of this invention and are not limiting examples. | A financial transaction network employs a shareholder network serviced by a host processor. The financial network maintains (n) number of mutual fund portfolios operating in different currencies. The host processor acts a communications switch validating incoming transaction requests and routing them to a central Transfer Agent system for execution. The host processor maintains central records that can be queried through the host. The Transfer Agent is responsible for updating the database. The financial network provides accessibility, speed and finality of settlement in transactions by using mutual fund shares in diverse currencies as substitutes for those currencies. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation application of prior application number PCT/DE2005/000646, filed Apr. 6, 2005 and claims the benefit under 35 U.S.C. §119 of prior foreign application number DE 20 2004 005 994.0, filed Apr. 8, 2004, which are hereby incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
[0002] The invention relates to a device for connection of an airbag module to a supporting vehicle component.
BACKGROUND OF THE INVENTION
[0003] A device of this type comprises an expanding element which is arranged on one of the two subassemblies to be connected; a latching opening which is provided on the other of the two subassemblies to be connected and into which the expanding element can be introduced in such a manner that, after being introduced into the latching opening, it can take up a latching position, in which in the expanded state it engages behind the edge of the latching opening; and a securing element which can be brought into engagement with the expanding element in such a manner that it secures the expanding element in the expanded state, in which the latter engages behind the edge of the latching opening. A latching connection of this type between an airbag module and an associated supporting vehicle component, for example a steering wheel, has the advantage that it can be produced very simply by the two subassemblies which are to be connected to each other being plugged together, with at least one expanding element on the one subassembly being introduced into at least one latching opening of the other subassembly and, in the process, being radially compressed, so that it can be guided through the latching opening, and subsequently widens again radially, so that there is a form-fitting connection (latching connection) between the two subassemblies to be connected to each other. However, latching connections of this type on the basis of an expanding element have the disadvantage that, when very high forces occur at the connecting points, there is a certain risk that the connection will be released (by deformation of the expanding element). Such forces may occur at the connecting points between an airbag module and a supporting component of a vehicle body, for example a steering wheel, in particular if, as a consequence of a sharp deceleration of the vehicle, i.e. a what is referred to as a crash event, the airbag module is triggered and the airbag of the airbag module is inflated within milliseconds in order to protect a vehicle occupant, in which case a corresponding recoil occurs.
[0004] In order to prevent an unintentional release of the connection between the airbag module and an associated supporting vehicle component, it is known to bring a securing element into engagement with the expanding element, said securing element holding the expanding element in the expanded state by engaging behind the edge of the associated latching opening. However, this securing of the connection between a particular expanding element and an associated latching opening has the disadvantage that an associated securing element, for example in the form of a securing pin, has to be brought into engagement with the particular expanding element, which is a drawback to installation if access to the individual connecting points is difficult. Furthermore, this may also make disassembly of the connection considerably more difficult. This is because, on account of the securing element, it is not possible simply to release this connection by the expanding element being compressed at its expanding section and being moved through the latching opening, since the securing element holds and locks the expanding element in the expanded position. It is therefore necessary, when the connection is disassembled, for example for repair or service purposes, first of all to remove from each expanding element the securing element located there. If access to the airbag module in a motor vehicle is difficult, this makes the disassembly significantly more difficult.
SUMMARY OF THE INVENTION
[0005] The invention is based on the problem of further improving a device for the connection of an airbag module to a supporting vehicle component of a motor vehicle of the type mentioned at the beginning.
[0006] This problem is solved according to the invention by the provision of a device as described hereinafter.
[0007] According thereto, the securing element is originally connected releasably to a component which is different from the subassembly provided with the expanding element and, in the process, is arranged behind the latching opening in such a manner that it can be brought into engagement with the expanding element when the latter is guided beyond its latching position through the latching opening.
[0008] The invention is based firstly on the finding that the bringing of the expanding element into engagement with a respectively associated securing element can be simplified and automated if the respective securing element is already held behind the latching opening during installation, i.e. when the expanding elements are introduced into the respectively associated latching openings. By the respective expanding element being guided beyond its latching position through the associated latching opening, it can be brought into engagement with the associated securing element at a suitable time. When the expanding elements are moved back (in particular pulled back) into the respective latching position, the securing elements can then be detached from the respective component to which they are releasably fastened. Each securing element is then in permanent engagement with an associated expanding element and holds the latter in the expanded state.
[0009] Furthermore, the number of cases in which the airbag module and an associated supporting motor vehicle component has to be removed from each expanding element by taking out the respective securing element can be reduced if the expanding element can be introduced into the associated latching opening and can be fixed thereon in the latching position while the associated securing element is initially still being held ready for securing this connection. The engagement between a respective expanding element and the associated securing element is only produced here when the expanding element is moved beyond its latching position (for example in the event of a crash), so that it enters into engagement with the securing element and is thereby permanently expanded.
[0010] According to a variant of the invention, it is provided that, when the airbag module is installed on an associated supporting vehicle component, each expanding element is only guided through the associated latching opening until it is in its latching position, in which it engages in the expanded state behind the edge of the latching opening. This connection is not then secured by a securing element. In the case of this embodiment of the invention, a connection secured by the securing element only takes place between a respective expanding element and a latching opening in the event of a crash, in which the respective expanding element is moved beyond its latching position under the action of the recoil occurring on the airbag module when the airbag is inflated, and, in the process, grasps a securing element and carries along the latter during the return into its latching position after it has been released from the component to which it was initially releasably connected. In the case of this embodiment of the invention, the connection, produced by expanding elements and associated latching openings, between an airbag module and a supporting vehicle component is therefore only secured by additional securing elements if this connection is actually exposed to particular loads in the event of a crash.
[0011] According to another variant of the invention, the securing of the connection between airbag module and supporting vehicle component can also take place at a suitable time of the installation by the respective expanding element being moved beyond its latching position to an extent such that it grasps the associated securing element, which is connected releasably to a component, and is thereby held in the expanded state.
[0012] In both embodiments, it is preferably provided that the expanding element, when introduced into the latching opening, can be brought into a first position, which is referred to as the latching position and in which it engages in a form-fitting manner behind the edge of latching opening and bears against said edge, and that the expanding element can be brought beyond the latching position into a second position, which is referred to as the engagement position and in which it enters into engagement with the securing element in order to grasp the securing element, to be detached from the associated component and thus to fix the expanded state of the expanding element.
[0013] According to a preferred embodiment, the expanding element has a stem and an elastically compressible expanding section, the stem of the expanding element reaching through the latching opening, after the expanding element is introduced into the latching opening until it reaches a latching position, and the expanding section engaging behind the edge of the latching opening.
[0014] In this case, the stem of the expanding element is preferably of such a length that the expanding element can be brought (beyond its latching position) with respect to the latching opening into an engagement position, in which the stem of the expanding element reaches through the latching opening and the expanding section of the expanding element is spaced apart from the edge of the latching opening (in the axial direction, i.e. along the direction of extent of the latching opening), with it being possible, in the engagement position of the expanding element, for its expanding section to grasp the securing element which is still connected releasably to an associated component. Put another way, the extent of the stem in the direction of extent of the latching opening is greater than the extent of the latching opening itself in this direction. This gives rise to the possibility that the expanding element can be brought into different longitudinal positions with respect to the latching opening by the stem being displaced in the latching opening, with the expanding element bearing against the edge of the latching opening in one longitudinal position, referred to as the latching position, and engaging behind said latching opening in a form-fitting manner and, in another longitudinal position, referred to as the engagement position, the expanding element grasping the securing element, which is arranged behind the latching opening and is connected releasably to a component.
[0015] The two subassemblies to be connected to each other are elastically braced against each other, for example by means of at least one elastic element in the form of a spring (helical spring), in such a manner that the expanding element has the tendency, after being introduced into the latching opening, of taking up its latching position. The spring element, which is preferably designed as a helical spring, can engage here around the stem of the expanding element.
[0016] The transfer of the expanding element into its engagement position, in which it can grasp the securing element, which is arranged releasably behind the latching opening, follows in this case counter to the action of the elastic prestress between the two subassemblies, with the restoring action of this elastic prestress also leading to the respective expanding element being guided back into its latching position after grasping a securing element (with the securing element being taken along).
[0017] The two subassemblies to be connected to each other may be, for example, firstly a component of the module housing of an airbag module, for example a receptacle for an airbag to be inflated and for a gas generator, and, secondly, a component of a steering wheel, such as, for example, a what is referred to as a contact bridge which serves to trigger a signal horn which can be actuated on the steering wheel. The signal horn can be actuated, for example, by the airbag module being displaced, by force being applied to its covering cap, relative to the contact bridge counter to the action of an elastic element and acting on said contact bridge, with mutually assigned electric contact elements entering into contact and triggering the signal horn. The force typically associated with the actuation of the signal horn (by action upon the cap of the airbag module by means of the particular driver's hand) here is not to be of such a magnitude that a movement of the airbag module relative to the contact bridge is brought about in an extent in which the expanding elements provided on the airbag module could enter into engagement with the associated securing element located behind the respective latching opening—at least if such an engagement is only to be produced, according to the invention in the event of a crash by the corresponding larger recoil force which then acts on the airbag module.
[0018] The securing element is preferably formed in a simple manner on the component, to which it is releasably connected, by injection molding. That component is preferably a component of the subassembly which is provided with the at least one latching opening.
[0019] In order to permit a defined detachment of the securing element from the associated component when the securing element is grasped by an expanding element and the expanding element is moved back into its latching position under the action of a restoring spring, the releasable connection between the securing element and the associated component comprises at least one predetermined breaking point.
[0020] In order to be able to hold the securing element permanently in the expanding element and thus to ensure the permanent expansion of the expanding element, the expanding element has (on its expanding section) a form-fitting region, in particular in the form of an undercut contour, with which it can grasp the securing element in a form-fitting manner. Furthermore, a guide section, for example in the form of one or more guide surfaces with a conical profile, can be provided on the expanding element and/or the securing element in order to facilitate the bringing of the expanding element into engagement with the securing element. A corresponding guide section can also facilitate the introduction of the respective expanding element into an associated latching opening.
[0021] The expanding element can be formed, for example, by means of at least two hooks (separated from each other by a slot), so that it can be compressed when introduced into the latching opening and can be elastically widened again after the latching position is reached.
[0022] The connection between the airbag module and the supporting vehicle component preferably has (at least two) connecting points at which a respective expanding element is in engagement in a form-fitting manner with an associated latching opening.
[0023] A connection between two motor vehicle subassemblies, namely an airbag module and a supporting vehicle component, using a connecting device according to the invention, is characterized by the features of claim 31 .
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Further details and advantages of the invention will become clear in the description below of an exemplary embodiment with reference to the FIGS.:
[0025] FIG. 1 shows a perspective illustration of an airbag module and a contact bridge of a steering wheel, to which the airbag module is to be connected;
[0026] FIG. 2 shows a cross section through an arrangement according to FIG. 1 after production of the connection;
[0027] FIG. 3 shows a diagrammatically perspective illustration of a possible embodiment of connecting means for connecting the airbag module to the contact bridge;
[0028] FIGS. 4 a - 4 c show different states of a connecting point according to FIG. 3 ;
[0029] FIG. 5 shows a graphical illustration of the forces acting on the connecting point in the event of a crash;
[0030] FIGS. 6 a and 6 b show a further embodiment of a connecting point for an arrangement according to FIGS. 1 and 2 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0031] FIGS. 1 and 2 diagrammatically illustrate a contact bridge 1 which can be fastened to a steering wheel skeleton L and an airbag module which is to be connected ( FIG. 1 ) or is connected ( FIG. 2 ) to the contact bridge 1 .
[0032] The contact bridge 1 comprises a basic body 10 with hooks 11 for fastening to the steering wheel skeleton L and with latching openings 3 in the form of passage openings on two hollow cylindrical latching bodies 30 provided on the basic body 10 of the contact bridge 1 .
[0033] The airbag module 2 comprises a module housing, comprising a receptacle 20 for the gas generator G with generator carrier T, for an associated diffuser D and for an airbag to be inflated with the gas generator G, and a cap 25 for closing the receptacle 20 . Two expanding elements 4 protrude from the module housing 20 , 25 on the lower side of the receptacle 20 and are assigned in each case to one of the latching openings 3 on the contact bridge 1 . The two expanding elements 4 each have a longitudinally extended stem 40 and an expanding section which is formed by two hooks 41 a, 41 b, which are separated from each other by means of a slot 42 , and is prestressed elastically in the direction of the expanded state.
[0034] In order to install the airbag module 2 on the contact bridge 1 , the two expanding elements 4 are introduced into the associated latching openings 3 , with the introduction being facilitated by mutually assigned introducing slopes 310 , 410 on the edge 31 of the latching opening 3 and on the expanding section 41 a, 41 b. When the expanding elements 4 are introduced into the associated latching openings 3 by movement of the airbag module 2 with respect to the contact bridge 1 along an introductory direction E ( FIG. 1 ), the expanding sections 41 a, 41 b of the latching elements 4 are compressed radially inward, with use being made of the elastic deformability of the latching hooks which form the expanding section 41 a, 41 b and are separated from each other by a gap 42 .
[0035] The expanding elements 4 have reached their latching position with respect to the latching openings 3 when the expanding sections 41 a, 41 b are passed through the respective latching opening 3 and engage in a form-fitting manner behind the edge 31 of the respective latching opening 3 . This is achieved by the expanding sections 41 a, 41 b automatically expanding again radially after penetrating the respective latching opening 3 . In this latching position, the expanding elements 4 each reach through the latching opening 3 by means of their stem 40 .
[0036] In this case, the airbag module 2 and the contact bridge 3 are braced against each other via elastic means in the form of helical springs 6 , which engage around the stem 40 of the respective expanding element 4 , in such a manner that the respective expanding element 4 has the tendency to rest with its expanding section 41 a, 41 b on the edge 31 of the latching opening 3 .
[0037] Furthermore, a securing element 5 in the form of a securing pin which is connected releasably to the contact bridge 1 is arranged behind a respective latching opening 3 , within the hollow cylindrical latching body 30 forming the latching opening.
[0038] If a respective expanding element 4 is in its latching position in which it bears with its expanding section 41 a, 41 b against the edge 31 of the associated latching opening 3 , then the securing element 5 is spaced apart from the expanding section 41 a, 41 b of the expanding element 4 in the axial direction a, i.e. the direction of extent of the latching opening 3 (perpendicular with respect to the area of the latching opening 3 ). Accordingly, in the state shown in FIG. 2 , the airbag module 2 and the contact bridge 1 are connected to each other in a form-fitting manner via latching connections, formed by a respective expanding element 4 which engages in an associated latching opening 3 , without the expanding elements 4 being permanently held in the expanded state by a securing element.
[0039] In normal operation of a motor vehicle, in which no particularly large forces act on said connecting points, a connection of this type between airbag module 2 and contact bridge 1 of a steering wheel L is entirely sufficient. However, problems with regard to the strength and reliability of the connection described may occur if, in the event of a crash, the airbag module is triggered, i.e. the gas generator G is ignited to inflate an associated airbag. In this case, the recoil forces occurring during the inflation of the airbag cause the airbag module 2 to move with respect to the contact bridge 1 in the introductory direction E (axial direction of the latching openings 3 ), so that the expanding section 41 a, 41 b of the respective expanding element 4 grasps the associated securing element 5 , the latter penetrating a distance into the slot or gap 42 of the expanding element 3 .
[0040] Under the action of the elastic elements 6 , which serve as restoring springs and are in the form of helical springs, the airbag module 2 is then moved with respect to the contact bridge 1 counter to the introductory direction E in such a manner that the expanding elements 4 pass again into their latching position. In this case, they take along the respectively associated securing element 5 , since the latter can be released from the contact bridge 1 owing to its releasable connection therewith (via a predetermined breaking point). The respective securing element 5 then remains in the central gap 42 of the associated expanding element 4 and holds the latter in the expanded state during the crash by engaging with its expanding section 41 a, 41 b behind the edge 31 of the latching opening 3 . Therefore, in the event of great crash forces occurring, a sufficiently secure connection of airbag module 2 and steering wheel L is ensured at the connecting points 3 , 4 .
[0041] In the case of all of the motor vehicles in which a crash leading to the airbag module 2 being triggered does not occur during operation, during the entire operating period the airbag module 2 remains secured to the steering wheel L or to the contact bridge 1 of the steering wheel L by means of expanding elements 4 and associated latching openings 3 without the use of securing elements 5 . The corresponding connections can therefore be disassembled very easily by the latching elements 4 being compressed radially inward at their latching sections 41 a, 41 b and then being pulled out of the associated latching openings 34 .
[0042] Furthermore, FIGS. 1 and 2 show mutually assigned (electric) contact elements K 1 and K 2 of the contact bridge 1 , on the one hand, and of the airbag module 2 or module housing 20 , 25 on the other hand, which contact elements can be brought into contact with one another by force being applied to the covering cap 25 of the module housing 20 , 25 of the airbag module 2 (counter to the action of the helical spring 6 ), as a result of which a signal horn can be electrically triggered.
[0043] FIG. 3 shows, diagrammatically in a perspective illustration, a further exemplary embodiment of an expanding element 4 ′ and of an associated latching opening 3 ′ which can be used in the case of a connecting device of the type illustrated in FIGS. 1 and 2 .
[0044] The expanding element 4 ′ has a stem 40 and an expanding section 41 a, 41 b, formed by two hooks separated from each other by means of a gap 42 , with it being possible for the expanding section 41 , 41 b to be compressed inward with the gap width being reduced. At its lower end in the introductory direction, the expanding section 41 a, 41 b is provided with introductory slopes 410 in order to facilitate the introduction into a latching opening 3 ′, which is formed on a latching body 30 , with deformation (radial compression) of the expanding section 41 a, 41 b.
[0045] Arranged behind the edge 31 of the latching opening 3 ′ in the introductory direction E is a securing element 5 in the form of a securing pin which can be grasped by a form-fitting region 45 , which is formed by an undercut contour, of the expanding element 4 ′ when the latter is moved in the introductory direction E beyond the latching position, in which it bears with its expanding section 41 a, 41 b against the edge 31 of the latching opening 3 ′.
[0046] FIG. 4 a shows, in a cross section, the arrangement from FIG. 3 in the latching position of the expanding element 4 ′ in which the latter bears with its latching section 41 a, 41 b against the edge 31 of the latching opening 3 ′ of the latching body 30 .
[0047] FIG. 4 b shows the arrangement in a state in which (caused by a crash, as a consequence of the recoil occurring when the airbag module is triggered) the expanding element 4 has been moved in the introductory direction E (axial direction a) beyond the latching position until, by means of its form-fitting region 45 , it grasps the securing element 5 . To this end, it is necessary for the stem 40 of the expanding element 4 ′ to be of sufficiently greater length (extending in the introductory direction E or axial direction a) than the latching opening 3 ′, so that the expanding element 4 ′ can take up different longitudinal positions with respect to the latching opening 3 ′.
[0048] The expanding element 4 ′ subsequently moves back into its latching position, for example under the action of a restoring spring 6 , as illustrated in FIG. 2 , with, according to FIG. 4 c, the securing element 5 being taken along in the form-fitting region 45 of the expanding section 41 a, 4 1 b after it has been released from the corresponding subassembly of the steering wheel (contact bridge 1 , compare FIG. 2 ), to which it was releasably fastened. In the state shown in FIG. 4 c, the expanding element 4 ′ is then secured in its latching position by being held permanently in the expanded state by means of the securing element 5 held in the form-fitting region 45 . There is then no risk that it could be compressed under the action of particularly great forces and could slide through the latching opening 3 ′, with the consequence that the airbag module 2 would no longer be reliably fastened to the steering wheel L.
[0049] FIG. 5 shows a typical force profile F as a function of the time t (in milliseconds) at a connecting point of the type illustrated in FIGS. 1 to 4 c after a crash event has occurred.
[0050] At the time t=0, a crash, i.e. a particularly sharp deceleration of the corresponding motor vehicle, is detected and the airbag module is triggered, i.e. the gas generator for inflating the airbag provided in the airbag module is ignited. After less than 10 milliseconds a first force peak K 1 occurs which represents the force exerted on the contact bridge (compare FIG. 2 ) by the airbag module 2 via the spring 6 due to the recoil caused by the gas generator. This force causes the displacement of the airbag module 2 with respect to the contact bridge 1 with the helical spring 6 being deformed, with the consequence that the expanding elements 4 ′ (as illustrated in FIG. 4 b ) can in each case grasp an associated securing element 5 . A second force peak K 2 acting in the opposite direction shows the tensile force acting on the airbag module 2 in the opposite direction after somewhat more than 10 milliseconds, the tensile force causing the expanding elements 4 ′ to return into their respective latching positions.
[0051] FIG. 6 a shows a development of a connecting point which is formed by a latching opening 3 and an expanding element 4 ″, the expanding element 4 ″ being in its latching position in the state according to FIG. 6 a, i.e. bearing with its expanding section 41 a, 41 b, which is formed by two latching hooks (arranged on both sides of a gap 42 ), against the edge 31 of the latching opening 30 and engaging behind said edge.
[0052] Arranged behind the latching opening and spaced apart in the introductory direction E or axial direction a from the expanding section 41 a, 41 b, which is in its latching position, is a securing element 5 which is connected releasably to a component of the contact bridge 1 , is designed as a securing pin and, on its side facing the latching section 41 a, 41 b (in the latching position), has a guide section tapering conically to the latching section 41 a, 41 b. Said guide section is assigned corresponding side walls 420 , which have a conical profile, of the gap 42 of the expanding element 4 ″ in order to facilitate the introduction of the securing element 5 into the form-fitting region 45 of the expanding element 4 ″. On its side facing away from the expanding section 41 a, 41 b, which is in the latching position, the securing element 5 furthermore has a supporting section 52 protruding from its cylindrical surface.
[0053] With reference to FIG. 6 a, it is furthermore clear that the expanding section 41 a, 41 b of the expanding element 4 ″ has, on its lower, outer edge, introductory slopes 410 which interact with corresponding introductory slopes 310 of the latching opening 3 in order to facilitate the introduction of the expanding element 4 ″ with its expanding section 41 a, 41 b into the latching opening 3 in the introductory direction E during assembly of the airbag module 2 and the contact bridge 1 . In this case, the expanding section 41 a, 41 b of the expanding element 4 ″ is deformed inward counter to the radial r and compressed in the above-described manner under constriction of the gap 42 until it expands again when the latching position illustrated in FIG. 6 a is reached.
[0054] FIG. 6 b shows the connecting point from FIG. 6 a with the expanding element 4 ″ again in its latching position, but the securing element 5 being held in the form-fitting region 45 of the expanding element 4 ″. Said securing element presses the two hooks of the expanding section 41 a, 41 b apart in such a manner and thereby widens the expanding section 41 a, 41 b in such a manner that the latter is held permanently in the expanded state in which it engages behind the edge 31 of the latching opening 3 . Put another way, the securing element 5 when it is situated in the form-fitting element 45 of the expanding element 4 ″ opposes a radial compression of the expanding section 41 a, 41 b, with the result that the latter cannot pass through the latching opening 3 . It is thereby avoided that the connection could become loose when particularly great forces occur.
[0055] The transition from the state of the connecting point that is shown in FIG. 6 a into the state shown in FIG. 6 b takes place in such a manner that (utilizing the length of the stem 40 of the expanding element 4 ″ in the axial direction a or introductory direction E, which length is larger than the extent of the latching opening 3 along this direction a or E) the expanding element 4 is displaced in the introductory direction E beyond its latching position until, by means of its form-fitting region 45 , which is formed in the gap or slot 42 and defines an undercut contour, it grasps the cylindrical basic body 50 (securing pin) of the securing element 5 . In this connection, the introduction of the securing element 5 into the gap 42 and finally into the form-fitting region 45 of the expanding element 4 ″ is facilitated by the interacting guide sections 410 , 51 of the expanding element 4 ″ and of the securing element 5 .
[0056] FIG. 6 b also shows the predetermined breaking point 55 at which the securing element 5 has been released from the associated component of the contact bridge 1 after being grasped by the form-fitting region 45 of the expanding element 4 ″.
[0057] The connecting point illustrated in FIGS. 6 a and 6 b can also be configured in such a manner that the grasping of the securing element 5 by the form-fitting region 45 of the expanding element 4 ″ is only caused in the event of a crash, in particular under the action of the recoil generated by the gas generator of the airbag arrangement. On the other hand, it may also be provided that the transfer of the expanding element 4 ″ from the state shown in FIG. 4 a, in which it is in its latching position in the expanded state, but without securing element, into the state shown in FIG. 6 b takes place at a certain time during the installation of the subassemblies to be connected to each other (contact bridge 1 and airbag module 2 ), the expanded state of the expanding section 41 a, 41 b being held in the last-mentioned state by the securing element 5 , so that the expanding section 41 a, 41 b cannot be guided out of its latching position through the latching opening 3 .
[0058] It can therefore be provided, for example, that the two subassemblies to be connected to each other are first of all assembled in such a manner that the respective connecting points are in the state shown in FIG. 6 a, in which the expanding element 4 ″ is in its latching position without the securing element 5 , in which latching position it engages with the latching section 41 a, 41 b behind the edge 31 of the latching opening 3 . At a later time, for example when the corresponding steering wheel and the associated airbag module are installed in a motor vehicle, the securing of the connecting points can take place by the expanding element 4 ″ being transferred, by grasping the securing element 5 , into the state illustrated in FIG. 6 b, in which the expanded state of the expanding section 41 a, 41 b is held by the securing element 5 .
[0059] The securing of the expanded state of the expanding section 41 a, 41 b can therefore take place in a specific manner at a time at which the installation process has been finished to the extent that an unlocking of the connecting points no longer appears to be necessary. As an alternative, the bringing of the expanding element 4 into engagement with the securing element 5 , which movement has already been described further above, can be provided in the event of a crash.
[0060] The arrangement illustrated in FIGS. 6 a and 6 b firstly has the advantage that the guide geometry assisting the introduction of the securing element 5 into the form-fitting section 45 of the expanding element 4 ″ together with the guide surfaces 51 and the extension 52 and the associated inner surfaces 420 on the gap 42 of the expanding element 4 ″ at the same time assists the expanding element on the latching plane in the absorption of shearing forces which may occur when subjected to a large load (in the event of a crash), so that an unlatching of the expanding element from its latching position is reliably prevented. Furthermore, in all of the exemplary embodiments previously described, the fixed latching of the securing element 5 on the expanding element 4 , 4 ′, 4 ″ avoids grinding noises when the signal horn is triggered.
[0061] Since the securing element which is connected releasably to an associated component, for example a component of the contact bridge 1 , can be formed on the corresponding component by injection molding, the provision of the securing element 5 does not require any additional outlay and, in particular, no additional, separate components, and so the logistic costs are minimized. The outlay on installation is also minimized, since the securing element 5 does not have to be introduced into the expanding element 4 , 4 ′, 4 ″ as a separate component, but rather is held ready from the start behind latching opening 3 as a component of one of the subassemblies to be connected (contact bridge 1 ). In this connection, in particular, a suitable pairing of material with the expanding element 4 , 4 ′, 4 ″ is also possible. | The invention relates to a device for connection of an airbag module to a supporting vehicle component, comprising an expanding element, arranged on one of the modules for connection, a clip opening, provided on one of the other modules for connection, and into which the expanding element may be introduced such as, in a clipping position in the expanded state, to engage behind the edge of the clip opening and a security element which may be engaged with the expanding elements such as to retain the expanding element in the expanded state. According to the invention, the security element, before being engaged with the expanding element, is detachably connected to a component of the module, provided with the expanding element and arranged behind the clip opening such as to be able to be brought into engagement with the expanding element when the latter is run through the clip opening over the clip position thereof. | 1 |
FIELD OF THE INVENTION
This invention relates to thermoplastic polymers having tetrafluoroethylene units and perfluoro alkyl vinyl ether units, mixtures of such polymers that contain low molecular weight and high molecular weight components, and to processes and articles that employ such polymers.
BACKGROUND
Copolymers of tetrafluoroethylene (TFEs below) and perfluoro alkyl vinyl ethers having from 1 to 4 carbon atoms in the alkyl moiety (PAVEs below), in particular perfluoro n-propyl vinyl ether (PPVEs below) have been known for a long time. Such copolymers are commercially available under the designation “PFA”. At a PAVE copolymer content of about 2% by weight and greater, these partially crystalline copolymers have excellent technical performance, for example exceptional chemical stability, combined with high service temperatures. They can be processed from the melt as thermoplastics, for example by compression molding, extruding or injection molding. Preferred applications are, inter alia, extruded pipes, tubes and cable sheathing. Processing from the melt takes place at temperatures of from 350 up to 450° C. Under these conditions, both thermal and mechanical degradation occur.
The thermal degradation takes place predominantly via the thermally unstable end groups formed in the polymerization, i.e. from the end of the chain. The mechanism of this degradation is described in more detail in “Modern Fluoropolymers”, John Wiley & Sons, 1997, K. Hintzer and G. Löhr, Melt Processable Tetrafluoroethylene-Perfluoropropylvinyl Ether Copolymers (PFA), page 223. The degradation can be substantially suppressed by converting the thermally unstable end groups into stable CF 3 end groups by postfluorination, as described, for example in U.S. Pat. No. 4,743,658 and DE-C-19 01 872.
Corrosive gases arise during the thermal degradation, and these considerably impair the quality of the final product by metal contamination or bubble formation, and can corrode tooling and processing machinery. The effect naturally increases with falling molecular weight (lower melt viscosity).
The mechanical degradation during processing takes place through chain breakage, recognizable by the increase of the melt flow index (MFI). It increases as extrusion speed (shear rate) rises. The resultant lowering of molecular weight considerably worsens the mechanical properties, in particular the flexural fatigue strength and other long-term properties, such as long-term failure (stress crack resistance). Keeping the mechanical degradation within acceptable limits places corresponding limitations on processing conditions. This applies in particular to the extrusion speed for pipes, tubes and cable sheathing. At higher extrusion speeds, melt fracture (shark skin) also occurs, as with all thermoplastics. Although it is possible to implement higher extrusion speeds without melt fracture by lowering the molecular weight (higher MFI values), such products do not have adequate mechanical properties. For this reason, PFA products with an MFI value >15 are currently not on the market.
It is known from WO-A-97/07147 that a marked rise in the extrusion rate is possible, while avoiding melt fracture and with retention of the mechanical properties, with partially crystalline copolymers which consist essentially of TFE and at least 3% by weight of perfluoro ethyl vinyl ether and which have a melt viscosity of not more than 25×10 3 Pas at 372° C., with the proviso that the melt viscosity may exceed this value if the content of the ether mentioned exceeds 10% by weight. The perfluoro ethyl vinyl ether is, however, difficult to obtain, and therefore all of the marketed products contain PPVE, which is easily obtainable industrially and is also preferred for the present invention.
DISCLOSURE OF THE INVENTION
A PFA has now been found which has good melt processability and which contains at least one high-molecular-weight PFA with an MFI≦15, preferably from 0.01 to 15, and at least one low-molecular-weight PFA with MFI≧30. The mixtures of the invention are particularly useful in applications where chemical resistance and high temperature resistance are important.
The invention therefore relates to mixtures of thermoplastic fluoropolymers essentially comprising units of TFE and subordinate amounts of units of one or more PAVEs having from 1 to 4 carbon atoms in the alkyl moiety and a total concentration of from 0.5 to 10 mol %, the mixture comprising A) at least one low molecular weight component with an MFI A ≧30 and B) at least one high molecular weight component with an MFI B ≦15. These components are selected in such a way that the ratio of the MFI A of component A) to the MFI B of component B) is in the range from 80 to 2500, preferably in the range of from 240 to 750.
“Essentially comprising units of TFE and of a PAVE” means that small amounts, up to about 5 mol %, of other fluoromonomers not containing hydrogen, such as hexafluoropropene or chlorotrifluoroethylene, are not to be excluded. The composition of the copolymer of the two components may differ within the limits mentioned above.
The mixing ratio of high- and low-molecular-weight components may vary within wide limits and can be determined for the desired application by means of simple preliminary experiments. The ratio is generally from 10:90 to 90:10, preferably in the range from 25:75 to 75:25 parts by weight and in particular from 60:40 to 40:60 parts by weight.
The invention also relates to a novel low-molecular-weight PFA with an MFI≧30, preferably ≧120 with preference from 120 to 1000, in particular from 120 to 700, especially from 200 to 600.
Another aspect of the invention relates to mixtures of the novel low-molecular-weight PFA(s) mentioned with the high-molecular-weight PFA(s) mentioned above, the MFI ratio mentioned above corresponding approximately to a molecular weight ratio of the high-molecular-weight to the low-molecular-weight component(s) ≧3.5, preferably from 3.5 to 10, in particular from 3.5 to 7.
The MFI gives the amount of a melt in grams per 10 min which is extruded from a holding cylinder through a die by the action of a piston loaded with weights. The dimensions of the die, the piston, the holding cylinder and the weights are standardized (DIN 53735, ASTM D-1238). All of the MFIs mentioned here have been measured with a die of diameter 2.1 mm and length 8 mm using a superimposed weight of 5 kg and a temperature of 372° C. The values 0.01 and 1000 are practically the limiting values of this measurement method.
For very high MFI values, therefore, it is expedient to reduce the superimposed weight to values down to 0.5 kg, and for very small MFI values to increase it to values up to 20 kg. The MFI values determined in this way are recalculated for a superimposed weight of 5 kg.
The present invention further provides a process for making a shaped article from the mixtures of the invention. This process involves providing the mixture, extruding, compression molding, or injection molding the mixture, and preferably, cooling the mixture to provide a self-supporting shaped article.
Still further the present invention provides shaped articles comprising the mixture. Examples of such articles include molded or extruded goods such as films, pellets, wire and cable insulation, tubes and pipes, containers, vessel liners, and the like.
DETAILED DESCRIPTION
The novel mixtures may be prepared in a conventional manner, i.e. for example by mixing the pulverulent products, mixing dispersions of the components, or by conducting the polymerization in an appropriate manner (“step polymerization”) with controlled use of initiator and chain transfer agent, such as short-chain alkanes and haloalkanes, and also hydrogen. An advantageous procedure here is as follows: at the start of the polymerization, for a low desired MFI, relatively little initiator and relatively little chain transfer agent are metered in. These polymerization conditions are changed at the desired juncture in the polymerization, depending on the type of composition by weight to be achieved, for example after 50% of the TFE addition, by metering in further initiator and chain transfer agent, so that the polymer produced as the polymerization continues has the desired high MFI. The desired high MFI may also be created by increasing the temperature during the polymerization. The advantage of this preparation process is that a “perfect” mixture of the two components is created in situ.
Preference is given to mixing dispersions of the components and working up the mixture in a manner known per se (U.S. Pat. No. 4,262,101) or advantageously by mechanical precipitation using a homogenizer, followed by agglomeration by petroleum fractions. After subsequent drying, the product is subjected to melt granulation.
Because the two components have very different MFI values, homogeneous mixtures of powders or of melt granules down to the micro range can be produced only with equipment which is relatively highly elaborate. However, homogeneous mixtures are essential for achieving excellent performance.
Compared with a PFA having comparable MFI, the novel mixtures are distinguished by considerably increased extrusion speed without melt fracture. However, as shown by MFI determination before and after processing, this is not at the cost of significantly increased degradation.
The novel mixtures have a noticeably increased zero-shear viscosity and a lower complex viscosity at higher shear rates, compared with a commercially available polymer component with identical MFI.
The PFA with MFI≧30 differs from the hitherto conventional grades of PFA in its low molecular weight. It therefore has a relatively large number of labile end groups, which limit the thermal stability of the material. For relatively stringent requirements therefore it is expedient to convert the unstable end groups to stable end groups in a manner known per se by reaction with elemental fluorine (GB A 1 210 794, EP-A-0 150 953 and U.S. Pat. No. 4,743,658). It is expedient here to dilute the fluorine with an inert gas and to use this mixture to treat the dry polymer or polymer mixture. The toxic fluorine is then removed by flushing with inert gas. This same process may be used to post fluorinate the mixtures of the invention.
The success of the postfluorination is checked by IR-spectroscopic determination of the residual carboxyl and/or carbonyl fluoride end groups, as described in U.S. Pat. No. 4,743,658. However, complete fluorination of the end groups is not necessary. Reduction of the thermally unstable end groups (COOH+COF) to from 10 to 15 end groups/10 6 carbon atoms is sufficient to achieve the desired improvements in properties. This significantly shortens the reaction time and therefore makes the postfluorination more cost-effective.
The novel PFA mixture postfluorinated in this way shows no discoloration, even at 450° C. It therefore permits higher processing temperatures and thus a rise in the throughputs in the extrusion of tubes and of sheathing for wires and cables, and also in injection molding. A further advantage of the increased high-temperature resistance is that when production failures occur, the novel PFA mixture remains for a longer residence time at high temperatures without degradation and thus there is no discoloration or bubble formation at elevated temperature and no corrosion of the processing machinery or of the substrates which come into contact with the polymer mixture.
The preferred process for preparing the novel mixtures consists in blending the two components as dispersions, agglomerating these, drying and melt granulation followed by water-treatment (DE-A-195 47 909) of the granules obtained from the melt and, if desired, postfluorination of the same.
The novel mixtures are advantageously suitable for producing thin-walled articles by extrusion or extrusion blow molding and injection molding. The higher processing speeds which are possible here do not have to be obtained at the cost of impairment of properties; on the contrary, the products obtained surprisingly have increased stiffness (increased modulus of elasticity) and yield stress, i.e. the novel mixtures can resist higher mechanical stresses in particular applications, since an increased yield stress means an enlargement of the elastic range of these materials. This makes it possible to create moldings with longer service lives, and this in turn permits the use of tubes with thinner walls.
The polymerization may be carried out by known processes of aqueous free-radical emulsion polymerization (U.S. Pat. Nos. 3,635,926, 4,262,101), or in a non-aqueous phase (U.S. Pat. No. 3,642,742).
The perfluoro propyl vinyl ether content is determined by IR spectroscopy (U.S. Pat. No. 4,029,868).
EP-B-362 868 has already disclosed mixtures of fluoropolymers, including investigation of high-molecular-weight and low-molecular-weight PFA grades. The low-molecular-weight component here is defined by a melt viscosity at 380° C. of from 5000 to 280,000 Poise, corresponding to an MFI at 372° C. of from 80 to 1.6. It is expressly mentioned here that a melt viscosity of less than 5000 Poise (MFI>80) leads to poor mechanical properties of the mixture. In the mixture described as example in EP-B-362 868, column 4, the mean molecular weights of the PFA grades used differ only slightly, to be specific approximately only by a factor of 1.5, corresponding to the melt viscosities of 8.1×10 4 and 1.9×10 4 Poise, respectively. Such materials are particularly suitable for thick-walled extruded articles, such as pipes.
The invention is described in more detail in the following examples. Percentage and ratio data are based on weight unless otherwise stated. Degradation behavior is assessed using the ratio of MFI after and before processing.
EXAMPLE 1
25 l of demineralized water and 122 g of ammonium perfluorooctanoate in the form of a 30% strength solution are placed in a polymerization reactor having a total volume of 40 l and provided with an impeller stirrer. After the reactor has been sealed, atmospheric oxygen is removed by alternate evacuation and flushing with nitrogen, and the vessel is heated to 60° C. 46 g of methylene chloride and 0.180 kg of PPVE are pumped in. The stirrer is set at 240 rpm. TFE is then introduced until the total pressure has reached 13.0 bar. The polymerization is initiated by pumping in 6.6 g of ammonium persulfate (APS below), dissolved in 100 ml of demineralized water. As soon as the pressure begins to fall, further TFE and PPVE are supplemented via the gas phase in accordance with the target ratio of PPVE (kg)/TFE (kg) of 0.042, in such a way that the total pressure of 13.0 bar is maintained. The heat liberated is dissipated by cooling the vessel wall, and in this way the temperature of 60° C. is held constant. After a total of 7.2 kg of TFE has been fed into the reactor, the monomer feed is interrupted, the pressure in the reactor is released and the reactor is flushed several times with N 2 .
The resultant amount of 31.5 kg of polymer dispersion with a solids content of 22.8% is discharged from the bottom of the reactor. After the dispersion has been transferred into a 180 l stirring vessel, its volume is increased to 100 l with demineralized water and it is mixed with 200 ml of concentrated hydrochloric acid and stirred until the solid has separated from the aqueous phase. The flocculant powder precipitated after stirring is granulated with 6.9 l of a petroleum fraction, the petroleum fraction is driven off using steam, and the granules are then washed six times by vigorous and thorough stirring with 100 l of demineralized water on each occasion. The moist powder is dried for 12 hours at 260° C. in a drying cabinet under nitrogen. This gives 7.1 kg of a low molecular weight bipolymer according to the invention which has a PPVE content of 3.9% and an MFI of 40.
EXAMPLE 2
A PFA mixture according to the invention having an MFI of 2.3 is prepared from a 50/50 mixture composed of a dispersion of the material from Example 1 and a dispersion of a PFA having an MFI of 0.5. The ratio of MFI A to MFI B is 80.
In preparing the PFA having an MFI of 0.5, the procedure is as in Example 1, but 6.7 g of methylene chloride and 1.8 g of APS are pumped in, giving a bipolymer which has 3.9% of PPVE and an MFI of 0.5.
The dispersion mixture is worked up as in Example 1. This gives a bipolymer which has a PPVE content of 3.9% and an MFI of 2.3. After melt granulation, the MFI rises to 2.4.
EXAMPLE 3
The PFA mixture of Example 2 is compared with a commercially available PFA having an MFI of 2 in the extrusion of a tube having an external diameter of 28.3 mm and an internal diameter of 27.7 mm. Extruder data:
Diameter:
50 mm
Length:
1200 mm (length: diameter ratio = 24)
Compression ratio:
2.5:1
Die:
Outer annulus diameter:
60 mm
Inner annulus diameter:
55 mm
Parallel portion:
25 mm
Calibration:
Diameter:
28.4 mm
Extrusion speed:
Standard setting:
2.3 m/min at 22 rpm
Throughput:
8 kg/h
Tube weight:
60 g/m
Temperature control:
Barrel 1 (Feed):
340° C.
Barrel 2:
355° C.
Barrel 3:
370° C.
Barrel 4:
375° C.
Flange:
310° C.
Head:
376° C.
Die:
388° C.
The results are shown in the following table, the meanings of abbreviations being
PFA2: Commercially available product with an MFI of 2
TS: Ultimate tensile strength N/mm 2
EB: Elongation at break %
Y: Yield stress N/mm 2
(in each case in accordance with DIN 53455/ASTM D 1708, measured in longitudinal and transverse direction on test specimens stamped out from the tube).
Through-
MFI
Mechanical properties
put
be-
af-
MFI
Longitudinal
Transverse
Material
(kg/h)
fore
ter
Rise
TS
EB
Y
TS
EB
Y
PFA2
8
2
2.7
1.35
26
300
12
32
350
12
PFA2
13.5*)
2
2.7
1.45
28
320
12
30
340
12
Exam-
8
2.4
2.8
1.17
28
340
13
29
360
13
ple 2
Exam-
20*)
2.4
3.3
1.38
27
320
13
30
390
13
ple 2
*)highest throughput possible without melt fracture
Therefore whereas the commercially available product PFA2 permits only a maximum throughput of 13.5 kg/h, the mixture of Example 2 allows a throughput of 20 kg/h, without adverse effects on the quality of the tube. The MFI change shows that the commercially available product, even at a low throughput of 8 kg/h, is degraded to about the same extent as the novel material from Example 2 at a throughput of 20 kg/h.
The yield stress of the novel material is increased. This means that the final article has a higher dimensional stability and/or stiffness.
The tubes extruded with the mixture of Example 2 prepared according to the invention also show, compared with the commercially available PFA2 material, increased cold bursting strength.
Using the mixture of Example 2 prepared according to the invention and the commercially available PFA2 material, and under the same conditions, pipes of 1 mm wall thickness and 10 mm diameter were extruded and their cold bursting strength determined.
The test took place on a bursting strength test apparatus (in-house construction), in which a firmly secured plastic pipe was filled with water and placed under pressure using a pneumatic pump. The pressure test is regarded as having been passed if the pipe survives without damage after pressure has been maintained for 6 min at a test pressure dependent on the dimensions of the pipe. After this test has been carried out, the test pressure is raised by 2 bar/min until the pipe bursts, in order to determine the residual bursting strength.
The specified test pressure for pipes of this size is 22 bar.
Residual bursting
Materials
Pressure test
strength [bar]
Example 2
Passed
27
PFA2
Some passes
24
Some buckling
EXAMPLE 4
The PFA mixture of Example 2 is processed to give a pressed sheet, and long-term failure is determined on specimens of this pressed sheet. The PFA2 defined in Example 3 served as comparison. Whereas the mean value of the times to failure for PFA2 is 194 h, after 793 h only two of three specimens of the mixture of Example 2 had failed.
The tests were long-term tensile creep tests based on the specification of the Deutscher Verband für Schweisstechnik [German Association for Welding Technology], DVS 2203, Part 4, on notched specimens. The specimens were compression-molded plates of 5 mm thickness. The force applied was 4 N/mm 2 . The medium used is demineralized water containing 2% of non-ionic surfactant (ARKOPAL® N 100). The tests are carried out at a temperature of 80° C. In each case, the measurements are carried out on three identical test specimens. This test method, and therefore also the results, permit correlation with DIN 8075 measurements of the effects of long-term internal hydrostatic pressure on pipes.
Material
Time to fracture (mean calculated from three values)
PFA 2
194 h
Example 2
>793 h
EXAMPLE 5
The procedure of Example 1 is followed, but 200 g of methylene chloride and 20 g of APS are pumped in, resulting in a low molecular weight bipolymer according to the invention having a PPVE content of 4% and an MFI of 500.
EXAMPLE 6
A PFA mixture according to the invention having an MFI of 9.8 is prepared as agglomerate from a 50/50 mixture composed of a dispersion of the material from Example 5 and a dispersion of a PFA with an MFI of 1.6. The ratio of MFI A to MFI B is 312.5.
In preparing the PFA with the MFI of 1.6, the procedure is as in Example 1, but 19 g of methylene chloride and 2 g of APS are pumped in, giving a bipolymer which has 4.2% of PPVE and an MFI of 1.6.
The dispersion mixture is worked up as in Example 1. This gives a bipolymer which has a PPVE content of 4.1 mol % and an MFI of 9.8.
EXAMPLE 7
The PFA mixture of Example 6 (MFI 9.8) is compared with commercially available products in pellet form having an MFI of 10 (for example PFA10) in the injection molding of specimens. For this the materials are firstly converted into melt pellets, the MFI changing as shown in the table.
Dumbbell Specimens
Heating:
Temperature in Zone 1:
390° C.
Temperature in Zone 2:
390° C.
Temperature in Zone 3:
420° C.
Temperature in Zone 4:
350° C.
Injection pressure:
600 bar (6-10 7 Pa)
Injection rate:
4 mm/s
Mold temperature:
210° C.
Results
Modulus
Yield
of
stress
TS
MFI
MFI in
elasticity
[N/
EB
[N/
Degra-
Material
pellets
specimen
[N/mm 2 ]
mm 2 ]
[%]
mm 2 ]
dation
Exam-
11.5
13.2
642
15.5
468
23.5
1.15
ple 6
PFA10
10
11.7
593
14.8
450
27.0
1.2
Modulus of elasticity and yield stress are measured on dumbbell specimens (DIN 53455, Test specimen No. 3) by the DIN 53457 measurement method. The novel material shows lower degradation, higher modulus of elasticity and higher yield stress, without change in mechanical properties, such as TS and EB.
The improved flowability of the novel mixture is also apparent in the injection molding of spirals. The greater the length of the injected spiral, the better the flow performance. The degradation occurring in this procedure can be assessed from the MFI ratio.
The injection conditions are as follows:
Heating
Program 1
Program 2
Temperature in Zone 1
435° C.
(390° C.)
Temperature in Zone 2
435° C.
(390° C.)
Temperature in Zone 3:
420° C.
(380° C.)
Temperature in Zone 4:
350° C.
(350° C.)
Injection pressure
600 bar
700 bar
Results
Heating
Degradation
Material
program
Length
MFI spiral /MFI starting material
Example 6
1
26.1
2.5
PFA10
1
22.9
2.45
Example 6
2
23.1
2.2
PFA10
2
severe delamination
Compared with standard material, the PFA mixture of Example 6 shows markedly better flowability with the same degradation and a lower tendency to delaminate when lower temperatures and higher injection rates are used.
EXAMPLE 8
The PFA mixture of Example 6 is converted into melt pellets which show an MFI of 11. 1.5 kg of this mixture is melted in the melt container in a convection heating cabinet at 370° C. for 5 h, and injection molded within a period of 4 min into a mold, likewise heated to 370° C. and having complicated injection geometry. The shape to be encapsulated is that of a magnetic coupling. After cooling for 30 min with water, the molded specimen has no defects, in particular neither gas inclusions nor any discoloration. The MFI of the molding is 11.3. In contrast, a standard PFA with MFI 10 or 15 showed delaminations in the molding, making the component unusable.
EXAMPLE 9
125 kg of PFA mixture from Example 6 are placed in a 300 l tumbler dryer. During heating to 220° C., atmospheric oxygen and moisture are removed by alternate evacuation and flushing with nitrogen. The reactor is then filled with an F 2 /N 2 mixture containing 10% of F 2 . The reaction proceeds for 5 hours, and after each hour the F 2 /N 2 mixture is renewed. During cooling from 220° C. to room temperature, unreacted fluorine in removed by alternate evacuation and flushing with N 2 . The resultant product has only about 15 remaining COOH end groups, corresponding to about 10% of the thermally unstable end groups initially present.
The resultant product was injection molded essentially as described in Example 7. It is apparent during this that the postfluorinated PFA mixture of Example 9 can withstand higher thermal stresses.
Dumbbell specimens: DIN 53455, Test specimen No. 3
Heating
Temperature in Zone 1: x 1
Temperature in Zone 2: x 2
Temperature in Zone 3: 420° C.
Temperature in Zone 4: 350° C.
Temperature [° C.]
Material from
Zone x 1
Zone x 2
Example 6
Example 9
390
390
colorless
colorless
400
400
colorless
colorless
410
410
yellowish
colorless
420
420
brownish
colorless
430
430
brown
colorless
440
440
brown
colorless
450
450
deep brown
colorless
EXAMPLE 10
The procedure (i.e. the preparation of the polymerization reactor, the polymerization conditions, and the work-up) of Example 1 is followed. However, for preparing a novel mixture by step polymerization, at the start of the polymerization 7 g of methylene chloride and 2 g of APS are added. Following 50% of the amount of TFE to be run in, 35 g of methylene chloride and 10 g of APS are metered in. This gives a bipolymer having a PPVE content of 3.9% and an MFI of 2.1.
The first part of the polymerization gives a PFA having an MFI of 0.3. The MFI created in the second step is calculated from the MFI of 2.1 of the end product via the following equation: MFI A = ( MFI End - 0.294 - x · MFI B - 0.294 x ) x = proportion by weight
The MFI is therefore 75. The ratio of MFI A to MFI B is 250.
The PFA mixture of the invention created in this step polymerization was compared with a standard material PFA2 in a high-pressure capillary rheometer, in relation to the shear rate at which melt fracture occurs.
Compared with the commercially available material PFA2, the shear rate at which melt fracture just becomes visible is increased by a factor of 2 in the material of Example 10.
Shear rate at start of melt
fracture in s −1
PFA2
15
Example 10
30
EXAMPLE 11
The procedure (i.e., the preparation of the polymerization reactor, the polymerization conditions, and the work-up) of Example 1 is followed. However, for preparing a novel mixture by step polymerization, at the start of the polymerization 3 g of methylene chloride and 2 g of APS are added. Following the addition of 30% of the amount of TFE to be run in, 100 g of methylene chloride and 10 g of APS are metered in. This gives a bipolymer having a PPVE content of 3.9% and an MFI of 2.6, and a swell index of 1.54. The swell index is defined by the following formula: [DE/DD−1]100, where DE is the diameter of the extrudate and DD the diameter of the die.
The first part of the polymerization gives a PFA having an MFI of 0.1. An MFI of 130 created in the second stage is calculated from the MFI of 2.6 of the end product, using the equation given in Example 10. The ratio of MFI A to MFI B is 1300.
The material was processed on a continuous extrusion blow molding plant to give 1 l volumetric flasks and compared with a commercially available product having MFI=2 and a swell index of 1.1. High swell indices are particularly advantageous for this processing technology.
The processing conditions are as follows:
Melt temperature:
370° C.
Extrusion speed:
100 mm/min
Tube diameter:
60 mm
Maximum blow-up ratio:
2.5:1
Using the novel material, in contrast to the commercially available product, it was possible continuously to produce, without scrap, 1 l volumetric flasks with uniform wall thickness and wall thickness distribution. Using the commercially available product, this is successful only with volumetric flasks having a volume of up to 100 ml. | A low-molecular-weight copolymer of tetrafluoroethylene with units of perfluoro alkyl vinyl ethers having a melt index of ≧30 suitable as a mixing component with a higher-molecular-weight copolymer of the same monomers for producing moldings in injection molding or by extrusion. | 8 |
COPYRIGHT NOTICE
Contained herein is material that is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction of the patent disclosure by any person as it appears in the Patent and Trademark Office patent files or records, but otherwise reserves all rights to the copyright whatsoever.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates generally to the field of digital halftoning. More particularly, the invention relates to a method and apparatus for digital halftoning that provides flexibility in terms of pattern choices by enabling a position in the threshold matrix to make multiple transitions between on (e.g., printed with toner/ink) and off (e.g., not printed) thereby allowing visually displeasing patterns to be avoided without loss of gray levels
2. Description of the Related Art
Image processing apparatus and processes are evaluated in part, by their capability of delivering a complete gray scale at normal viewing distances. This capability is to a certain extent based upon the halftoning techniques employed. Halftoning is a widely used mechanism for converting input pixels represented with multiple bits of information (usually 8 bits) into bilevel picture elements (“pels”). The goal in halftoning continuous-tone images or multi-level computer generated graphics is to give an illusion of the many shades contained in the original or interpolated multi-bit values per component sample while using only one bit per sample. One traditional technique for halftoning is to create a threshold matrix (usually a different one for each color component) and use it to select a threshold value per sample. The threshold matrix is generally of much smaller dimensions than the image. Halftoning is accomplished by progressing through the input line and the threshold matrix simultaneously, comparing each input gray value with the corresponding threshold value in the threshold matrix. If the input gray value is greater than or equal to the threshold value, a black (i.e., fully saturated) corresponding output pel is generated, otherwise the corresponding output pel is white. For each line in the image, a given threshold matrix row is cycled through repetitively. The next row is used for the next line. After the last row in the threshold matrix is used, the top row of the threshold matrix is used again.
These threshold matrices are generally referred to as “supercells.” An exemplary supercell and its relationship to basic cells are discussed briefly with reference to FIGS. 1A and 1B . FIG. 1A illustrates the structure of a basic cell 100 . In FIG. 1A , the basic cell 100 comprises a 4×4 pel matrix. As described further below, at present, element positions within the basic cell structure 100 are manipulated in a sequential manner (as indicated by the numbers within the elements) to achieve output gray levels. Incrementing from one output gray level to the next is accomplished by preserving the current pattern represented by the elements of the basic cell structure 100 and turning on one additional element.
FIG. 1B illustrates an exemplary supercell that is made up of much smaller basic cells such as that depicted in FIG. 1A . The four quadrants of the supercell are labeled to show the order in which the basic cells are filled. In this example, the supercell 150 comprises four basic cells 151 – 154 . The basic cells 151 – 154 set the halftone's lines per inch thereby determining the level of detail that may be preserved while the size of the supercell 150 determines the number of shades obtainable. According to the current state of the art, a single halftone threshold matrix is used to convert grayscale images and graphics into binary images. The density of the pels in a region is indicative of the original values in that region.
FIG. 1C illustrates using four basic cells to achieve 64 levels by incrementally filling the basic cells in accordance with the ordering of FIG. 1B . If the input image only had 65 levels, i.e., 0 to 64, then FIG. 1C could represent a traditional threshold matrix. Each element contains the comparison, i.e., threshold, value used to determined whether to print the corresponding position in the input image or not. For purposes of this application, the convention of the input value being greater than or equal to the comparison value is employed for the output to be a one (e.g., printed). Of course, this convention is arbitrary and other conventions may be employed. For example, an alternative convention would be to enable (e.g., print) the output pel when the input value is less than or equal to the threshold value.
As illustrated by the prior art basic pattern growth example of FIG. 2 , N×M+1 output gray levels may be represented with an N×M halftone matrix. For example, a 4×4 halftone matrix allows the generation of 17 levels, i.e., white 201 plus 16 other levels 202 – 217 , to be achieved by turning one and only one element on for each subsequent level. Currently, subsequent gray levels are generated based upon previous gray levels by turning one and only one additional element on, thereby requiring patterns for each subsequent gray level to be a superset of those patterns corresponding to preceding gray levels. For example, once element 220 of the pattern is turned on, it remains on for the rest of the basic patterns. As a result, it can be difficult to avoid bad patterns, such as those that produce visual artifacts and/or undesirable textures or are otherwise visually displeasing, while also seeking to maximize the number of gray levels.
BRIEF SUMMARY OF THE INVENTION
A method and apparatus are described for implementing flexible digital halftoning. According to one embodiment, a new data structure is employed for use during halftoning. The new data structure is referred to as a flexible, halftoning, threshold array and is configured to allow more than one transition in output values as a function of possible input values for at least one position in the halftoning threshold array.
According to another embodiment, a flexible halftoning technique is provided. An input image is received and for each pel of an output image corresponding to the input image, a level to be output for the pel is determined by applying a novel threshold array to the input image. The novel threshold array is configured to cause more than one transition at one or more pel positions as a function of input values.
According to yet another embodiment, halftoning processing includes receiving an input image and determining a level to be output for each pel of a corresponding output image by applying multiple threshold matrices to each sample for each component of the given input image.
Other features of the present invention will be apparent from the accompanying drawings and from the detailed description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
The appended claims set forth the features of the invention with particularity. The invention, together with its advantages, may be best understood from the following detailed description taken in conjunction with the accompanying drawings of which:
FIG. 1A illustrates an exemplary basic cell.
FIG. 1B illustrates an exemplary supercell.
FIG. 1C illustrates the use of four basic cells within the supercell structure of FIG. 1B to achieve 65 output levels.
FIG. 2 illustrates exemplary prior art basic pattern growth.
FIG. 3 is a simplified block diagram depicting a local area network (LAN) printing environment.
FIG. 4 illustrates a more detailed block diagram of a printer system according to one embodiment of the present invention.
FIG. 5 illustrates a device in the form of a computer system in which features of the present invention may be implemented.
FIG. 6 is a block diagram of a halftoning system according to one embodiment of the present invention.
FIG. 7 illustrates a basic pattern growth example according to one embodiment of the present invention.
FIG. 8A conceptually illustrates how multiple threshold matrices are employed according to one embodiment of the present invention.
FIG. 8B illustrates a special case of FIG. 8A in which the input matrix is constant.
FIG. 9 is a flow diagram illustrating halftoning processing using multiple threshold arrays according to one embodiment of the present invention.
FIG. 10A illustrates a table of bit-vectors for creating the basic patterns of FIG. 7 according to one embodiment of the present invention.
FIG. 10B illustrates an output optimization of FIG. 10A according to one embodiment of the present invention in which one access yields 8 pels of output assuming constant input values.
FIG. 11 illustrates a table organized for more efficient output pel retrieval according to one embodiment of the present invention.
FIG. 12 is a flow diagram illustrating halftoning processing via table lookups according to another embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
A method and apparatus are described for implementing flexible digital halftoning. Broadly stated, embodiments of the present invention seek to solve or at least alleviate the above-referenced problems of conventional halftoning approaches by employing a thresholding mechanism that allows flexibility in terms of pattern choices. For example, according to one embodiment, rather than being constrained to a superset of those patterns corresponding to preceding gray levels, one or more positions in a threshold matrix may make multiple transitions between on (e.g., printed with toner/ink) and off (e.g., not printed). Advantageously, this novel halftoning approach allows bad patterns, such as those that produce visual artifacts and/or undesirable textures or are otherwise visually displeasing, to be avoided in basic pattern growth without loss of gray levels.
In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well-known structures and devices are shown in block diagram form.
The present invention includes various steps, which will be described below. The steps of the present invention may be performed by hardware components or may be embodied in machine-executable instructions, which may be used to cause a general-purpose or special-purpose processor programmed with the instructions to perform the steps. Alternatively, the steps may be performed by a combination of hardware and software.
The present invention may be provided as a computer program product that may include a machine-readable medium having stored thereon instructions, which may be used to program a computer (or other electronic devices) to perform a process according to the present invention. The machine-readable medium may include, but is not limited to, floppy diskettes, optical disks, CD-ROMs, and magneto-optical disks, ROMs, RAMs, EPROMs, EEPROMs, magnetic or optical cards, flash memory, or other type of media/machine-readable medium suitable for storing electronic instructions. Moreover, the present invention may also be downloaded as a computer program product, wherein the program may be transferred from a remote computer to a requesting computer by way of data signals embodied in a carrier wave or other propagation medium via a communication link (e.g., a modem or network connection).
For convenience, embodiments of the present invention will be described with reference to a 8×8 supercell comprising four 4×4 basic cells. However, the present invention is not limited to any particular representation of the threshold matrix. In addition, while embodiments of the present invention are described with reference to a bilevel printer, aspects of the present invention are equally applicable to other types of output devices as well, such as multitone printers, monochrome and color display devices, and the like.
In addition, the concepts apply to the IBM InfoPrint Color 130 Plus printer which prints fourteen intermediate values plus a fully saturated value (i.e. 4-bits per output) per color component. This printer uses a threshold matrix to determine when to allow printing. Input values less than the threshold value are forced to zero (i.e., printing off). The input value minus the threshold value is used to index a downloadable table for all input values greater than or equal to the threshold value. This table could contain a ramp of increasing intermediate values and finish with the fully saturated value.
Terminology
Before describing an illustrative printing environment in which various embodiments of the present invention may be implemented, brief definitions of terms used throughout this application are given below.
“Halftoning” is a widely used mechanism for converting input pixels represented with multiple bits of information (usually 8 bits) into bilevel pels to give the illusion of multitones. For color images, each color component is usually halftoned separately as if it were a monochrome image. For the purposes of this specification, the examples are given for pixels (or samples) with only one component. Those skilled in the art will understand how to extend the concepts to multi-component images.
A “threshold matrix” is a conventional data structure used in connection with halftoning. Traditionally, a threshold matrix is represented as a two dimensional (2D) array of threshold values. The threshold values determine the input level for which the output (e.g., a bilevel pel) transitions from the off to on output state.
As used herein, a “threshold array” generally refers to a data structure that is conceptually tiled, both horizontally and vertically, to cover an input image thereby defining a pel output level for each input sample of the input image. In one embodiment, the threshold array may be an array of threshold matrices. The maximum number of transitions for any position determines the number of matrices needed whose outputs are voted (e.g., exclusive ORed to determine the appropriate output level). For example, three traditional threshold matrices may be used in combination to allow any given position to be turned on and then off before remaining on. In another embodiment, the threshold array may be conceptually thought of as a three dimensional (3D) array indexed by u, v, and gray level; where u, and v are the x and y position in the input image modulo N and M (the dimensions of the supercell or the basic cell).
“Voting” is any process of reducing more than one result, input or output to a single result, input or output. The “Exclusive OR” function is one example of such a process.
For multitone (per component) printers the threshold array can be used to specify a gradual change (i.e., a ramp) from off (no printing) to fully saturated on and then another gradual change from on to off. In this case, the output is multi-bit rather than one bit. When the threshold array is composed of multiple threshold matrices, the first matrix could initiate a ramp of increasing intensities. The next matrix could initiate a ramp of decreasing intensities and so on.
Exemplary Printing Environment
A simplified printing environment 300 will briefly be described with reference to FIGS. 3 and 4 . In this example, a personal computer workstation 310 is coupled to a printer system 330 via a LAN 320 . According to one embodiment, the printer system 330 includes a spooler 430 for controlling the spooling of data files and presentation services 440 for generating appropriate commands to drive an attached printer 450 . The printer system 330 may also include other components that are not shown for performing basic tasks, such as monitoring and configuring attached printers, and providing print job management. At any rate, when the PC workstation 310 has data to print, it sends print data to the print server 420 . Among the functions typically provided by the print server 420 is the conversion of the data stream containing the print data to a data stream supported by the printer 450 to which the print data is destined. For instance, the printer 450 may accept the Intelligent Printer Data Stream (IPDS), PostScript, or some other printer data stream. As a result, the printer system 330 may also include a means for converting between the various input data streams that may be received and the data streams accepted by the printer 450 . The print server 420 may also be configured to perform digital halftoning to allow a halftone image representation of an input image to be output by the printer 450 . Alternatively, the novel, flexible, halftoning processing described herein may be performed local to the printer 450 , e.g., by the printer controller 460 .
An Exemplary Computer Architecture
Having briefly described an exemplary environment in which the present invention may be employed, an exemplary machine in the form of a computer system 500 in which features of the present invention may be implemented will now be described with reference to FIG. 5 . Computer system 500 may represent a workstation, host, server, print server, or printer controller. Computer system 500 comprises a bus or other communication means 501 for communicating information, and a processing means such as processor 502 coupled with bus 501 for processing information. Computer system 500 further comprises a random access memory (RAM) or other dynamic storage device 504 (referred to as main memory), coupled to bus 501 for storing information and instructions to be executed by processor 502 . Main memory 504 also may be used for storing temporary variables or other intermediate information during execution of instructions by processor 502 . Computer system 500 also comprises a read only memory (ROM) and/or other static storage device 506 coupled to bus 501 for storing static information and instructions for processor 502 .
A data storage device 507 such as a magnetic disk or optical disc and its corresponding drive may also be coupled to bus 501 for storing information and instructions. Computer system 500 can also be coupled via bus 501 to a display device 521 , such as a cathode ray tube (CRT) or Liquid Crystal Display (LCD), for displaying information to an end user. Typically, an alphanumeric input device 522 , including alphanumeric and other keys, may be coupled to bus 501 for communicating information and/or command selections to processor 502 . Another type of user input device is cursor control 523 , such as a mouse, a trackball, or cursor direction keys for communicating direction information and command selections to processor 502 and for controlling cursor movement on display 521 .
A communication device 525 is also coupled to bus 501 . Depending upon the particular presentation environment implementation, the communication device 525 may include a modem, a network interface card, or other well-known interface devices, such as those used for coupling to Ethernet, token ring, or other types of physical attachment for purposes of providing a communication link to support a local or wide area network, for example. In any event, in this manner, the computer system 500 may be coupled to a number of clients and/or servers via a conventional network infrastructure, such as a company's Intranet and/or the Internet, for example.
The present invention is related to the use of computer system 500 to direct the execution of one or more software and/or firmware routines to perform halftoning via multiple threshold arrays or via a table lookup as discussed herein. As computer system 500 executes the one or more routines, the processor 502 may access an input image stored within main memory 504 , ROM 506 , or another storage device to manipulate the input image in accordance with desired presentation attributes. Importantly, the present invention is not limited to having all of the routines located on the same computer system. Rather, individual objects, program elements, or portions thereof may be spread over a distributed network of computer systems. Additionally, it is appreciated that a lesser or more equipped computer system than the example described above may be desirable for certain implementations. Therefore, the configuration of computer system 500 will vary from implementation to implementation depending upon numerous factors, such as price constraints, performance requirements, and/or other circumstances. For example, according to one embodiment of the present invention, an embedded printer controller may comprise only a processor and a memory for storing static or dynamically loaded instructions and/or data.
An Exemplary Halftoning System
FIG. 6 illustrates a block diagram of a halftoning system according to one embodiment of the present invention. In this example, an input image 610 is scanned by a scanner 620 and stored in image storage 630 . A halftoning processor 640 processes the stored image, if needed, to match the spatial sample frequency of the stored image to the spatial frequency of the printer's pels. Halftoning processor 640 then processes this modified image by using a novel threshold array to determine whether a pel from the input image will be printed as a dot as discussed further below. The output of the halftoning processor 640 is input to the printer 650 .
Basic Pattern Growth
Referring now to FIG. 7 , a basic pattern growth example according to one embodiment of the present invention will be described. As in the previous example, a 4×4 halftone matrix allows 17 output levels to be generated, i.e., white 701 and 16 other levels 702 – 717 . Importantly, however, in this example, elements of the basic pattern may make multiple transitions between on and off. For example, element 740 in the upper left transitions from the off state in basic pattern 709 to the on state in basic pattern 710 , back to off in basic pattern 711 , and on to stay in basic pattern 712 . Advantageously, in this manner, more flexibility in terms of pattern choices is provided.
Halftoning via Multiple Threshold Arrays
FIG. 8A illustrates an example of using multiple threshold matrices to allow basic cell patterns to be built by other than subsets of each other. The number of threshold matrices is set by the maximum number of transitions for any particular position in the basic cell. The five threshold matrices illustrated in FIG. 8A have been derived based upon the patterns of FIG. 7 . The convention used by this example is if the input value is less than the threshold at a given position, then a zero is output; otherwise a one is output. In this example, the five transitions experienced by element 750 in the second row, fourth column dictate the number of matrices needed. If the input image is smaller than the output image, the halftoning processor 640 may first scale it (e.g., interpolate it) to the appropriate size.
At any rate, a 4×4 sample 800 from an input image is input to threshold matrices 811 – 815 . The resulting patterns 821 – 825 , respectively, are subsequently combined via an exclusive OR operation, for example, to produce a final pattern 830 which is used to cause the output device (e.g., a bilevel printer) to appropriately deposit ink or toner as shown by output pattern 840 .
While there are a very large number of possible combinations of threshold matrices, in this example, the convention has been adopted that the first time a position has non-zero output is in the top matrix, the next matrix down turns it off, it is turned on again in the third, and so on. Additionally, while in practice the dynamic range of the input data is usually from 0 to 255 and is thresholded with much larger cells, e.g., supercells, for convenience, the dynamic range of the input image in this example is limited to between 0 and 16, inclusive.
FIG. 8B illustrates a special case of FIG. 8A in which the input matrix 850 is constant. In this example, because the 4×4 sample 850 has constant input, the output 890 matches the eighth gray level 709 shown in FIG. 7 . As above, each threshold matrix 811 – 815 is applied to the sample 850 to create a binary output 871 – 875 . These outputs 871 – 875 are then XORed to generate the output image (illustrated both as a binary image 880 and as black and white pels 890 ).
FIG. 9 is a flow diagram illustrating halftoning processing using multiple threshold arrays according to one embodiment of the present invention. In one embodiment, the processing blocks described below may be performed under the control of a programmed processor, such as processor 502 . However, in alternative embodiments, the processing blocks may be fully or partially implemented by any programmable or hardcoded logic, such as Field Programmable Gate Arrays (FPGAs), TTL logic, or Application Specific Integrated Circuits (ASICs), for example.
At processing block 900 , an input grayscale image, such as 4×4 sample 800 , is received. At processing block 910 , a threshold array (e.g., threshold matrices 811 – 815 ) is applied to the input grayscale image producing intermediate outputs (e.g., binary outputs 821 – 825 ). Finally, the intermediate outputs are voted (e.g., combined by an exclusive OR) in block 920 to produce the final output (e.g., binary image 830 ).
Halftoning via Table Lookup FIG. 10A illustrates a table of bit-vectors for creating the basic patterns of FIG. 7 according to one embodiment of the present invention. In this example, each index accesses sixteen bits representing a 4×4 pattern of FIG. 7 . A constant input level of zero corresponds to pattern 701 , a 4×4 square of zero outputs, where zero is white and one is black. A constant input level of eight corresponds to pattern 709 , which has eight elements on and the remainder off. Such a table unambiguously defines the output for each constant input. This may be useful when large areas of graphics are employed. However, other organizations may be more efficient for rapidly changing image data, such as from cameras and scanners.
FIG. 10B illustrates an output optimization of FIG. 10A according to one embodiment of the present invention in which one access yields eight pels of output assuming constant input values. In general, the idea is to gather rows of data together to provide more efficient cache access as the output is generated on a row-by-row basis. Specifically, in this example, two copies of each row are provided in each table entry. As a result, when constant input values are encountered, a single table lookup provides eight pels of output. If the input is not constant, the extra information can be masked off and ignored. Of course, with a larger matrix, it may not be convenient to store two copies of the output. For example, one row of a 32×32 matrix would typically be stored as a 32-bit word rather than duplicating the data as depicted in FIG. 10B .
FIG. 11 illustrates a table organized for more efficient output pel retrieval according to one embodiment of the present invention. In this example, for convenience, a threshold array 1100 has been derived based upon the patterns of FIG. 7 . For each row and column (R,C) 1101 and each input level 1102 , the threshold array 1100 includes an array of bytes 1103 . According to the convention used by this example, the array of bytes 1103 includes a one in the least significant bit (LSB) (i.e., the right most bit) if the input level 1102 corresponds to a pel in the on state at the appropriate position (row 2, columns 1–4, in this example) in the corresponding basic pattern 701 – 717 . For example, when the input pel sample corresponds to basic pattern 701 (e.g., the input level is 0), then row 2, column 1 represents an output pel in the off state and therefore the array of bytes is all zeroes. In contrast, when the input pel sample corresponds to basic pattern 706 (e.g., input level 5), then row 2, column 1 represents an output pel in the on state and therefore the array of bytes has a one in the LSB.
It is contemplated that various other threshold array organizations may be employed. For example, rather than indexing the threshold array by (R,C) and input level, an alternative threshold organization would be to index the threshold array based upon three parameters: the input level, the x coordinate of the pel, and the y coordinate of the pel. For example, as mentioned above, according to one embodiment, the threshold array may be conceptually thought of as a three dimensional (3D) array indexed by u, v, and gray level; where u, and v are the x and y position in the input image modulo N and M (the dimensions of the supercell or the basic cell).
FIG. 12 is a flow diagram illustrating halftoning processing via table lookups according to one embodiment of the present invention. At processing block 1200 , an input grayscale image, such as input levels 1111 – 1118 , is received. At processing block 1210 , an array of bytes is retrieved from the threshold array 1100 based upon the input level of the current pel and the position of the pel in the input image. Then, at processing block 1220 , the array of bytes retrieved is shifted to appropriately align the output pel value.
Referring back to FIG. 11 , a concrete example of how an input sample is transformed into appropriate halftoned output values will now be described with reference to threshold array 1100 (specifically, threshold array entries 1131 – 1138 ), input levels 1111 – 1118 , and output pels 1121 – 1128 . In order to determine the output pel value for input level 1111 , the array of bytes 1103 from entry 1131 is retrieved from threshold array 1100 and the LSB is shifted 7 bits to the left. Similarly, to determine the output pel value for input level 1112 , the array of bytes 1103 from entry 1132 is retrieved and then shifted 6 bits to the left. The output pel value from input level 1113 is determined by retrieving entry 1133 and left shifting the LSB of the array of bytes 1103 by 5 bits. The upper nibble of output pels is completed with the LSB of the array of bytes 1103 corresponding to entry 1134 left shifted 4 bits. The lower nibble of output pels is similarly generated based upon entries 1135 – 1138 left shifted 3, 2, 1, and 0 bits respectively. Finally, the eight shifted bytes are combined to produce one output byte.
In an alternative embodiment, the one bit in the array of bytes 1103 may be positioned such that it is already in the appropriate position for the output pel vector if the output pel corresponds to the lower nibble of the output pel vector and can be adjusted for the upper nibble of the output pel vector by a constant shift.
In the foregoing specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense. | Apparatus and methods for flexible digital halftoning are provided in which novel pattern choices are allowed by not restricting the basic halftone patterns to grow sequentially. Rather, positions in a threshold array allow multiple transitions between on (i.e., printed with toner/ink) and off (not printed) as a function of the input value at the corresponding position. In one embodiment, multiple threshold matrices are employed and the output decision is a vote (e.g., exclusive OR) of the outputs of the individual threshold matrices. In another embodiment, each position contains an arbitrary bit vector to express the output for each input. In yet another embodiment, space efficiency may be achieved by sorting the arbitrary bit vectors into collections of adjacent decisions for a given input value, such as into bytes. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of Ser. No. 11/029,580, filed Jan. 5, 2005, which application is a divisional application of Ser. No. 10/671,845 filed Sep. 25, 2003, now U.S. Pat. No. 6,886,773, which is a standard patent application claiming the benefit of Provisional Patent Application Ser. No. 60/418,520, filed Oct. 15, 2002, the contents of which are incorporated herein by reference.
[0002] This application also relates to U.S. application Ser. No. 10/027,325 filed Dec. 20, 2001, now U.S. Pat. No. 6,779,796; U.S. application Ser. No. 10/027,352 filed Dec. 20, 2001, now U.S. Pat. No. 6,672,543; and U.S. application Ser. No. 10/105,716 filed Mar. 25, 2002, now U.S. Pat. No. 6,683,555.
BACKGROUND OF THE INVENTION
[0003] 1. Technical Field
[0004] The present invention relates to aeronautics and more particularly to trailing devices used on aircraft. Even more particularly, the invention relates to a system and apparatus in which a decoy stored on the aircraft is rapidly deployed for protecting the aircraft and is subsequently retrievable back into the aircraft, ready for subsequent deployment.
[0005] 2. Background Information
[0006] Aerial towed objects are used for a variety of purposes, including decoys, testing, and scientific investigations. In one embodiment, a towed decoy is used to draw various types of guided weapons, such as missiles, away from an aircraft that the weapons are intended to destroy. These towed targets and decoys contain various types of electronic circuits to create an apparent target to a weapon which attracts the weapon to the decoy rather than the aircraft. These types of decoys include devices which counter infrared guided and radar guided missiles that pose the primary threats to military aircraft engaged in a combat environment. It will be appreciated that these missiles use their radar guidance systems to get within striking distance of the aircraft, thereby substantially increasing their probability that the system on the missile will be able to lock onto the target.
[0007] Current military aircraft are vulnerable to attack from surface-to-air and air-to-air missiles. Statistical data on aircraft losses in hostile actions since 1980 show that almost 90 percent of these losses have been the result of missile attacks. As a result, the ability to deploy decoys that can counter guidance systems on these missiles is of great value to protect aircraft during combat situations. To do this, the missile is deflected away by generating a signal that causes the radar guidance system in the missile to think that the target is actually elsewhere than it actually is.
[0008] As the complexity and cost of bodies deployed and towed from various aircraft increases, it becomes increasingly desirable to be able to retrieve them for reuse, while not losing the fast deployment capability that currently exists with non-retrievable deployment systems. The current invention retains the existing fast deployment capability while enabling retrieval and reuse.
[0009] The growth of fast deploy/retrievable technology requires a change in the maintenance philosophy of the system. This change requires that any mechanism used for the deployment, tow and retraction of the body be completely recoverable, ensuring that the body resume it's original pre-deployed state within it's housing. The existing approach of pyrotechnic launch and sever is no longer appropriate. The existing approach of an ejecting aft weather shield is no longer appropriate. The existing approach of blind mating connectors to facilitate rapid stores replacement is no longer worth the cost and reduced reliability.
[0010] The slow speed capability of some craft creates the need for a means of severing the towed body with little or no tension on the towline. The existing pyrotechnic approach becomes less reliable as the tension on the cable is decreased.
[0011] There are also existing devices employing spring loaded booms to help control the separation phase of deployment. However, none are known that use spring loaded fins to accomplish a share of the energy storage.
[0012] In one prior art method to fast deploy, a towed body uses a solenoid braking system. This process is not recoverable and no retrieval mechanism is available. Another prior art fast deploy launch approach uses a pyrotechnic. The existing sever approach uses a pyrotechnic. The existing weather protection approach uses an ejecting aft weather shield. These approaches are not recoverable and require service to the assembly before subsequent deployments. The existing connection approach uses blind mating connectors to facilitate rapid stores replacement. This approach is costly and unreliable and is no longer required.
BRIEF SUMMARY OF THE INVENTION
[0013] The system and apparatus of the present invention provides for the rapid deployment of a decoy from a moving object, such as an aircraft, which is connected to the aircraft by a towing cable preferably containing high voltage and fiber optic conductors to provide radar jamming signals to the decoy for disrupting the flight of a weapon, such as a missile, being guided to the aircraft by radar or other guidance signals.
[0014] Another aspect of the invention is to provide the system with an ejection device which rapidly deploys the decoy from its housing, which subsequently unwinds the cable from a spool containing a length of the towing cable by rotating an outer, generally cylindrical or cup-shaped bailer tube about the cable supply spool, and wherein the cable passes through a passage in the bailer tube and then through a cutter mechanism for severing the cable to detach the decoy from the aircraft should the need arise.
[0015] Another feature of the invention is to mount the cable supply spool in a non-rotational manner on a double helix rotatable shaft which reciprocates the spool along the shaft for removal of the cable from the spool, and wherein a DC motor is operatively connected to the rotatable shaft to control its rotational speed and consequently the payout speed of the cable from the spool reciprocally mounted on the shaft.
[0016] A further aspect of the invention is to provide a cutting mechanism containing a pair of solenoid actuated blades, one of which grips the cable to maintain tension thereon, while a second blade cuts the tensioned cable. This avoids problems occurring in prior severing systems wherein there is insufficient tension on the cable when the severing blade is engaged thereby eliminating the requirement for tension to be provided on the payload end of the system in order to efficiently sever the cable should the need arise after deployment of the decoy from the aircraft.
[0017] A further feature of the invention is to utilize a decoy with spring loaded fins biased to a fully extended position, which fins are engaged with the housing to assist in ejecting or deploying the decoy from the housing to increase the speed of deployment, and wherein the fins are automatically retractable into their loaded state upon the decoy being retrieved and restored in its storage housing beneath the aircraft.
[0018] Still another aspect of the invention is to provide one or more spring biased closure doors mounted on the discharge end of the storage housing which automatically close after the decoy has been retrieved to assist in keeping the decoy and components free of contaminants and harsh weather conditions, and in which the spring biased doors automatically open upon ejection of the decoy and boom from the storage housing.
[0019] A further aspect of the invention is to provide a locking mechanism which secures the cable payout bailer in a locked position upon the decoy reaching its extended position, and in which the lock remains engaged even should electric power be lost to the locking solenoid.
[0020] In further accordance with the invention, the energy stored in the springs which bias an extension boom to a deployment position in combination with the energy stored in the springs of the decoy fins, replace the energy heretofore obtained from pyrotechnic to rapidly deploy the decoy. Likewise, the towed body equipped with spring loaded fins which extend upon deployment, is augmented by the use of spring loaded boom to further eject the decoy and control its position throughout the separation phase of the deployment.
[0021] Furthermore, a DC motor is used to augment and control an optional centrifugal brake for the deployment of the decoy. A feedback and control system controls the speed of the deploying body by allowing it to fall away from the craft and accelerates it to the craft speed by matching separation speed to a predetermined velocity profile. This allows a fast deployment of the body without requiring the use of a transmission to disconnect the retrieval system and a separate braking control mechanism. A cable spool is locked by means of a fail safe pawl mechanism to tow the body without requiring a powered holding mechanism. Retrieval is accomplished by powering the DC motor to rewind the cable onto the spool. The device is fail safe such that in an unpowered condition the body will continue to be towed, and in the event of a failure of the spool lock actuator the body may still be retrieved.
[0022] The foregoing advantages, construction and operation of the present invention will become more readily apparent from the following description and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] A preferred embodiment of the invention, illustrative of the best mode in which applicant contemplates applying the principles, is set forth in the following description and is shown in the drawings and is particularly and distinctly pointed out and set forth in the appended claims.
[0024] FIG. 1 is a diagrammatic view of an aircraft with a decoy being deployed therefrom;
[0025] FIG. 2 is a perspective view of the canister, which houses the decoy and deployment/retrieval mechanism therefor removed from the aircraft;
[0026] FIG. 3 is a diagrammatic sectional view of the decoy and deployment/retrieval mechanism therefor mounted within the canister, which is shown in section;
[0027] FIG. 4 is an enlarged diagrammatic view of the DC motor and cable bailer assembly removed from the canister of FIG. 3 ;
[0028] FIG. 5 is a block diagram of three enlarged fragmentary sectional views of the system components shown in FIG. 3 ;
[0029] FIG. 5A is an enlarged fragmentary sectional view of the bailer assembly of the deployment/retrieval mechanism;
[0030] FIG. 5B is an enlarged fragmentary sectional view showing the towing cable cutter mechanism and bailer locking mechanism of FIG. 3 ;
[0031] FIG. 5C is an enlarged fragmentary sectional view of a portion of the decoy and extendable boom of FIG. 3 ;
[0032] FIG. 6 is a fragmentary diagrammatic perspective view of the decoy mounted within the extendable boom of the deployment/retrieval mechanism with the boom in a retracted position;
[0033] FIG. 7 is a diagrammatic perspective view showing a portion of the boom mechanism shown in FIG. 6 , with the decoy being removed therefrom;
[0034] FIG. 8 is a fragmentary perspective view showing the discharge end of the canister with the decoy starting to be deployed from the open end thereof;
[0035] FIG. 9 is an enlarged diagrammatic exploded perspective view showing the bailer locking mechanism and cutter mechanism;
[0036] FIG. 10 is an enlarged perspective view of the bailer locking mechanism;
[0037] FIG. 11 is an enlarged diagrammatic perspective view of the cutter mechanism and adjacent towing cable removed from the deployment/retrieval mechanism; and
[0038] FIG. 12 is a schematic drawing of a feedback/control system used in a preferred embodiment of the method and apparatus of the present invention.
[0039] Similar numerals refer to similar parts throughout the drawings.
DETAILED DESCRIPTION OF THE INVENTION
[0040] FIG. 1 illustrates one type of aircraft indicated at 1 , in which the improved payout and retrieval system and apparatus of the present invention can be utilized. The system includes a housing or canister 3 , which can have a rectangular shape as shown in FIG. 2 , or other configurations without affecting the invention. Housing 3 preferably is attached to and beneath the body of the aircraft. A decoy or other type of towed device or body indicated generally at 5 , is connected to the deployment/retrieval apparatus by a cable 7 . Decoy 5 can have various constructions, and preferably contains various electronic circuitries and apparatus which sends out various jamming signals to confuse the control signals supplied to an incoming missile intended to strike the aircraft. In order to provide decoy 5 with the desired radar or other missile control jamming signals, cable 7 will contain a source of voltage as well as fiber optics to supply various signals thereto. One example of cable 7 can be of a type described in pending patent application Ser. No. 60/428,156, filed Nov. 21, 2002, the contents of which are incorporated herein by reference.
[0041] Housing 3 has top and bottom walls 9 and 10 and spaced side walls 11 and 12 which form a hollow interior 14 . As shown in FIG. 3 , interior 14 is divided into a forward decoy storage compartment 15 , and an apparatus compartment or chamber 16 .
[0042] In accordance with one of the features of the invention, a bailer mechanism indicated generally at 18 ( FIGS. 4 and 5 ), is mounted within chamber 16 . Bailer mechanism 18 includes a spool 20 which contains a supply length of cable 7 and which is mounted for oscillation along a helix shaft 22 . Shaft 22 preferably is formed with a double helix, and is operatively connected to spool 20 by one or more pawls 23 which are engaged in helical grooves 24 of shaft 22 . A main control shaft 26 is telescopically mounted within and extends through a hollow interior 27 of helix shaft 22 and is connected by a coupler 28 to a DC drive motor 30 . Control shaft 26 is operatively connected to helix shaft 22 by a gear train indicated generally at 31 ( FIG. 5A ), so that rotation of shaft 26 by motor 30 will also rotate helix shaft 22 , but at a slower speed than that of control shaft 26 . Control shaft 26 is mounted by a rear bearing 33 in a fixed bulkhead 34 , which is securely mounted within the interior of housing 3 . The forward end of control shaft 26 ( FIG. 5B ) terminates in a squared end 36 , which secures shaft 26 to a forward hub 37 so that hub 37 rotates with shaft 26 . The forward end of helix shaft 22 is rotatably supported by a bearing 28 on forward hub 37 .
[0043] An outer bailer tub 40 is mounted about control shaft 26 , helix shaft 22 , and spool 20 , and is secured at its forward end to hub 37 by fasteners 41 ( FIG. 5B ) and at its rear end ( FIG. 5A ) by fasteners 42 to a collar 43 , which is rotatably mounted by a bearing ring 44 on bulkhead 34 . Thus, rotation of shaft 26 will rotate bailer tube 40 , as well as rotating helix shaft 22 , all of which in turn are connected directly to DC motor 30 through coupler 28 . A plurality of cable guide rollers 46 , 47 , and 48 are mounted on bailer tube 40 or forward hub 37 to guide the cable from spool 20 through a solenoid locking mechanism and cutter mechanism described further below, for subsequent attachment to decoy 5 .
[0044] An anti-rotation tube 35 is rigidly mounted at one end to bulkhead 34 ( FIG. 5A ) and extends about spool 20 and is formed with a plurality of longitudinally extending slots 39 into which pins 45 extend to prevent rotation of spool 20 and assist in its oscillating movement along helix shaft 22 . Pins 45 are fixedly mounted in spool hub 49 and extend outwardly therefrom and into slots 39 .
[0045] Referring to FIGS. 5A and 5B , when decoy 5 is deployed from housing 3 as discussed further below, tension is applied to cable 7 and will begin to unwind from spool 22 , causing it to oscillate along helix shaft 22 , which in turn will rotate control shaft 26 through gear train 31 , which as shown in FIG. 12 , will supply signals to the control circuitry which controls the speed of the deploying decoy. The control circuitry allows decoy 5 to fall away from the aircraft and accelerate to the aircraft's speed by matching separation speed to a predetermined velocity profile. This allows a fast deployment of the decoy without requiring the use of a transmission to disconnect the retrieval system in a separate braking control mechanism as described further below. U.S. Pat. No. 5,014,997 discloses one method of monitoring the velocity and total deployment distance of the ejected object for subsequent actuation of a braking mechanism upon the ejected body reaching the desired deployment speed and distance. The contents of U.S. Pat. No. 5,014,997 are incorporated herein by reference.
[0046] In accordance with another feature of the invention, the system of the present invention includes a unique deployment mechanism, shown particularly in FIGS. 5C-8 . Decoy 5 , when stored in housing 3 rests upon an extendable boom, which is indicated generally at 50 . Boom 50 is moveably mounted in decoy storage compartment 15 ( FIG. 3 ) and includes a plurality of guide rollers 51 ( FIG. 6 ) which moveably suspend boom 50 on a pair of guide rails 53 which are attached to housing top wall 9 . As shown in FIG. 7 , boom 50 includes a pair of spaced side walls 55 and front and rear decoy rests 56 and 57 extending therebetween. An intermediate decoy capstan 59 is slidably mounted between front and rear decoy rests 56 and 57 by a pair of spaced slide rods 60 . A pair of constant force coil springs 61 are mounted on a bottom wall 62 of boom 50 and a pair of deployment spring strips 63 extend along boom 50 and connect to a pair of posts 64 which are secured to the housing side walls 11 and 12 so that springs 61 bias boom 50 in an outward forward decoy deployment direction as shown by arrow A in FIG. 7 . Thus, springs 61 bias boom 50 in the deployment direction of arrow A which supports decoy 5 in an at-rest retracted stored position within housing 3 , ready for deployment upon a deployment signal being transmitted to the bailer locking solenoid as described further below.
[0047] In further accordance with another feature of the invention, when decoy 5 is supported on extendable boom 50 and stored within housing 3 , a plurality of decoy stabilizing fins 66 are in a retracted position as shown in FIGS. 6 and 8 . Fins 66 are spring biased toward an outward extended position as shown by arrows B in FIG. 8 , and when in the stored position, will engage ejection angled blocks 68 , which are mounted on housing 3 adjacent an open discharge end 69 . This relationship between spring biased fins 66 and blocks 68 further bias decoy 5 in the eject direction of arrow C, as shown in FIG. 8 , in addition to the biasing force exerted thereon by springs 61 .
[0048] In accordance with another feature of the invention, discharge end 69 of housing 3 is closed by a pair of closure doors 71 which are spring biased by springs 72 toward a closed position as shown in FIG. 3 . Doors 71 protect decoy 5 , including the associated components and electronic connections, etc. from exposure to the harsh surrounding atmosphere and weather which will be encountered when mounted beneath aircraft 1 . Two such closure doors 71 are shown in FIG. 8 , which when in the closed position, form a complete closure for end opening 69 . Doors 71 are opened automatically to a position as shown in FIG. 8 , upon boom 50 moving outwardly from housing 3 by the action of ejection springs 61 and spring biased fins 66 .
[0049] In accordance with still another feature of the invention, a cutter mechanism indicated generally at 75 , is mounted within housing 3 , between decoy storage compartment 15 and bailer compartment 16 , for severing cable 7 should the need arise after the decoy has been deployed. Although the present invention contemplates the retrieval of decoy 5 back into housing 3 , certain situations can arise after it has been deployed, where it becomes necessary to detach the decoy from the towing aircraft by severing cable 7 . Heretofore, pyrotechnics was utilized to sever the cable, which has various drawbacks.
[0050] Cutter mechanism 75 includes an electric actuated rotary solenoid 77 which is mounted between a front solenoid mounting plate 78 and a rear solenoid lock plate 79 . Lock plate 79 is rigidly mounted within housing 3 and is connected to bulkhead 34 by a plurality of stabilizing rods 80 ( FIG. 5 ) extending therebetween. Solenoid 77 ( FIG. 11 ) includes a pair of rotatable disks, including a front grabber disk 81 and a spaced rear cutter disk 82 . Solenoid 77 is located adjacent a cable guide bracket 84 which is formed with a pair of slots 85 and 86 . Cable 7 moves through a passage 88 formed in bracket 84 and through slots 85 and 86 . A grabber blade 90 , having a saw tooth edge 91 , is mounted by a fastener 92 on disk 81 and extends outwardly therefrom, and is adapted to move into slot 85 of bracket 84 to grip cable 7 therein. A cutter blade 94 is attached to and extends outwardly from cutter disk 82 and moves into guide bracket slot 86 upon solenoid 77 being actuated. Should the necessity arise for severing cable 7 , solenoid 77 is actuated which rotates disks 81 and 82 in a clockwise direction as shown in FIG. 11 , bringing saw tooth edge 91 into gripping engagement with cable 7 which will maintain tension on cable 7 until blade 94 moves into slot 86 to sever the cable.
[0051] Heretofore, if a blade, whether actuated by pyrotechnics or other type of force, engages cable 7 , the cable may not have sufficient tension thereon to enable the blade to completely sever the cable, depending upon the particular position of the decoy at the time the blade is moved into severing engagement with the cable. However, by first gripping cable 7 with blade 90 , it maintains the cable under tension regardless of the position of the decoy, enabling blade 94 , which follows immediately after blade 90 grips cable 7 , to completely sever the cable. A torsional spring (not shown) is located between disks 81 and 82 to bias disk 81 and blade 90 in the clockwise direction so that blade 90 maintains a gripping engagement with cable 7 as cutter blade 82 rotates into cutting engagement with the cable. A plurality of arcuate slots 95 preferably are formed in grabber disk 81 and have stop pins 96 extending therethrough. This maintains grabber disk 81 in its forward-most gripping position after solenoid 77 is energized and the torsional spring continues to bias disk 81 in this grabbing direction.
[0052] In accordance with still another feature of the invention, a bailer lockout mechanism indicated generally at 100 , is provided to lock bailer mechanism 18 in a fixed non-rotatable condition after the decoy has been deployed to its desired length. Bailer lockout mechanism 100 is best shown in FIGS. 9 and 10 , and includes a rotary solenoid 101 , which is mounted in an offset relationship between plates 78 and 79 . Solenoid 101 includes a rotatable disk 106 which drivingly engages a rotatably mounted cam or gear 111 , which in turn rotates a shaft 102 which is rotatably mounted in and extends through plate 79 . Shaft 102 which is provided with gear teeth 103 ( FIG. 5B ), which matingly engage complementary gear teeth 104 formed on the inner end of a plurality of cams 105 . Cams 105 extend radially outwardly with respect to shaft 102 , and are located within an annular recess 107 formed in the rear of plate 79 . The outer ends of cams 105 are formed with a tooth 108 which is adapted to matingly engage gear teeth 109 formed in a control ring 110 ( FIG. 9 ) which extends into recess 107 and is fixedly connected to forward hub 37 of bailer mechanism 18 as shown in FIG. 5B . The extended ends of cams 105 are formed with holes 112 through which pins 113 extend to pivotally mount cams 105 on plate 79 . Thus, as best shown in FIG. 10 , upon actuation of solenoid 101 , rotation of shaft 102 will pivot cams 105 , moving teeth 108 into engagement with gear teeth 109 of control ring 110 , coupling the solenoid and in particular, cams 105 , with bailer mechanism 18 . Thus, when teeth 108 are engaged with teeth 109 of control ring 110 , it will prevent the rotation of bailer tube 40 which is attached to ring 110 , and correspondingly prevent the further deployment of cable 7 from spool 20 . Thus, upon the control circuitry of FIG. 12 and as discussed in U.S. Pat. No. 5,014,997, detecting that the decoy has reached the desired extended position, lock solenoid 101 is actuated by de-energizing the solenoid, which will rotate lock teeth 108 into engagement with control ring 110 to prevent any further rotation of bailer tube 40 .
[0053] Solenoid shaft 102 is formed with a central hole 115 through which cable 7 extends for connecting the cable to decoy 5 as shown in FIGS. 5B and 5C . A plurality of posts 116 extend between spaced plates 78 and 79 to provide the desired spacing and stability thereto. Front plate 78 is formed with a central hole 118 , which aligns with hole 115 formed in solenoid shaft 102 , to permit the passage of cable 7 therethrough. When decoy 5 is at rest within housing 3 and supported on extendable boom 50 , cable 7 is under sufficient tension to maintain the decoy in housing 3 , in which position outer doors 71 will be closed. In this position, bailer locking mechanism 100 is engaged, preventing the rotation of bailer tube 40 , and thus maintaining the desired tension on cable 7 .
[0054] When in an at rest position, decoy 5 is retained within storage compartment 15 by cable 7 which is wrapped about spool 20 and which is in a locked position by bailer lockout mechanism 100 as discussed above. Upon the appropriate signal being supplied to lockout mechanism 100 , solenoid 101 is energized which rotates shaft 102 in a counterclockwise direction ( FIG. 10 ) to disengage teeth 108 from control ring teeth 109 . Torsional springs 61 and spring biased fins 66 will immediately move boom 50 and supported decoy 5 forwardly in the direction of arrow C ( FIG. 8 ) to eject decoy 5 from housing 3 . The unique combination of coil springs 61 and spring biased fins 66 increases the ejection speed of the decoy from the housing without the use of pyrotechnics. Cable 7 will continue to unwind from spool 20 by oscillating along helix shaft 22 as bailer tube 40 rotates, with cable 7 moving along and in between rollers 46 , 47 , and 48 and through rotary solenoid shaft hole 102 of the bailer lockout mechanism, and through cable passage 88 formed in guide bracket 84 . Decoy 5 continues to be deployed until the desired speed and length of cable 7 has been reached, as discussed above, whereupon appropriate signals are forwarded to DC motor 30 . Motor 30 is energized and provides a reverse or braking effect to the motor shaft and correspondingly, to main drive shaft 26 ( FIG. 5A ). Shaft 26 in turn, slows the rotation of helix shaft 22 through gear train 31 , and correspondingly slows the reciprocal movement of spool 20 therealong. After DC motor 30 has stopped the rotation of shafts 26 and 22 and the movement of the spool 20 preventing further payout of cable 7 therefrom, bailer lockout mechanism 100 is actuated and in particular, rotary solenoid 101 , which moves pawl teeth 108 into locking engagement with teeth 109 of control ring 110 which is fixed to bailer tube 40 , preventing any further rotation of the bailer assembly. As discussed above, should the need arise, cutter mechanism 75 can be actuated to sever the cable to release decoy 5 from being towed by aircraft 1 .
[0055] However, in most situations, it is desired to retrieve decoy 5 back into housing 3 ready for redeployment. This is accomplished easily by energizing rotary solenoid 101 of bailer lockout mechanism 100 , and energizing DC motor 30 to rotate control shaft 26 in an opposite direction from that of the deployment direction, which in turn will rotate helix shaft 22 and oscillate spool 20 therealong to wind cable 7 about the spool, bringing decoy 5 back into position on decoy rests 56 and 57 and decoy capstan 59 of extended boom 50 . After decoy 5 has come to rest on extendable boom 50 , continued tension on cable 7 will move the extended boom back into housing 3 by decoy 5 being drawn further into the housing. Retraction of boom 50 will rewind spring strips 63 within torsional springs 61 so that the springs are ready again to extend boom 50 should the need arise. After boom 50 is retracted, closure doors 71 are automatically pivoted to a closed position by springs 72 , sealing the end of housing 3 from contaminants. Fins 66 will fold in automatically upon entering housing 3 , and will engage angled blocks 68 so that they are also in a biasing position, attempting to eject decoy 5 from housing 3 . Thus, decoy 5 is in position for subsequent deployment should the need arise without requiring any further maintenance or reloading as in prior deployment systems. As shown in FIG. 5A , the retraction force which is exerted by control shaft 26 is coupled directly to the motor, which provides both the retraction force for retrieving decoy 5 , as well as the dynamic braking as the decoy is being deployed from housing 3 .
[0056] There are existing devices employing spring loaded booms to help control the separation phase of deployment. However, none of these devices are known to use spring loaded fins to provide a share of the energy storage. Also, there is no known apparatus which provides for the fast deploy, towed body assembly that uses spring loaded weather doors, zero tension cutter functionality as that of the present invention. The present invention also provides a cutter assembly that uses a holding mechanism to insert zero tension cutter functionality, and provides for severing a towed body with zero tension on the towline.
[0057] Also, as best shown in FIG. 3 , the present invention provides a deployment/retrieval system and apparatus wherein the deployment and retrieval apparatus are in alignment with the decoy instead of being in a stacked relationship as in prior systems. This provides for a more streamlined and compact housing, as shown in FIG. 2 , for mounting on an aircraft.
[0058] The method of the present invention also provides for a controlled fast deployment, tow and retrieval of a towed body behind a craft without the use of a transmission to disengage the retrieval mechanism or separate brake mechanism. The device is fail safe such that in an unpowered condition the body will continue to be towed, and in the event of a failure of the spool lock actuator the body may still be retrieved.
[0059] The method of the present invention also provides all the required functionality in completely recoverable form. Each function operates on deployment in one direction and reverses on retraction such that the initial conditions for subsequent launches is the same as for the initial launch.
[0060] While the present invention has been described in connection with the preferred embodiments of the various figures, it is to be understood that other similar embodiments may be used or modifications and additions may be made to the described embodiment for performing the same function of the present invention without deviating therefrom. Therefore, the present invention should not be limited to any single embodiment, but rather construed in breadth and scope in accordance with the recitation of the appended claims.
[0061] In the foregoing description, certain terms have been used for brevity, clearness, and understanding. No unnecessary limitations are to be implied therefrom beyond the requirement of the prior art because such terms are used for descriptive purposes and are intended to be broadly construed.
[0062] Moreover, the description and illustration of the invention is an example and the invention is not limited to the exact details shown or described. | In a method and apparatus for controlling the deployment of a towline connecting a mooring craft to an ejected object comprising the steps of monitoring velocity to determine when a point for optimum braking has been achieved and then engaging a brake system to retard deployment of the towline, a DC motor augments and controls the brake system. The DC motor further controls the retrieval of the object. A cutter mechanism uses a first blade to grip the towing cable to maintain tension thereon as a second blade cuts the cable. A spring biased boom in combination with spring biased fins on the ejected object rapidly deploys the object from its storage housing. A locking mechanism secures the deployment mechanism in a stable locked position upon the object reaching its fully extended position. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the priority benefit of Taiwan application serial no. 93102569, filed on Feb. 5, 2004.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a semiconductor chip packaging technology. More particularly, the present invention relates to a method of forming a stack package and structure thereof.
2. Description of the Related Art
In recent years, the technology developments and the popularity of portable, handheld and consumer electronic products has almost overshadowed the conventional personal computer (PC) products. To facilitate the manufacturing of these electronic products, most devices are designed towards higher storage capacity and smaller line width to increase the packing density, the operational frequency, to reduce the power consumption and to achieve the integration of multi-functions. In the packaging technology of the integrated circuits (ICs), the chip scale package (CSP) and the wafer level package have been invented to meet the requirements for higher input/output pin count, higher heat-dissipating capacity and reduction of the package size. Furthermore, associated packaging techniques for reducing the weight and cost are also being developed.
In the development of the chip scale package (CSP), a variety of techniques such as the single chip package, the stack chip package and the planar multi-chip package (MCM) are developed. The aforementioned techniques can reduce the dimension of a package to a size only slightly larger than the original size of the chip. However, the technology of the stack chip packages and the planar multi-chip packages must be combined with the known good die (KGD) technique to produce a high yield.
Unlike the conventional chip scale package (CSP) method, the waver level package or wafer level chip scale package (WL-CSP) method packages an entire wafer before dicing up the wafer. Hence, the WL-CSP method can eliminate many process steps such as underfilling, assembling, substrate processing, chip attaching and wire bonding so that the overall fabrication cost can be substantially reduced. In general, the wafer can be packaged regardless of the size of the chip or the pin count. In other words, the wafer level packaging is able to reduce the process steps to thereby shorten the fabrication cycle time, to improve the performance and to lower down the cost. In addition, the amount of saving increases correspondingly with the size of the wafer. Therefore, the wafer level packaging method is particularly advantageous to the wafer processing plants shifting from 8-inch wafer production to 12-inch wafer production.
System on chip (SOC) and system in a package (SIP) are regarded as two principal techniques for producing miniaturized and multi-functional semiconductor devices in the future. In particular, the system on chip (SOC) technique has some promising applications in manufacturing digital information products. At present, the multi-chip package modules with high operating frequency, low cost, small size and short fabrication cycle are the dominant packaging type. For example, a drawing chip or a memory chip is often fabricated by the multi-chip package technology to achieve the high processing frequency, super-fast processing speed and the capacity of integration of multi-functions. Therefore, the known good die technique is important in the packaging process of the multi-chip package technology. After a number of chips are packaged, and the electrical properties of each packaged chip is tested. The chips that fail the test are immediately discarded and the chips that pass the test are integrated by attaching to a packaging product. In this way, the area of the printed circuit board of the package system is reduced and the yield of a conventional multi-chip package is increased.
SUMMARY OF THE INVENTION
Accordingly, at least one object of the present invention is to provide a method of forming an ultra-thin wafer level stack package capable of simplifying the packaging process and increasing overall yield and throughput of the package.
To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, the present invention provides a method of forming an ultra-thin wafer level stack package and package structure thereof. The package structure of the present invention comprises an independent chip set. The independent chip set is obtained by dicing an selectively adhered wafer. The selectively adhered wafer comprises a first wafer and a second substrate attached to the first wafer by using a plurality of adhesives, wherein the second substrate may comprise a plurality of chips, and the positions of the chips are matched with the first wafer. The first wafer has a plurality of base chips formed thereon. The first wafer separates from the second substrate by a distance equal to the thickness of the adhesive glue layer. Accordingly, each independent chip set comprises a base chip and a portion of the second substrate. In addition, a method of forming the adhesives may comprise, for example, a dispensing method. Moreover, a method of forming the adhesives may comprise forming a double side tape having a region comprising the adhesives. Thereafter, after the selectively adhered wafer is obtained and before the independent chip sets are formed, a thermal curing step may further be performed for curing the adhesives.
The method of forming an ultra-thin wafer level stack packages, providing a first wafer having a plurality of base chips thereon, and a second substrate. Next, a first surface of the first wafer is bonded to a first surface of the second substrate by using a plurality of adhesives to form an selectively adhered wafer, wherein a distance between the first wafer and the second substrate is equal to a thickness of the adhesives. Next, a plurality of independent chip sets are formed, wherein each of the independent chip sets comprises the base chip and a portion of the second substrate. The independent chip set is formed by cutting a second surface of the first wafer of the selectively adhered wafer and cutting a second surface of the second substrate of the selectively adhered wafer. In addition, a method of cutting the selectively adhered wafer may comprise a diamond blade cutting method or a laser cutting method. Finally, the independent chip sets are packaged to achieve a packaged IC or chip.
In a preferred embodiment of the present invention, a process of detecting a known good die (KGD) of the base chips of the first wafer is carried out before the commencement of the packaging.
In another preferred embodiment of the present invention, one or more stacked chips are bonded to the base chip after the step of forming the independent chip sets but before the step of packaging the independent chip sets.
In another preferred embodiment of the present invention, the second surface of the first wafer is polished after the step of forming the selectively adhered wafer but before the step of cutting the second surface of the first wafer of the selectively adhered wafer.
According to an aspect of the present invention, at least a stack chip is also attached to the base chip of each independent chip set.
According to another aspect of the present invention, the first wafer has a thickness between 200 μm to 500 μm.
According to another aspect of the present invention, a polishing process is performed over the surface of the first wafer after producing the selectively adhered wafer but before dicing a surface of the first wafer in the selectively adhered wafer.
According to another aspect of the present invention, the first wafer has a thickness between 30 μm to 250 μm after polishing the first wafer in the selectively adhered wafer.
According to another aspect of the present invention, the first wafer preferably has a thickness between 30 μm to 80 μm after polishing the first wafer in the selectively adhered wafer.
According to another aspect of the present invention, a ‘known good die’ (KGD) inspection of the stack chip or base chip is performed.
It is to be understood that both the foregoing general description and the following detailed description are exemplary, and are intended to provide further explanation of the invention as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
FIGS. 1 to 8 are top views and cross-sectional views illustrating a process of forming an ultra-thin wafer level stack package and package structure according to the preferred embodiment of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Like numbers refer to like elements throughout.
FIGS. 1 to 8 are top views and cross-sectional views illustrating the process of forming an ultra-thin wafer level stack package according to a preferred embodiment of the present invention. First, referring to FIG. 1 , a first wafer 102 having a plurality of base chips 112 thereon is provided. As shown, an area marked by the intersection of a solid horizontal line and a solid vertical line defines each base chip 112 . A second substrate 104 is also provided, wherein the second substrate 104 may comprise no chip, or one or more chips previously formed thereon, and the size and position of the chips previously formed has been preset to match with the first wafer 102 . The second substrate 104 can be a transparent or a non-transparent glass substrate comprised of, for example, but not limited to, a silicon wafer substrate, a plastic substrate, an acrylic substrate or a polymer substrate. Thereafter, the second substrate 104 is adhered to the surface of the first wafer 102 with the base chips 112 through a plurality of adhesives 106 to form a selectively adhered wafer 108 . Referring to FIG. 1 , only a few specific areas on the first wafer 102 are adhered to the adhesive 106 . The first wafer 102 separates from the second substrate 104 by a distance equal to the thickness of the adhesives 106 . In one embodiment of the present invention, the method of forming the adhesives 106 comprises, for example, dispensing method. In another embodiment of the present invention, a specific double side tape, for example, having a shape the same as the first wafer 102 may be provided. In addition, the adhesives 106 may be disposed on a portion of the specific double side adhesive tape, for example, the portion corresponding to the first wafer 102 . Therefore, after the first wafer 102 is adhered to the second substrate 104 by the adhesives 106 , a thermal curing process may further be performed for curing the adhesives 106 .
In one preferred embodiment of this invention, a known good die (KGD) inspection of the base chips 112 on the first wafer 102 is carried out prior to the commencement of the packaging process.
After attaching the first wafer 102 to the second substrate 104 using the adhesives 106 , the exposed surface of the first wafer 102 of the selectively adhered wafer 108 facing the direction indicated by the cutting direction 222 in FIG. 2 is polished. The original thickness of the first wafer 102 is in a range of about 200 μm to about 500 μm. After the polishing process, the first wafer 102 of the selectively adhered wafer 108 has a thickness in a range of about 30 μm to about 250 μm. Preferably, the thickness of the first wafer 102 after the polishing process is in a range of about 30 μm to about 80 μm.
Referring to FIG. 2 , the first wafer 102 of the selectively adhered wafer 108 is polished before proceeding with the following steps. However, it is to be noted that even if the polishing step is skipped, the following process steps are the same.
Next, the first wafer 102 of the selectively adhered wafer 108 is diced along the direction indicated by the cutting direction 222 . The depth of the cut is greater than the thickness of the polished first wafer 102 but smaller than the total thickness of the first wafer 102 and the adhesive 106 . Hence, the saw in the dicing process is prevented from cutting into the second substrate 104 . Thereafter, the structure as shown in FIG. 3A and FIG. 3B may be obtained. In one embodiment of the present invention, the method of dicing the selectively adhered wafer 108 may comprise a diamond blade cutting method or a laser cutting method.
After the dicing process, the first wafer 102 is cut into a plurality of first base chips 302 as shown in FIGS. 3A and 3B . Thereafter, the second substrate 104 is diced along the direction indicated by the cutting direction 324 in FIGS. 3A and 3B . The depth of the cut is greater than the thickness of the second substrate 104 but smaller than the total thickness of the second substrate 104 and the adhesive 106 . Thus, the saw in the dicing process is prevented from cutting into the first base chips 302 . Referring to FIGS. 4A and 4B , after the second substrate 104 is diced up, the selectively adhered wafer 108 is cut into a plurality of independent chip sets, wherein each independent chip set comprising at least a first base chip 302 , an adhesive 106 and a portion of the second substrate 404 .
In a preferred embodiment of the invention, as shown in FIG. 5A , after the second substrate 104 is diced up along the cutting direction as shown in FIGS. 3A and 4A , an external stack chip 502 may be bound to the surface of the first base chip 302 of each or some of the independent chip sets. Thereafter, the whole structure as shown in FIG. 5A may be wired and packaged, wherein every packaged integrated circuits (IC) may comprise, the first base chip 302 and the stack chip 502 stacked on the first base chip 302 . In one preferred embodiment of the present invention, a known good die (KGD) inspection of the stack chip 502 can be performed before the stack chip 502 is bound to the independent chip set. In addition, the thickness of the IC package is substantially similar to the whole thickness of the second substrate 404 and the first base chip 302 .
As shown in FIG. 6A , after binding the stack chip 502 to the first base chip 302 of the independent chip set, the independent chip set may be wired and packaged to form an integrated circuit (IC) package that at least comprises a first base chip 302 , a stack chip 502 stacked on the first base chip 302 , and one or more chips 522 on the cut second substrate 404 . In addition, the thickness of the IC is substantially similar to the whole thickness of the second substrate 404 and the first base chip 302 .
In an alternative embodiment as shown in FIG. 5B , a plurality of stack chips may bind to the surface of the first base chip 302 of the independent chip sets after the second substrate 104 is diced up. Here, only two stack chips 512 and 514 are shown, however, more than two stack chips can be provided in the present invention. In one preferred embodiment of this invention, a known good die (KGD) inspection of the stack chips 512 and 514 can be carried out before the stack chips are bound to the independent chip set. In addition, the thickness of the IC is substantially similar to the whole thickness of the second substrate 404 and the first base chip 302 .
After binding the stack chips 512 and 514 to the first base chip 302 of the independent chip set, the excess portion of the second substrate 404 is removed to form a second base plate 604 as shown in FIG. 6B . Thereafter, the independent chip set is packaged to form an integrated circuit (IC) package at least comprising a first base chip 302 , a plurality of stack chips 512 and 514 , and one or more chips 522 on the cut second substrate 404 . In addition, the thickness of the IC package is substantially similar to the whole thickness of the second substrate 404 and the first base chip 302 .
In another embodiment as shown in FIGS. 7 and 8 , a plurality of independent chip sets may be obtained after the surface of the second wafer 104 of the selectively adhered wafer is diced along the directions shown in FIGS. 3B and 4B . In every independent chip set, the overlapped region between the second substrate 404 and the bas chip 302 may be dependent on the demand of the process. In addition, whether the chips 522 , the stack chips 512 and 514 are disposed on the second substrate 404 may be dependent on the demand of the process.
In summary, the present invention provides an ultra-thin wafer level stack packaging structure as shown in FIGS. 7 and 8 . The package structure comprises a base chip 302 , a second base plate 604 and a stack chip 502 or a plurality of stack chips 512 and 514 . The base chip 302 has a plurality of areas with the second base plate 604 bonded to one area of the base chip 302 by an adhesive 106 , and with the stack chip 502 or the stack chips 512 , 514 bonded to another area of the base chip 302 . In addition, one or more chips 522 may be disposed on the second substrate 404 . Moreover, the thickness of the IC package is substantially similar to the whole thickness of the chip 522 , the second substrate 404 and the base chip 302 .
This invention provides a method of forming an ultra-thin wafer level stack package. The advantages of the invention is that the selectively adhering of a second substrate to a first wafer having a plurality of base chips thereon can provide the reduction of the thickness of the first wafer, wherein the second substrate may be pre-designed to match with the first wafer. The thickness of the second substrate need not be too thick but need to be thick enough to maintain the selectively adhered wafer of the first wafer and prevent the second substrate from any deformation during the dicing process of the first wafer. Thus, for example, the second substrate may have a thickness close to that of a conventional wafer. By dicing the first wafer of the selectively adhered wafer, the problem caused from cutting a thin polished first wafer can be avoided. After binding a stack chip to the base chip, the entire assembly is packaged to form an integrated circuit (IC) package. The IC package may comprise at least a base chip and one or more stack chips, wherein the size of the IC package is substantially similar to the whole size of the base chip and the stack chip(s). In addition, the package has a size similar to the base chip and a thickness close to the combined thickness of the second substrat, the polished base chip and the adhesive. In other words, the package has a thickness close to a conventional wafer. Therefore, the package method of the present invention may provide a stack chip package structure.
Furthermore, through the packaging method of the present invention, chips fabricated by different processes can be integrated to form a single package. The circuits that can be fabricated by the same processing steps can be fabricated on the same chip to shorten the fabrication cycle thereof. In addition, chips manufactured by different processes may be packaged together, therefore, the packaged structure is light, thin, and small. Furthermore, if a ‘known good die’ inspection is incorporated to check the stack chips or the base chips, the yield will be improved significantly and the cost will be lowered considerably.
It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the present invention cover modifications and variations of this invention provided they fall within the scope of the following claims and their equivalents. | A method of forming an ultra-thin wafer level stack package and structure thereof are provided. The method includes providing a first wafer having a plurality of base chips thereon, selectively binding the first wafer to a second substrate, lapping the first wafer to reduce its thickness, dicing the lapped first wafer, bonding a plurality stack chips to each base chip and packaging the base chip with the bonded stack chips to form an IC package. Thus, each IC package comprises at least a base chip and a stack chip. The IC package has a size almost identical to the base chip and a thickness a little larger than the combined thickness of the base chip and the stack chip. If a known good die inspection of the base chips and stack chips are carried out prior to wafer level packaging, overall yield of the IC package is increased. | 7 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of copending U.S. patent application Ser. No. 657,222, filed Feb. 11, 1976 now abandoned.
BACKGROUND OF THE INVENTION
Field of the Invention
Compounds of this invention are analogues of natural prostaglandins.
Natural prostaglandins are twenty-carbon atom alicyclic compounds related to prostanoic acid which has the following structure: ##STR1## By convention, the carbon atoms of I are numbered sequentially from the carboxylic carbon atom. An important stereo-chemical feature of I is the trans-orientation of the side-chains C 1 -C 7 and C 13 -C 20 . All natural prostaglandins have this orientation. In I, as elsewhere in this specification, a dashed line (---) indicates projection of a convalent bond below the plane of a reference carbon atom (alpha-configuration), while a wedged line ( represents direction above that plane (beta-configuration). Those conventions apply to all compounds subsequently discussed in this specification.
In one system of nomenclature suggested by N. A. Nelson (J. Med. Chem., 17: 911 (1974), prostaglandins are named as derivatives or modifications of the natural prostaglandins. In a second system, the I.U.P.A.C. (International Union of Pure and Applied Chemistry) system of nomenclature, prostaglandins are named as substituted heptanoic acids. Yet a third system of nomenclature is frequently used by those skilled in the prostaglandin art. In this third system (also described by Nelson), all prostaglandins are named as derivatives or modifications of prostanoic acid (structure I) or prostane (the hydrocarbon equivalent of structure I). This system is used by Chemical Abstracts and may become an I.U.P.A.C. accepted system.
Natural prostaglandins have the structures, ##STR2## in which:
L and M may be ethylene or cis-vinylene radicals and the five-membered ring ##STR3##
Prostaglandins are classified according to the functional groups present in the five-membered ring and the presence of double bonds in the ring or chains. Prostaglandins of the A-class (PGA or prostaglandin A) are characterized by an oxo group at C 9 and a double bond at C 10 C 11 (A 10 , 11); those of the B-class (PGB) have an oxo group at C 9 and a double bond at C 8 -C 12 (Δ 8 ,12); compounds of the C-class (PGC) contain an oxo group at C 9 and a double bond at C 11 -C 12 (Δ 11 ,12); members of the D-class (PGD) have an oxo group at C 11 and an alpha-oriented hydroxy group at C 9 ; prostaglandins of the E-class (PGE) have an oxo group at C 9 and an alpha-oriented hydroxyl group at C 11 ; and members of the F-class (PGF) have an alpha-directed hydroxyl group at C 9 and an alpha-oriented hydroxyl group at C 11 . Within each of the A, B, C, D, E, and F classes of prostaglandins are three subclassifications based upon the presence of double bond in the side-chains at C 5 -C 6 , C 13 -C 14 , or C 17 -C 18 . The presence of a trans-unsaturated bond only at C 13 -C 14 is indicated by the subscript numeral 1; thus, for example, PGE 1 (or prostaglandin E 1 ) denotes a prostaglandin of the E-type (oxo group at C 9 and an alpha-hydroxyl at C 11 ) with a trans-double bond at C 13 -C 14 . The presence of both a trans-double bond at C 13 -C 14 and a cis-double bond at C 5 -C 6 is denoted by the subscript numeral 2; for example, PGE 2 . Lastly, a trans-double bond at C 13 -C 14 , a cis-double bond at C 5 -C 6 and a cis-double bond at C 17 -C 18 is indicated by the subscript numeral 3; for example, PGE 3 . The above notations apply to prostaglandins of the A, B, C, D, and F series as well, however, in the latter the alpha-orientation of the hydroxyl group at C 9 is indicated by the subscript Greek letter α after the numerical subscript.
The three systems of nomenclature as they apply to natural PGF 3 α are shown below: ##STR4## Nelson System:
Prostaglandin F 3 α or PGF 3 α (shortened form) I.U.P.A.C. System:
7-[3R, 5S-Dihydroxy-2R-(3S-hydroxyl-1E,5Z-octadienyl)cyclopent-1R-yl]-5-Z-heptenoic acid Third System (Chemical Abstracts):
(5Z, 9α, 11α, 13E, 15S, 17Z)-9,11,15-trihydroxyprosta-5,13,17-trien-1-oic acid.
It is important to note that in all natural prostaglandins there is an alpha-oriented hydroxyl group at C 15 . In the Cahn-Ingold-Prelog system of defining stereochemistry, that C 15 hydroxyl group is in the S-configuration. The Cahn-Ingold-Prelog system is used to define stereochemistry of any asymmetric center outside of the carbocyclic ring in all three systems of nomenclature described above. This is in contrast to some prostaglandin literature in which the α,β designations are used, even at C 15 .
11-Deoxy derivatives of PGE and PGF molecules do not occur as such in nature, but constitute a class of compounds which possess biological activity related to the parent compounds. Formula II represents 11-deoxy PGE and PGF compounds when: ##STR5## In this formula, and others of this patent specification a swung dash or serpentine line (˜) denotes a covalent bond which can be either in the alpha configuration (projecting below the plane of a reference carbon atom) or in the beta configuration (projecting above the plane of a reference carbon atom).
PGF.sub.β molecules also do not occur as such in nature, but constitute a class of compounds which possess biological activity related to the parent comounds. Formula II represents PGF.sub.β compounds when: ##STR6##
9-Deoxy derivatives of PGE do not occur as such in nature, but constitute a class of compounds which possess biological activity related to the parent compounds. Formula II represents 9-deoxy PGE compounds when: ##STR7##
9-Deoxy-Δ 9 ,10 derivaties of PGE do not occur as such in nature, but constitute a class of compounds which possess biological activity related to the parent compounds. Formula II represents 9-deoxy-Δ 9 ,10 PGE compounds when: ##STR8##
9a-Homo- and 9a-homo-11-deoxy-derivative of PGE and PGF molecules do not occur as such in nature, but constitute a class of compounds which possess biological activity related to the parent compounds. Formula II represents 9a-homo- and 9a-homo-11-deoxy-compounds of PGE and PGF when: ##STR9##
11a-Homo- derivatives of PGE, PGF and PGA molecules do not occur as such in nature, but constitute classes of compounds which are expected to posses biological activity related to the parent compounds. Formula II represents 11a-homo- derivatives of PGE, PGF and PGA molecules when: ##STR10##
11-Epi-PGE and PGF molecules do not occur as such in nature, but constitute classes of compounds which possess biological activity related to the parent compounds. Formula II represents 11-epi-compounds of PGE and PGF when: ##STR11##
8Iso-, 12iso or 8,12-bis iso (ent) prostaglandins do not occur as such in nature, but constitute classes of compounds which possess biological activity related to the parent compounds. Formula II represents 8iso-, 12iso- or 8,12-bis iso (ent) compounds when: ##STR12## These iso modifications of Formula II may be divided into all of the sub-classes with varying ring oxygenation as described above.
Recent research indicates that prostaglandins are ubiquitous in animal tissues and that prostaglandins, as well as their synthetic anlogues, have important biochemical and physiological effects in mammalian endocrine, reproductive, central and peripheral nervous, sensory, gastro-intestinal, hematic, respiratory, cardiovascular, and renal systems.
In mammalian endocrine systems, experimental evidence indicates prostaglandins are involved in the control of hormone synthesis or release in hormone-secretory glands. In rats, for example PGE 1 and PGE 2 increase release of growth hormone with PGA 1 increased synthesis of that hormone. In sheep, PGE 1 and PGF 1 α inhibit ovarian progesterone secretion. In a variety of mammals, PGF 1 α and PGF 2 α act as luteolytic factors. In mice, PGE 1 , PGE 2 , PGF 1 α and PGF 1 β increase thyroid activity. In hypophysectomized rats, PGE 1 , PGE 2 and PGF 1 α stimulate steroidogenesis in the adrenal glands.
In the mammalian male reproductive system, PGE 1 contracts the smooth muscle of the vas deferens. In the female reproductive system, PGE and PGF.sub.α compounds contract uterine smooth muscle. In general, PGE, PGB and PGA compounds relax in vitro human uterine muscle strips, while those of the PGF.sub.α class contact such isolated preparations. PGE compounds in general promote fertility in the female reproductive system while PGF 2 α has contragestational effects. PGF 2 α also appears to be involved in the mechanism of menstruation. In general, PGE 2 exerts potent oxytocic effects in inducing labor, while PGF 2 α induces spontaneous abortions in early pregnancy.
PGF.sub.α and PGE compounds have been isolated from a variety of nervous tissue and they seem to act as neurotransmitters. PGE 1 retards whereas PGF 2 α facilitates transmission in motor pathways in the central nervous system. It has been reported that PGE 1 and PGE 2 inhibit transmitter release from adrenergic nerve endings in the guinea pig.
Prostaglandins stimulate contraction of gastrointestinal smooth muscle in vivo and in vitro. In dogs, PGA 1 , PGE 1 and PGE 2 inhibit gastric secretion. PGA 1 exhibits similar activity in man.
In most mammalian respiratory tracts, compounds of the PGE and PGF class relax in vitro preparations of tracheal smooth muscle. In that preparation, PGE 1 and PGE 2 relax while PGF 2 α contracts the smooth muscle. PGE and PGF compounds are normally found in the human lung, and it is postulated that some cases of bronchial asthma involve an imbalance in the production or metabolism of those compounds.
Prostaglandins are involved in certain hematic mechanisms in mammals. PGE 1 , for example, inhibits thrombogenesis in vitro through its effects on blood platelets.
In a variety of mammalian cardiovascular systems, compounds of the PGE and PGA class are vasodilators whereas those of the PGF.sub.α class are vasoconstrictors, by virtue of their action on vascular smooth muscle.
Prostaglandins are naturally found in the kidney and reverse experimental and clinical renoprival hypertension.
The clinical implications of prostaglandins and their analogues are far-ranging and include, but are not limited to the following: in obstetrics and gynecology, they may be useful in fertility control, treatment of menstrual disorders, induction of labor, and correction of hormone disorders; in gastroenterology, they may be useful in the treatment of peptic ulcers and various disorders involving motility, secretion, and absorption in the gastrointestinal tract; in the respiratory area, they may be beneficial in therapy of bronchial asthma and other diseases involving bronchoconstriction; in hematology, they may have utility as anti-clotting agents in diseases such as venous thrombosis, thrombotic coronary occlusion and other diseases involving thrombi; in circulatory diseases they have therapeutic utility in hypertension, peripheral vasopathies, and cardiac disorders.
For a more complete review of chemical, physiological and pharmacological aspects of the prostaglandin, consult the following references: The prostaglandins, Vol. I., P. Ramwell, Ed., New York, Plenum Press, 1973; Ann, N.Y. Acad. Sci., 180: 1-568 (1971): and Higgins and Braunwald, J. Am. Med. Assn., 53: 92-112 (1972).
DESCRIPTION OF THE PRIOR ART
Great Britain patent application No. 027,844 filed June 14, 1971 discloses cycloalkyl or adamantyl derivatives of prostaglandins.
Netherland Pat. No. 7,315,307 discloses cycloalkyl, adamantyl or 2-norbornyl derivatives of prostaglandins.
Japan Pat. No. 75 58,036 discloses 16-butylprostadienoic acids.
U.S. Pat. No. 3,867,375 discloses a process and reagents for preparing prostaglandins and derivatives.
SUMMARY
Novel and useful monospiroalkyl analogues of prostaglandins having the following structural formula III constitute the subject matter of this invention: ##STR13## In formula III:
D is R-hydroxymethylene or S-hydroxymethylene radical;
J is a methylene, R-hydroxymethylene, S-hydroxymethylene or a methine radical such that J is methine only when K is methine;
K is a methylene, ethylene or a methine radical such that K is ethylene only when J is methylene and K is methine only when J is methine;
L is a carbonyl, R-hydroxymethylene or S-hydroxymethylene radical;
Q is an ethylene or Z-vinylene radical;
T is an alkoxycarbonyl having from 1 to 3 carbon atoms inclusive in the alkyl chain, carboxyl, or hydroxymethyl radical or pharmacologically acceptable nontoxic carboxy salts; and
B is a monospiroalkyl radical of the formula ##STR14## where m is an integer having a value of from 0 to 2; n is an integer having a value of from 1 to 4; p is an integer having a value of from 3 to 11; and the sum of the integers m and n is less than or equal to 4 and where G is hydrogen or lower alkyl of 1 to 3 carbon atoms.
The numbering system and the stereochemistry nomenclature used for the prostaglandins of this invention are according to the I.U.P.A.C. definitive and tentative rules which designate the carboxylic acid side chain as the parent compound. In Formula III, a swung dash or serpentive line (˜) denotes a covalent bond which can be either in the alpha configuration (projecting below the plane of a reference carbon atom) or in the beta configuration (projecting above the plane of a reference carbon atom). As used herein, cis or trans isomerism around double bonds respectively in designated by affixes Z (zusammen) and E (entgegen). Chirality around asymmetric carbon atoms is designated by affixes R (rectus) and S (sinister).
Analogues or derivatives of the A-, E-, and F- classes of the natural prostaglandins are represented by Formula III. Thus when, L is carbonyl, and both J and K are methine radicals, III represents analoges of the A- class of prostaglandins: ##STR15##
When L is carbonyl, K is methylene or ethylene and J is methylene or hydroxymethylene such that K is ethylene only when J is methylene, III represents analogues of the E-class, 11-deoxy-E- class or 9a-homo-11-deoxy-E-class of prostaglandins: ##STR16##
When L is carbonyl, K is methylene and J is R-hydroxymethylene or S-hydroxymethylene, III represents analogues of the E-class of prostaglandins: ##STR17##
When L is carbonyl and both J and K are methylene, III represents analogues of the 11-deoxy-E-class of prostaglandin: ##STR18##
When L is carbonyl, K is ethylene and J is methylene, III represents analogues of 9a-homo-11-deoxy-PGE class of prostaglandins. ##STR19##
When L is R-hydroxymethylene or S-hydroxymethylene; K is methylene or ethylene, such that K is ethylene only when J is methylene, J is R-hydroxymethylene, S-hydroxymethylene or methylene, III represents analogue of PGF.sub.α, PGF.sub.β, 11-deoxy-F.sub.α, 11-deoxy-F.sub.β, 9a-homo-11-deoxy F.sub.α and 9a-homo-11-deoxy F.sub.β : ##STR20##
When L is R-hydroxymethylene or S-hydroxymethylene; K is methylene; and J is R-hydroxymethylene or S-hydroxymethylene, III represents analogues of PGF.sub.α and PGF.sub.β ##STR21##
When L is formula IIIf above is S-hydroxymethylene and J is R-hydroxymethylene, analogues of the F.sub.α class of prostaglandins are represented.
When L in formula IIIf above is R-hydroxymethyl and J is R-hydroxymethylene, analogues of the F.sub.β class of prostaglandins are represented.
When J is formula IIIf above is methylene, analogues of the 11-deoxy-F.sub.α and 11-deoxy-F.sub.β are represented.
When in formula IIIf above, K is ethylene and J is methylene, then analogues of the 9a-homo-11-deoxy F.sub.α and 9a-homo-11-deoxy F.sub.β classes of prostaglandin are represented.
When Q, in formulae IIIa, IIIb, IIIc, IIId, IIIe, IIIf and IIIg above is ethylene, then analogues of the A 1 , E 1 , 11-deoxy-E 1 , 9a-homo-11-deoxy-E 1 , F 1 α, F 1 β, 11-deoxy-F 1 α, 11-deoxy-F 1 β, 9a-homo-11-deoxy-F 1 α and 9a-homo-11-deoxy-F 1 β classes of prostaglandins are respectively represented.
When Q in formulae IIIa, IIIb, IIIc, IIId, IIIe, IIIf and IIIg above is Z-vinylene, then analogues of the A 2 , E 2 , 11-deoxy-E 2 , 9a-homo-11-deoxy-E 2 , F 2 α, F 2 β, 11-deoxy-F 2 α, 11-deoxy-F 2 β, 9a-homo-11-deoxy-F 2 α and 9a-homo-11-deoxy-F 2 β classes of prostaglandins are respectively represented.
When T in formulae IIIa, IIIb, IIIc, IIId, IIIe, IIIf and IIIg above is an alkoxycarbonyl having from 1 to 3 carbon atoms inclusive in the alkyl chain, carboxyl, or pharmacologically acceptable nontoxic carboxy salts, then the C 1 esters, acids and salts of the various A-, E- and F- classes of prostaglandins are represented.
When T in formulae IIIa, IIIb, IIIc, IIId, IIIe, IIIf and IIIg above is hydroxymethyl, then the C 1 alcohols of the various A-, E- and F- classes of prosgaglandins are represented.
When formula III above is ##STR22## then III represents the natural configuration of prostaglandins about the C 8 and C 12 positions, and when formula III is ##STR23## then III represents the 8, 12-bis iso (ent) class of prostaglandins.
The term (dl) as used herein refers to racemic mixtures and where used as a prefix to a particular isomer structure, it designates a racemic mixture of the indicated isomer and its mirror image.
Useful intermediates in the preparation of compounds of formula III are represented by the formula: ##STR24## wherein: X is an iodo or bromo radical;
A is an acid-labile hydroxyl-protecting group selected from the class consisting of 1-ethoxyethyl, trimethylsilyl, tert-butyl-dimethylsilyl, 2-ethoxy-prop-2-yl, tetrahydropyran-2-yl, or triphenylmethyl radicals; and
B is selected from the class of monospiroalkyl radicals of the formula ##STR25## where m is an integer having a value of from 0 to 2; n is an integer having a value of from 1 to 4; p is an integer having a value of from 3 to 11; and the sum of the integers m and n is less than or equal to 4 and where G is hydrogen or lower alkyl of 1 to 3 carbon atoms.
DESCRIPTION OF THE INVENTION
Compounds having Formula III are prepared via the 1,4-conjugate addition of organocopper reagents to cyclopentenones as reported by Sih, et al., (J. Amer. Chem. Soc., 97: 857,865 (1975) and references cited therein). The novel compounds of Formula III are prepared according to the reaction sequence depicted in Table A.
TABLE A__________________________________________________________________________ ##STR26## ##STR27## ##STR28##__________________________________________________________________________
In Table A, Compound IV, where X is an iodo or bromo radical and A is an acid-labile hydroxyl-protecting group, is contacted and reacted with Metallic lithium or lower alkyl lithium (Compound V) at from about -80° C to 0° C for about 0.25 to 3.0 hours in an inert solvent, such as ether, tetrahydrofuran, hexane, pentane, toluene, mixtures thereof and the like, under an inert atmosphere, such as argon, nitrogen and the like. Copper(I) complex (Compound VI) is added, usually as a solution in an inert solvent, to the reaction mixture and the mixture is then stirred at less than about -20° C for about 0.25 to 1.0 hour. A solution of Compound VII, where J' is methylene or ═CHOA and T' is alkoxycarbonyl or --CH 2 OA, usually in an inert solvent, is added to the reaction mixture which is then allowed to warm to about -20° C to 25° C over a 0.5 to 5 hour period to yield the intermediate Compound VIII after quenching with a proton donor. Treatment of the latter compound under hydrolysis conditions such as with a weakly-acidic water mixture, such as acetic acid-water (65:35 V/V) with 10% tetrahydrofuran, under an inert atmosphere at a temperature of about 20° C to 45° C for about 0.5 to 48 hours cleaves the acid-labile hydroxyl-protecting groups (described in J. Amer. Chem. Soc., 94:6194[1972]) to yield Compound IIIb.
Where J and K of Compound IIIb are respectively hydroxymethylene and methylene, dehydration of Compound IIIb with a weakly-acidic water mixture, such as acetic acid-water, at about 60° C to 80° C (described in J. Org. Chem., 34:3552 [1969]) yields Compound IIIa. Compound IIIa is also obtained as a byproduct of the acidic hydrolysis of Compound VIII.
Reduction of Compound IIIB with sodium borohydride in an alcoholic or other suitable polar solvent (described in J. Org. Chem., 34:3552[1969]) yields Compound IIIf.
When T of Compound IIIb (where J is methylene) or IIIf is alkoxycarbonyl, cleavage of the ester group with a base, such as sodium hydroxide or potassium hydroxide in a mixed organic solvent such as water-tetrahydrofuran, water-p-dioxane or water-alcohol (described in J. Amer. Chem. Soc., 94:7823 [1973]) yields the corresponding acid, i.e. where T is carboxyl. Where J and T of Compound IIIb are respectively hydroxymethylene and alkoxycarbonyl, cleavage of the ester group by exposure to Rhizopus oryzae (described in J. Amer. Chem. Soc. 95:1676[1973] or with a suitable esterase or lipase (described in U.S. Pat. No. 3,769,166 and German patent application No. 2,242,792) yields the corresponding acid, i.e. where T is carboxyl.
Treatment of Compounds IIIa or IIIb, where T is carboxyl or alkoxycarbonyl group, with a carbonyl protecting group followed by reduction and treatment with nitrous acid yields the corresponding primary alcohol, i.e. where T is hydroxymethyl (described in U.S. Pat. No. 3,636,120). Suitable carbonyl protecting groups include lower alkoxyamines, semicarbazide or thiosemicarbazides. Suitable reducing agents include lithium aluminum hydride, lithium borohydride, and diisobutyl aluminum hydride.
Non-toxic, pharmacologically acceptable salts of Compound III can be prepared by neutralization of III, where T is carboxyl, with an equivalent or an excess amount of the corresponding non-toxic salt-forming organic or inorganic base. The salts are prepared by procedures which are well-known in the art. Suitable salts include sodium, potassium, ammonium and the like. The salts may be isolated by lyophilization of the resulting mixture, or by filtration if sufficiently unsoluble, or by similar well-known techniques.
All compounds of this invention can be isolated from reaction mixtures and purified by well-known organic chemistry procedures. For example, the compounds can be isolated by dilution of the reaction mixture with water; extraction with a water-immiscible solvent, such as benzene, cyclohexane, ether, ethyl acetate, methylene chloride, toluene and the like; chromatography; distillation and the like or a combination of these procedures. Purfication of these compounds can be accomplished by methods which are well-known in the art for the purification of prostaglandins, lipids, fatty acids, and fatty esters. For example, such methods as reverse phase partition chromatography; countercurrent distribution; adsorption chromatography on acid washed magnesium silicate, neutral or acid washed silica gel, alumina or silicic acid; preparative paper chromatography; preparative thin layer chromatography; high pressure liquid-liquid chromatography; gas-liquid chromatography and the like or combinations thereof can be used to purify the compounds produced by the processes of this invention.
The starting reactants used in the above procedures are well-known or easily prepared by known methods. For instance, in the reaction sequence depicted in Table A, Compound V, i.e. metallic lithium or lower alkyl lithium such as t-butyllithium, sec-butyllithium or n-butyllithium are commercially available or prepared by well-known organic chemistry methods. Examples of Compound VI, i.e. copper(I) complexes, include: [hexamethylphosphorous triamide] 2 copper(I)pentyne (preparation described in J. Amer. Chem. Soc., 94:7210[1972]; and J. Org. Chem., 31:4071[1966]); tri-n-butylphosphine-copper(I)iodide (preparation described in Inorg. Synth., 7:9[1963]); hexamethylphosphorus triamide-copper(I)iodide (preparation described in Prostaglandins, 7:387[1974]); copper(I) thiophenolate (preparation described in Synthesis 662[1974]) and the like. Examples of Compound VII which are employed in the synthesis of III include: Methyl 7-(5-oxocyclopent-1-enyl)heptanoate (preparation described in Tet. Let., 24:2435[1972]); methyl 7-[3R-(tetrahydropyran-2-yloxy)-5-oxocyclopent-1-enyl]heptanoate (preparation described in J. Amer. Chem. Soc., 95:1676[1973]); 1-(tetrahydropyran-2-yloxy)-7-(5-oxocyclopent-1-enyl)heptane (preparation described in Tet. Let., 773[1972]); Methyl 7-(5-oxocyclopent-1-enyl)hept-5Z-enoate (preparation described in J. Org. Chem., 38: 3413[1973]); Methyl 7-[3R-(tetrahydropyran-2-yloxy)-5-oxocyclopent-1-enyl]hept-5Z-enoate (preparation described in Tet. Let., 2313[1973] ); Methyl 7-(6-oxocyclohex-1-enyl)hept-5Z-enoate (preparation described in copending U.S. Ser. No. 657,221, filed Feb. 11, 1976; 1-(tetrahydropyran-2-yloxy)-7-[3R-tetrahydropyran-2-yloxy)-5-oxocyclopent-1-en-1R-yl]heptane (preparation described in copending U.S. Ser. No. 657,221, filed Feb. 11, 1976); and 1-(tetrahydropyran-2-yloxy)-7-[3R-(tetrahydropyran-2-yloxy)-5-oxocyclopent-1-enyl]hept-5Z-ene (preparation described in copending U.S. Ser. No. 651,221, filed Feb. 11, 1976, which is incorporated herein by reference.
Compound IV of Table A is prepared according to the reaction sequence depicted in Table B. Examples of compounds having formula IV which are used in the reaction IV → III include: 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro-[3.3]hept-2-yl)-1E-propene; 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[5.5]undec-3-yl)-1E-propene and the like. The synthesis of Compound IV from the corresponding spiroalkyl acid IVa can be accomplished via the reaction sequence of Table B by well-known organic chemistry procedures.
TABLE B______________________________________ ##STR29## ##STR30## ##STR31## ##STR32## ##STR33## ##STR34##In IVa → IVb, the monospiroalkyl acid IVa is converted to the acidchloride IVb using an acid chloride forming reagent such as thionylchloride, oxalyl chloride, phosphorus trichloride and the like asdescribed in Fieser & Fieser, Reagents For Organic Synthesis, I:1158, J.Wiley & Sons Inc. (1967). In IVb → IVc, the acid chloride IVb isreacted with acetylene in an inert solvent, such as carbon tetrachloride,methylene chloride or the like, in the presence of a Lewis acid such asaluminum chloride, stannic chloride or the like to produce theβ-chlorovinyl ketone IVc as described in Chem. Revs., 161(1965) andOrg. Synth., IV:186, J. Wiley & Sons Inc. (1963). In IVc → IVd,the β-chlorovinyl ketone IVc is converted into the correspondingβ-iodo-or β-bromo-vinyl ketone IVd, where X is an iodo or bromoradical, using a soluble salt, such as sodium iodide, sodium bromide,lithium bromide or the like, in a polar inert solvent, such as acetone,acetonitrile and the like, as described in J. Amer. Chem. Soc., 94:7210(1972). In IVd → IVe, Compound IVd is reduced to thecorresponding β-iodo- or β-bromo-vinyl alcohol using a suitablereducing agent, such as sodium borohydride in alcohol solvent or lithiumaluminum hydride in ether solvent as described in J. Amer. Chem. Soc.,94:7210(1972). In IVe → IV, Compound IVe is contacted and reactedwith a suitable acid-labile hydroxyl-protecting group (A) such asdihydropyran as ethylvinyl ether in the presence of an acid catalyst suchas p-toluenesulfonic acid, 98% sulfuric acid or phosphorus oxychloride;or a trialkylsilylchloride, such as trimethylsilylchloride ort-butyldimethylsilylchloride, or triphenymethylbromide in the presence ofa basic catalyst such as triethylamine or imidazole. Any protecting groupwhich is removable under mildly acid conditions and is stable toalkyllithium and alkylcopper(I)reagents can also be suitably used, see J.
In Table B, compound IVc can be prepared from compound IVa, where B is ##STR35## by reacting IVa with methyl lithium in an inert solvent such as ethyl ether to produce the sprioalkyl methyl ketone as described in Org. Reactions, 18:1(1970). The spiroalkyl methyl ketone is then dissolved in ethyl ether and methyl formate and treated with sodium hydride to form the spiroalkyl hydroxyvinyl ketone as described in J. Amer. Chem. Soc. 76:552 (1954). The hydroxyvinyl ketone is then treated with an acid chloride forming reagent such as thionyl chloride to form the β-chloro-vinyl ketone IVc as described in Chem. Revs., 161(1965).
Examples of the corresponding monospiroalkyl compounds having formula IVa include: spiro[3.3]heptyl-2-carboxylic acid: spiro[5.5] undecyl-3-carboxylic acid and 2-methylspiro [3.3]heptyl-2-carboxylic acid. The compounds of formula IVa are either commercially available or easily prepared by well-known techniques from commercially available materials. For example, the compound 1,1-cyclobutanedicarboxylic acid (Beil. 9:725; available from Aldrich Chemical Co., Inc.) is reduced with lithium aluminum hydride to produce 1,1-di(hydroxymethyl)cyclobutane by a similar procedure as described in Fieser & Fieser, Reagents for Org. Synth., 1:581, J. Wiley & Sons, (1967). This compound is then esterified with p-toluenesulfonyl chloride to produce 1,1-di(toluenesulfonylmethyl)cyclobutane. This latter compound is cyclized with diethyl malonate to produce spiro[3.3]heptane-2,2-dicarboethoxy ester followed by hydrolysis in ethanolic potassium hydroxide to produce spiro[3.3]heptyl-2,2-dicarboxylic acid. This compound is then thermally decarboxylated to produce spiro[3.3]heptyl-2-carboxylic acid which is used in the reaction sequence depicted in Table B to produce 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[3.3]hept-2-yl)-1E-propene. These procedures are described collectively in J. Org. Chem., 29:2914(1964); J. Org. Chem., 31:4069 (1966); and Justus Liebigs Ann. Chem., 685:74(1965).
Spiro[5.5]undecyl-3-carboxylic acid (either commercially available or prepared by well-known methods such as described in U.S. Pat. No. 3,350,442) is used in the reaction sequence depicted in Table B to produce 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[5.5]undec-3-yl)-1E-propene.
The compound 2-methylspiro[3.3]heptane-2-carboxylic acid can be prepared from the spiro[3.3]heptane-2-carboxylic acid as described in Tet. Let, 2221 (1974) and J. Org. Chem., 35:262 (1970).
The compounds represented by Formula III inhibit aggregation of human platelets in vitro as demonstrated in the following Example 15. It is that feature which distinguishes the compounds of this invention over the natural prostaglandins. Of the natural prostaglandins, only PGE 1 displays a similar activity. Preferred compounds of those represented by formula III which inhibit aggregation of platelets are compounds TR-4120 and TR-4845. It should be noted that while the natural PGE 1 compounds display a similar activity, the compounds of the present invention do not exhibit the undesirable side effects observed in the natural PGE 1 compounds.
The prostaglandin analogues of this invention also stimulate in vitro and in vivo smooth muscle preparations derived from a variety of tissues and organs of experimental animals. Such smooth muscle assays are widely utilized to determine the activity of natural prostaglandins as well as prostaglandin analogues (Bundy et al., Ann. N.Y. Acad. Sci., 180:76[1961]; Bergstrom et al., Pharmacol. Revs., 20:1[1968]). Details of the activity of certain compounds having Formula III are presented in Example 15 below.
Compounds of the formulae, collectively referred to as IIIx, ##STR36## wherein J is R-hydroxymethylene or methylene; T is an alkoxycarbonyl having from 1 to 3 carbon atoms inclusive in the alkyl chain, carboxyl, hydroxymethyl or pharmacologically acceptable nontoxic carboxy salts; and G is hydrogen or methyl, are useful in a therapeutic method of inhibiting gastric secretion in an individual for whom such therapy is indicated by administering to that individual an amount of a compound having structure IIIx that is effective in inhibiting or decreasing gastric secretion. The term "individual" as utilized in this specification means a human being or a standard experimental animal that is a model for a human being. Indications for use of compounds IIIx are any conditions in which inhibition or decrease of gastric secretion is desirable, such as peptic or duodenal ulcers, hyperacidity, and the like. The term "effective antisecretory amount" or any equivalent of the term means a dose or a series of doses that will decrease or inhibit gastric secretion. Although that amount will vary from individual to individual and from indication to indication, it is easily determined by one skilled in the art without undue experimentation. Compounds IIIx may be administered by known conventional modes of therapeutic administration such as intravenous, parenteral, buccal, rectal or oral. The oral mode, however, is preferred. Dose forms for administration of compounds IIIx can be prepared by recognized methods in the pharmaceutical sciences. Use of methyl 7-{3R-hydroxy-5-oxo-2R-[3R-hydroxy-3-(spiro[3.3]hept-2-yl)-1E-propenyl]cyclopent-1R-yl}heptanoate; 7-{3R-hydroxy-5-oxo-2R-[3R-hydroxy-3-(spiro[3.3]hept-2-yl)-1E-propenyl]cyclopent-1R-yl}heptan-1-ol; methyl 7-{3R-hydroxy-5-oxo-2R-[3R-hydroxy-3-(2-methylspiro[3.3]hept-2-yl)-1E-propenyl]cyclopent-1R-yl}heptanoate; 7-{3R-hydroxy-5-oxo-2R-[3R-hydroxy-3-(2-methylspiro[ 3.3]hept-2-yl)-1E-propenyl]cyclopent-1R-yl}heptan-1-ol; and dl 7-{5-oxo-2R-[3R-hydroxy-3-(spiro[3.3]hept-2-yl)-1E-propenyl]cyclopent-1R-yl}heptanoic acid are preferred.
The preferred compounds TR-4120 and TR-4845 mentioned above are represented by the formula IIIy ##STR37## where G is hydrogen or methyl, and are particularly useful in a therapeutic method of inhibiting platelet aggregation in an individual for whom such therapy is indicated by administering to that individual an amount of compound IIIy that is effective in inhibiting or decreasing platelet aggregation. Indications for use of compound IIIy are any condition in which inhibition or decrease of platelet aggregation is desirable, such as ischemic heart disease, high blood pressure, post surgical conditions and the like. The term "effective antiaggregating amount" or any equivalent of the term means a dose or a series of doses that will decrease or inhibit platelet aggregates. Although that amount will vary from individual to individual and from indication to indication, it is easily determined by one skilled in the art without undue experimentation. Compounds IIIy may be administered by known conventional modes of therapeutic administration such as intravenous, rectal, oral and the like. Dose forms for administration of compounds IIIy can be prepared by recognized methods in the pharmaceutical science.
The compound, 7-{3R-hydroxy-5-oxo-2R-[3R-hydroxy-3-(2-methylspiro[3.3]hept-2-yl)-1E-propenyl]cyclopent-1R-yl}heptan-1-ol (TR-4852), which is represented by the formula ##STR38## is particularly useful in a therapeutic method for inducing uterine contractions in an individual for whom such therapy is indicated by administering to that individual an amount of Compound TR-4852 above that is effective in inducing uterine contractions. Indications for use of Compound TR-4852 are any condition in which inducement of uterine contraction is desirable, such as inducement of labor. The term "effective uterine contracting amount" or any equivalent of the term means a dose or a series of doses that will induce uterine contraction. Although that amount will vary from individual to individual and from indication to indication, it is easily determined by one skilled in the art without undue experimentation. Compound TR-4852 may be administered by known conventional modes of therapeutic administration such as intravenous, rectal, oral and the like. Dose forms for administration of Compound TR-4852 can be prepared by recognized methods in the pharmaceutical science.
The following Table C illustrates preferred embodiments of the present invention compiled by Compound No., Example No. and identified by the I.U.P.A.C. system of nomenclature.
TABLE C__________________________________________________________________________Compound ExampleNo. No. I.U.P.A.C. Nomenclature Chemical Abstracts Nomenclature__________________________________________________________________________TR-4126 2A Methyl 7-{5-oxo-2R-[3S-hydroxy-3- Methyl 15S-Hydroxy-16,18-methano-18,20- (spiro[3.3]hept-2-yl)-1E-propenyl]- methano-9-oxoprosta-10, 13E-dien-1-oate cyclopent-3-en-1R-yl}heptanoate.TR-4127 2B Methyl 7-{5-oxo-2R-[3R-hydroxy-3- Methyl 15R-hydroxy-16, 18-methano-18, (spiro[3.3]hept-2-yl)-1E-propenyl]- 20-methano-9-oxoprosta-10, 13E-dien- cyclopent-3-en-1R-yl}hepanoate. 1-oateTR-4120 1A Methyl 7-{3R-hydroxy-5-oxo-2R-[3R- Methyl 11α, 15R-Dihydroxy-16, 18-methano- hydroxy-3-(spiro[3.3]hept-2-yl)-1E- 18, 20-methano-9-oxoprost-13E-en-1-oate propenyl]cyclopent-1R-yl}heptanoate.TR-4121 1B Methyl 7-{3R-hydroxy-5-oxo-2R-[ 3S- Methyl 11α, 15S-dihydroxy-16, 18-methano- hydroxy-3-(spiro[3.3]hept-2-yl)-1E- 18, 20-methano-9-oxoprost-13E-en-1-oate propenyl]cyclopent-1R-yl}heptanoate.TR-4713 7A 7-{3R-hydroxy-5-oxo-2R-[3R-hydroxy- 16, 18-Methano-18, 20-methano-1, 11α, 3-(spiro[3.3]hept-2-yl)-1E-propenyl]- 15R-trihydroxyprost-13E-en-9-one cyclopent-1R-yl}heptan-1-ol.TR-4714 7B 7-{3R-hydroxy-5-oxo-2R-[3S-hydroxy- 16, 18-Methano-18, 20-methano-1, 11α, 3-(spiro[3.3]hept-2-yl)-1E-propenyl]- 15S-trihydroxyprost-13E-en-9-one cyclopent-1R-yl}heptan-1-ol.TR-4020 5A dl 7-{5-oxo-2R-[3R-hydroxy-3- (±) 15R-Hydroxy-16, 19-ethano-19, 20- (spiro[5.5]undecan-3-yl)-1E- butano-9-oxoprost-13E-en-1-oic acid propenyl]cyclopent-1R-yl}heptanoic acid.TR-4021 5B dl 7-{5-oxo-2R-[3S-hydroxy-3- (±) 15S-Hydroxy-16, 19-ethano-19, 20- (spiro[5.5]undecan-3-yl)-1E- butano-9-oxoprost-13E-en-1-oic acid propenyl]cyclopent-1R-yl} heptanoic acid.-TR-4136 4A dl 7-{5-oxo-2R-[3S-hydroxy-3- (±) 15S-Hydroxy-16, 18-methano-18, 20- (spiro[3.3]hept-2-yl)-1E-propenyl]- methano-9-oxoprost-13E-en-1-oic acid cyclopent-1R-yl}heptanoic acid.TR-4137 4B dl 7-{5-oxo-2R-[3R-hydroxy-3- (±) 15R-Hydroxy-16, 18-methano-18, 20- (spiro[3.3]hept-2-yl)-1E-propenyl]- methano-9-oxoprost-13E-en-1-oic acid cyclopent-1R-yl}heptanoic acid.TR-4146 6A dl 7-{5-oxo-2R-[3S-hydroxy-3- (±) 15S-Hydroxy-16, 18-methano-18, 20- (spiro[3.3]hept-2-yl)-1E-propenyl]- methano-9-oxoprosta-5Z, 13E-dien-1-oic cyclopent-1R-yl}hept-5Z-enoic acid.TR-4147 6B dl 7-{5-oxo-2R-[3R-hydroxy-3- (±) 15R-Hydroxy-16, 18-methano-18, 20- (spiro[3.3]hept-2-yl)-1E-propenyl]- methano-9-oxoprosta-5Z, 13E-dien-1-oic cyclopent-1R-yl}hept-5Z-enoic acid.TR-4139 3A Methyl 7-{3R,5S-dihydroxy-2R-[3S- Methyl 16, 18-methano-18, 20- hydroxy-3-(spiro[3.3]hept-2-yl)-1E- methano-9α, 11α, 15S-trihydroxyprost- propenyl]cyclopent-1R-yl}heptanoate. 13E-en-1-oateTR-4138 3B Methyl 7-{3R, 5R-dihydroxy-2R-[3S- Methyl 16, 18-methano-18, 20-methano- hydroxy-3-(spirol[3.3]hept-2-yl)-1E- 9β, 11α, 15S-trihydroxyprost-1 3E-en-1-oate propenyl]cyclopent-1R-yl}heptanoate.TR-4726 8A Ethyl 7-{3R-hydroxy-5-oxo-2R-[3R- Ethyl 11α, 15R-dihydroxy-16, 18-methano- hydroxy-3-(spiro[3.3]hept-2-yl)-1E- 18, 20-methano-9-oxoprosta-5Z, 13E-dien- propenyl]cyclopent-1R-yl}hept-5Z-enoate. 1-oateTR-4727 8B Ethyl 7-{3R-hydroxy-5-oxo-2R-[3S- Ethyl 11α, 15S-dihydroxy-16, 18-methano- hydroxy-3-(spiro[3.3]hept-2-yl)-1E- 18, 20-methano-9-oxoprosta-5Z- 13E-dier- propenyl]cyclopent-1R-yl}hept-5Z-enoate. 1-oate4841 12A 7-{3R-hydroxy-5-oxo-2R-[3S-hydroxy- 16-Methyl-16,18-methano-18,20-methano- 3-(2-methylspiro[3.3]hept-2-yl)-1E- 1,11α,15S-trihydroxyprost-13E-en-9- one propenyl]cyclopent-1R-yl}heptan-1-olTR-4852 12B 7-{3R-hydroxy-5-oxo-2R-[3R-hydroxy- 16-Methyl-16,18-methano-18,20-methano- 3-(2-methylspiro[3.3]hept-2-yl)-1E- 1,11α,15R-trihydroxyprost-13E-en-9- one propenyl]cyclopent-1R-yl}heptan-1-ol4842 13A Methyl 7-{3R-hydroxy-5-oxo-2R-[3S- Methyl 11α,15S-dihydroxy-16-methyl- 16,18- hydroxy-3-(2-methylspiro[3.3]hept-2- methano-18,20-methano-9-oxoprost-13E- yl)-1E-propenyl]cyclopent-1R-yl} en-1-oate heptanoate4845 13B Methyl 7-{3R-hydroxy-5-oxo-2R-[3R- Methyl 11α,15R-dihydroxy-16-methyl- 16,18- hydroxy-3-(2-methylspiro[3.3]hept- methano-18,20-methano-9-oxoprost-13E- 2-yl)-1E-propenyl]cyclopent-1R-yl} en-1-oate heptanoateTR-4758 11B dl Methyl-7-{6-ozo-2R-∂3S-hydroxy-3- dl Methyl-15S-hydroxy-9-oxo-9a-homo- (spiro[3.3]hept-2-yl)-1E-propenyl] 16,18-methano-18,20-methanoprost-5Z, cyclohex-1R-yl}hept-5Z-enoate 13E-dien-1-oateTR-4759 11A dl Methyl-7-{6-oxo-2R-[3R-hydroxy-3- dl Methyl-15R-hydroxy-9-oxo-9a-homo- (spiro[3.3]hept-2-yl)-1E-propenyl] 16,18-methano-18,20-methanoprost-5Z, cyclohex-1R-yl}hept-5Z-enoate 13E-dien-1-oate__________________________________________________________________________
In order to further illustrate the novel aspects of the present invention, the following examples are presented. It should be recognized that these examples are provided by way of illustration only and are not intended to limit in any way the invention disclosed herein. Compounds identified by compound number in the following examples refer to the compounds compiled in Table C.
EXAMPLE 1
This example illustrates a typical preparation of Prostaglandin E 1 Analogues.
Compounds TR 4120 and TR 4121 were prepared according to the procedure which follows. A mixture containing 2.62 grams (0.0059 moles) of 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro-[3.3]hept-2-yl)-1E-propene (see Example 9 for preparation) and 24 ml. of dry ether (distilled from benzophenone ketyl) was prepared and cooled to -78° C. with stirring under an argon atmosphere. Then 6.95 ml of 1.7 M t-butyllithium (0.0118 mole) in n-pentane was added and the mixture was stirred at a temperature of -78° C for 2 hours. A solution of 0.766 grams of Copper(I)pentyne (0.0059 moles) and 1.66 ml of hexamethyl phosphorus triamide in 8 ml of dry ether was added to the reaction flask with stirring at -78° C. The resulting mixture was stirred 30 minutes at -78° C and 1.74 grams (0.0536 mole) of methyl 7[3R-(tetrahydropyran-2 -yloxy)-5-oxocyclopent-1-enyl]heptanoate in 4.0 ml of dry ether was added thereto. The mixture was stirred for 30 minutes at -78° C and subsequently brought to -20° C and stirred for 1.5 hours. The mixture was quenched by the addition of 115 ml of 20% (v/v) aqueous ammonium sulfate and extracted with 50 ml of ether. The aqueous material was extracted with 100 ml (2×50 ml) of ether. The ether extracts were combined and washed with 50 ml of 2% (v/v) sulfuric acid. The aqueous material was back-extracted with 100 ml (2×50 ml) of ether. The combined ether extracts were filtered through diatomaceous earth (Celite), washed with 50 ml of saturated sodium bicarbonate solution and subsequently washed with 50 ml of saturated sodium chloride solution. The washed ether extract was then dried over anhydrous magnesium sulfate, filtered through diatomaceous earth (Celite) and the solvent removed in vacuo. The residue was stirred with 12 ml of acetic acid-water-tetrahydrofuran (65:35:10 v/v) at 22° C for 15 hours. The solvents were removed in vacuo and the residue was taken up in 50 ml of water. The water mixture was extracted with 150 ml (3×50 ml) of ether-ethyl acetate (1:1 v/v). The organic mixture was washed with 50 ml of saturated sodium bicarbonate solution and then washed with 50 ml of saturated sodium chloride solution. The washed organic mixture was then dried over anhydrous magnesium sulfate, filtered through diatomaceous earth (Celite) and the solvents was removed in vacuo. The residue was chromatographed by column chromatography using an 85:15 (w/w) silicic acid: diatomaceous earth (Celite) support and using a benzene-ethyl acetate gradient elution to yield 168.4 mg of Compound TR 4120 and 162.8 mg of Compound TR 4121.
A. Compound TR 4120 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 3600-3300 cm -1 , 2950 cm -1 , 1740 cm -1 and 1710 cm -1 .
NMR(CDCl 3 ): δ1.1-2.9, multiplet, 27H; δ3.65, singlet, 3H; δ3.6-4.2, multiplet, 3H; δ4.6, multiplet, 1H; δ5.6 ppm, multiplet, 2H;
[α] D (CDCl 3 , c. 0.87): -61.1°.
B. Compound TR 4121 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 3600-3300 cm -1 , 2950 cm -1 , 1740 cm -1 and 1710 cm -1 .
NMR(CDCl 3 ): δ1.0-2.9, multiplet, 27H; δ3.6, singlet, 3H; δ3.6-4.1, multiplet, 3H; δ4.6, multiplet, 1H; δ4.5 ppm, multiplet, 2H.
[α] D (CHCl 3 , c. 1.0): -56.5°.
EXAMPLE 2
This Example illustrates the preparation of Prostaglandin A analogues.
A mixture, containing 0.1234 grams (0.315 m mole) of Compounds TR 4120 and TR 4121, prepared as described in Example 1, and 3.5 ml of glacial acetic acid and 0.7 ml of water was heated at 60° C for 24 hours. The solvents were removed in vacuo and the residue was taken up in 20 ml of water and 20 ml of ether-ethyl acetate (1:1 v/v). The ether-ethyl acetate extract was washed with 20 ml of saturated sodium bicarbonate solution and then washed with 20 ml saturated sodium chloride solution. The washed extract was dried over anhydrous magnesium sulfate and filtered. The solvents were removed from the extract in vacuo. The residue was chromatographed by column chromatography using a silicic acid-diatomaceous earth (85:15 w/w) support and using a benzene-ethyl acetate gradient to yield 15.9 mg of compound TR 4126 and 27.6 mg of Compound TR 4127.
A. Compound TR 4126 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 2940 cm -1 , 1730 cm -1 , and 1705 cm -1 .
NMR(CDCl 3 ): δ0.9-2.5, multiplet, 25H; δ3.3, multiplet, 1H; δ3.7, singlet, 3H; δ3.8-4.0, multiplet, 2H; δ5.5, multiplet, 2H; δ6.1, multiplet, 1H; δ7.25 ppm, multiplet, 1H.
[α] D (CHCl 3 , c. 0.96): + 83.5°.
B. Compound TR 4127 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 2930 cm -1 , 1730 cm -1 , and 1710 cm -1 .
NMR(CDCl 3 ): δ1.1-2.4, multiplet, 25H; δ3.2, multiplet, 1H; δ3.63, singlet, 3H; δ3.7-4.1, multiplet, 2H; δ5.5, multiplet, 2H; δ6.1, multiplet, 1H; δ7.4 ppm, multiplet, 1H.
[α] D (CHCl 3 , c. 0.92); + 77°.
EXAMPLE 3
This Example illustrates the preparation of Prostaglandin F 1 α and F 1 β analogues.
About 10 ml of anhydrous methanol was mixed with 0.11 grams (0.28 mmol) of Compound TR 4120 prepared in the manner described in Example 1. The mixture was cooled in an ice-methanol bath and a mixture of 0.0635 grams (0.168 mmol) of sodium borohydride partially dissolved in 15 ml of anhydrous methanol was added. The mixture was stirred for 30 minutes at -20° C then brought to room temperature and stirred for an additional 2.5 hours. The solvents were removed in vacuo. The residue was taken up in 30 ml of water and extracted with 120 ml (4×30 ml) of ether-ethyl acetate (1:1 v/v). The ether-ethyl acetate extract were combined and washed with 30 ml of saturated sodium chloride solution. The washed extract was dried over anhydrous magnesium sulfate and filtered and the solvents were then removed in vacuo. The residue was chromatographed by column chromatograply using silicic acid: diatomaceous earth (Celite) 85:15 (w/w) support and using a benzene-ethyl acetate gradient elution to yield 32.2 mg of TR 4139 and 28.2 mg of TR 4138.
A. Compound TR 4139 had the following spectral properties
Analysis -- IR: ν max CHCl .sbsp.3 : 3600-3100 cm -1 , 2950 cm -1 , and 1700 cm -1 .
NMR(CDCl 3 ): δ1.1-2.6, multiplet, 27H; δ3.6-4.2, multiplet, 5H; δ5.5, multiplet, 1H; δ5.45 ppm, multiplet, 2H.
[α] D (CHCl 3 c. 1.26): +32.2°.
B. Compound TR 4138 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 3600-3100 cm -1 , 2950 cm -1 , and 1730 cm -1 .
NMR(CDCl 3 ): δ1.1-2.6, multiplet, 27H; δ3.7, singlet, 3H; δ3.7-4.1, multiplet, 5H; δ5.5 ppm, multiplet, 2H.
[α] D (CHCl 3 , c. 1.41): +6.8°.
EXAMPLE 4
Preparation of Compounds TR 4136 and TR 4137
A mixture containing 1.31 grams, (0.00295 mole) of 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[3.3]hept-2-yl)-1E-propene (see Example 9 for preparation of this compound) and 12 ml of dry ether (distilled from benzophenone ketyl, b.p. 34° C) was prepared and cooled to -78° C with stirring under an argon atmosphere. Then 3.475 ml (0.0059 mole) of a solution (1.7M) of t-butyllithium in pentane was added. The resultant mixture was stirred for 2 hr at -78° C. Copper(I) pentyne (0.383 g, 0.00295 mole) and 0.83 ml of dry hexamethylphosphorus triamide in 4 ml of dry ether was added to the reaction flask. The resulting reaction mixture was stirred for 30 minutes at -78° C and 0.6 grams (0.00268 mole) of methyl 7-(5-oxocyclopent-1-enyl)heptanoate in 2 ml of dry ether was added thereto. The mixture was stirred for 30 minutes at -78° C and subsequently brought to -20° C and stirred for 90 minutes. The mixture was quenched with 80 ml of 20% (w/v) aqueous ammonium sulfate solution. The mixture was shaken for 10 minutes with 30 ml of ether. The aqueous material was extracted with 150 ml (2×75 ml) of ether. The ether extracts were combined and washed with 30 ml of cold 2% (v/v) aqueous sulfuric acid. The aqueous material was back-extracted with 100 ml (2×50 ml) of ether. The combined ether extracts were filtered through diatomaceous earth (Celite), washed with 75 ml of saturated sodium bicarbonate solution and subsequently with 75 ml of saturated sodium chloride solution. The washed extract was then dried over anhydrous magnesium sulfate, and filtered through diatomaceous earth (Celite) the solvents were removed from the extract in vacuo. The residue was stirred with 25 ml of acetic acid-water-tetrahydrofuran (65:30:10 v/v/) at about 22° C for 1 hour. The solvents were removed in vacuo and the residue was taken up in 30 ml of water and 30 ml of ether-ethyl acetate (1:1 v/v). The aqueous material was extracted with 70 ml (2×35 ml) of ether-ethyl acetate (1:1 v/v). The ether-ethyl acetate extracts were combined and washed with 50 ml of saturated sodium bicarbonate solution and then washed with 50 ml of saturated sodium chloride solution. The washed ether-ethyl acetate extracts were dried over anhydrous magnesium sulfate and filtered through diatomaceous earth (Celite). The solvents were removed from the extract in vacuo. The residue was stirred with 25 ml of 5% (w/v) potassium hydroxide-methanol-water (1:1 v/v) for 2.5 hours. The methanol was removed in vacuo. The residual material was taken up in 50 ml of water and extracted with 90 ml (3×30 ml) of ethyl acetate. The organic material was backextracted with 50 ml (2×25 ml) of water. The aqueous material was acidified with 10% (w/v) aqueous hydrochloric acid and the products were extracted with 150 ml (3×50 ml) of ether. The ether extracts were combined and washed with 50 ml of saturated sodium chloride. The washed extract was dried over anhydrous magnesium sulfate and filtered through diatomaceous earth. The solvents were removed from the extract in vacuo. The residue was chromatographed by column chromatography using a silicic acid-diatomaceous earth (85:15 w/w) support and using a benzene-ethyl acetate elution gradient to yield 45.7 mg of Compound TR 4136 and 52.7 mg of Compound TR 4137.
A. Compound TR 4136 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 2940 cm -1 , 1730 cm -1 and 1710 cm -1 .
NMR(CDCl 3 ): δ1.0-2.9, multiplet, 29H; 3.95, multiplet, 1H; 5.5, multiplet, 2H; 7.75 ppm, broad singlet, 2H.
B. Compound TR 4137 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 3600 cm -1 , 2940 cm -1 , 1730 cm -1 , and 1710 cm -1 .
NMR(CDCl 3 ): δ1.1-2.7, multiplet, 29H; 3.9, multiplet, 1H; 5.5, multiplet, 2H; 6.95 ppm, broad singlet, 2H.
EXAMPLE 5
Preparation of Compounds TR 4020 and TR 4021
Repeating in a similar manner the procedure of Example 4, but replacing 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro-[3.3]hept-2-yl)-1E-propene with 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[5.5]undec-3-yl)-1E-propene (see Example 10 for preparation) yields the following 11-deoxy Prostaglandin E 1 analogues:
A. Compound TR 4020 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 3600-2400 cm -1 , 2950 cm -1 , 1740 cm -1 , and 1720 cm -1 .
NMR(CDCl 3 ): δ0.7-2.6, multiplet, 37H; δ3.9, multiplet, 1H; δ5.6, multiplet, 2H; δ6.1 ppm, multiplet, 2H.
B. Compound TR 4021 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 3500-2400 cm -1 , 1730 cm -1 , and 1710 cm -1 .
NMR(CDCl 3 ): δ0.7-2.6, multiplet, 37H; δ3.95, multiplet, 1H; δ5.7, multiplet, 2H; δ6.01 ppm, multiplet, 2H.
EXAMPLE 6
Preparation of Compounds TR 4146 and TR 4147
Repeating in a similar manner the procedure of Example 4, but replacing methyl 7-(5-oxocyclopent-1-enyl)heptanoate with methyl 7-(5-oxocyclopent-1-enyl)hept-5Z-enoate yields the following 11-desoxy Prostaglandin E 2 analogues.
A. Compound TR 4146 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 2950 cm -1 , 1730 cm -1 , and 1710 cm -1 .
NMR(CDCl 3 ): δ1.8-3.0, multiplet, 25H; δ4.0, multiplet, 1H; δ5.45, multiplet, 4H; δ7.2 ppm, broad singlet, 2H.
B. Compound TR 4147 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 2950 cm -1 , 1740 cm -1 and 1715 cm -1 .
NMR(CDCl 3 ): δ0.8-3.0, multiplet, 25H; δ3.9 multiplet, 1H; δ5.45, multiplet, 4H; δ6.9 ppm, broad singlet, 2H.
EXAMPLE 7
Preparation of compounds TR 4713 and TR 4714
A solution of 606 mg (2.0 mmol) of 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[3.3]hept-2-yl)-1E-propene in 11.0 ml of dry ether was stirred under argon at -78°, and 3.6 ml of 1.18M t-butyllithium in pentane was injected. The reaction mixture was stirred for 2.5 hr at -78°, then was transferred into a stirred, -78° solution of 250 mg of copper(I) pentyne in 6.2 ml of dry ether (solubilized at 25° with 0.74 ml of hexamethylphosphorous triamide). The resultant complex was stirred for 0.5 hr at -78°, then a solution of 685 mg of 1-tetrahydropyran-2-yloxy-7-{3R-(tetrahydropyran-2-yloxy)-5-oxocyclopent-1-enyl}heptane in 3.7 ml of ether was injected dropwise over 10 min. The reaction mixture was stirred for 0.5 hr at -78°, and 1.5 hr at -10°. The reaction was quenched by the addition of 20% aqueous ammonium sulfate and the mixture extracted with ether. The ether extracts were combined and washed with 2% aqueous sulfuric acid, saturated aqueous sodium bicarbonate and brine, then dried (MgSO 4 ), filtered and solvent removed in vacuo to yield an orange oil. The oil was stirred with 54 ml of 65:35:10 acetic acid-water-THF for 18 hr at 25°. The solvents were removed by evaporation in vacuo and water added to the residue. The mixture was extracted with ether. The ether extracts were washed with saturated aqueous sodium bicarbonate and brine, then dried (MgSO 4 ), filtered and ether evaporated in vacuo to afford 629 mg of crude products as a yellow oil. The products were purified by column chromatography to afford 82.8 mg of Compound TR 4714; and 103 mg of Compound TR 4713
A. Compound TR 4713 had the following spectral properties:
Analysis -- IR: λ max CHCl .sbsp.3 : 2.78, 2.95(broad), 5.75, 10.40μ.
NMR(CDCl 3 ): 5.66, multiplet, 2, CH═CH 3.2-4.3, multiplet, 7H, CHOH
[α] D (CHCl 3 , c. 0.94): -57.9°
Ms (70eV) 346(p-H 2 O); 328(p-2H 2 O).
B. Compound TR 4714 had the following spectral properties:
Analysis -- IR: λ max CHCl .sbsp.3 2.78, 5.75, 10.40μ
NMR(CDCl 3 ): δ5.74, multiplet, 2H, trans-CH═CH) 3.2-4.7, multiplet, 7H, CHOH
[α] D (CHCl 3 , c. 1.0): -53.5°
Ms(70eV) 346(p-H 2 O); 328(p-2H 2 O).
EXAMPLE 8
Preparation of Compounds TR 4726 and TR 4727
Repeating in a similar manner the procedure of Example 1, but replacing methyl 7-[3R-(tetrahydropyran-2-yloxy)-5-oxocyclopent-1-enyl]heptanoate with ethyl 7-[3R-tetrahydropyran-2-yloxy)-5-oxocyclopent-1-enyl]hept-5Z-enoate yields the prostaglandin E 2 analogues TR 4726 and TR 4727.
A. Compound TR 4726 had the following spectral properties:
Analysis -- IR: ν max CHCl .sbsp.3 : 910, 970, 1075, 1160, 1740, 2840, 2950, 3400(broad), and 3600 cm -1 .
NMR(CDCl 3 ): δ1.24, t, 3H, J=7HZ; 1.4 to 3,0, m, 23H; 3.3 to 4.3, m, 6H; 5.2 to 5.7, m, 4H.
Ms (70eV): m/e 386 (p-H 2 O); 368 (p-2H 2 O); 341 (p-H 2 O--OC 2 H 5 ); 309 (p-C 7 H 11 ); 291 (p-C 7 H 11 --H 2 O).
[α] D (CHCl 3 , c 0.95): -53.1°.
B. Compound TR 4727 had the following spectral properties:
Analysis -- NMR,IR,Ms are essentially the same as for the compound 4726 above. [α] D (CHCl 3 , c 0.95): -60.0°.
EXAMPLE 9
This Example illustrates the preparation of the intermediate compound 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[3.3]hept-2-yl)-1E-propene using the following procedure.
A. Preparation of 1,1-di(Hydroxymethyl)cyclobutane
Lithium aluminum hydride (63.4 g, 1.67 mole) was slurried in 600 ml of dry ether (distilled from benzophenone ketyl, bp 34° C). The slurry was cooled in an ice-water bath and a mixture of 100 g (0.69 mole) of 1,1-cyclobutanedicarboxylic acid (commercially available from Aldrich Chemical Co., Inc.) and 250 ml of dry ether was slowly added. The mixture was stirred at reflux for 1 hr, cooled and the excess hydride was destroyed by ethyl acetate addition. The mixture was treated with 1 liter of 6N hydrochloric acid and the products were extracted with 2 liters (4×500 ml) of ether. The organic material was washed with 250 ml of saturated sodium bicarbonate solution and 250 ml of saturated sodium chloride solution. It was dried over anhydrous magnesium sulfate, filtered and evaporated in vacuo to yield 49 g of pure 1,1-di(hydroxymethyl)cyclobutane.
Analysis -- NMR(CDCl 3 ): δ1.85, multiplet, 6H; δ3.3-3.8 ppm, multiplet, 4H.
B. Preparation of 1,1-di(Toluenesulfonyloxymethyl)cyclobutane
1,1-di(Hydroxymethyl)cyclobutane (1.16 g, 0.01 mole) was mixed with 10 ml of dry pyridine (distilled from calcium hydride). The mixture was cooled to approximately 0° C and 5.0 g (0.0263 mole) of p-toluenesulfonyl chloride was added portion wise. The mixture was stirred for 3 hrs at 0° C then poured into 70 ml of cold 6N hydrochloric acid. Crude ditosylate was isolated by filtration. The crude material was recrystallized from methanol to yield 2.76 g (64.7%) of 1,1-di(toluenesulfonyloxymethyl)cyclobutane.
Analysis: NMR(CDCl 3 ): δ1.8, broad singlet, 6H; δ2.45, singlet, 6H; δ3.95, singlet, 4H; δ7.5, AB pattern, J=8HZ, 8H.
C. Preparation of Spiro[3.3]heptane-2,2-dicarboethoxy ester
Sodium metal (0.5 g, 0.022 mole) was dispersed in 10 ml of dry xylene (distilled from sodium hydride) by rapid stirring at 110° C. Diethyl malonate (6 g, 0.0375 mole, 5.67 ml) was added and the mixture was heated at 100° C until the sodium was consumed. 1,1-di(toluenesulfonyloxymethyl)-cyclobutane (4 g, 0.009425 mole) was added and the mixture was heated at 157° C for 18 hr with stirring. The mixture was cooled and 20 ml of water was added. The phases were separated and the aqueous material was extracted with 150 ml (2×75 ml) of xylene. The organic material was washed with 50 ml of 6N hydrochloric acid and 50 ml of saturated sodium sulfate solution. It was dried over anhydrous magnesium sulfate, filtered and evaporated in vacuo. The residue was distilled at reduced pressure to yield 0.99 g (44%) of spiro[3.3]heptane-2,2-dicarboethoxy ester.
Analysis -- bp: 98°-98.5° C/0.35 mm.
NMR(CDCl 3 ): δ1.25, triplet, 6H,J=7HZ; δ1.5-2.2, multiplet, 6H; δ2.48, multiplet, 4H; 4.2 ppm, quartet, 4H,J=7HZ.
D. Preparation of Spiro[3.3]heptane-2,2-dicarboxylic acid
Spiro[3.3]heptane-2,2-dicarboethoxy ester (14.4 g, 0.6 mole) was mixed with 13.45 g (0.24 mole) of potassium hydroxide and 114 ml of ethanol. The mixture was refluxed for 1 hr, cooled and then filtered. The cake was washed with 80 ml of absolute ethanol. The residue was dissolved in 50 ml of water and acidified with 60 ml of 50% aqueous sulfuric acid. The mixture was cooled and filtered to yield 10.4 g of spiro[3.3]heptane-2,2-dicarboxylic acid.
Analysis -- NMR(CDCl 3 ): δ1.3-2.2, multiplet, 6H; 2.5, multiplet, 4H; 8.0-9.0 ppm, broad singlet, 2H.
E. Preparation of Spiro[3.3]heptane-2-carboxylic acid
Crude spiro[3.3]heptane-3,3-dicarboxylic acid (8.3 g, 0.046 mole) was thermally decarboxylated by heating the material at 220° C for 30 min. Heating was discontinued when the evolution of carbon dioxide ceased. The mixture was cooled to yield 5.38 g of spiro[3.3]heptane-2-carboxylic acid.
Analysis -- NMR(CDCl 3 ): δ1.5-2.3, multiplet, 11H; 11.0 ppm, broad singlet, 1H.
F. Preparation of Spiro[3.3]heptane-2-carboxylic acid chloride
Spiro[3.3]heptane-3-carboxylic acid (8.5 g, 0.06 mole) was mixed with 14.5 g (0.124 mole, 9.2 ml) of thionyl chloride. The mixture was allowed to stir overnight at room temperature. The excess thionyl chloride was removed by distillation at atmospheric pressure. Spiro[3.3]heptane-2-carboxylic acid chloride (8.3 g, 86.4%) was isolated by distillation at reduced pressure.
Analysis -- NMR(CDCl 3 ): δ1.8-2.6, multiplet, 10H; 3.45 ppm, multiplet, 1H.
G. Preparation of 1-Chloro-3(spiro[3.3]hept-2-yl)-1E-propen-3-one
A 100 ml 3-neck round bottom flask was fitted with a mechanical stirrer, gas inlet tube extending below the solvent surface and a water condenser with a gas outlet. The system was flushed with acetylene gas (bubbled through an activated aluminum oxide trap, two concentrated sulfuric acid traps and an empty trap for 3 min. Carbon tetrachloride (70 ml) was added to the flask and the system flushed with acetylene for 3 min. The flask was cooled in an ice-water bath and 8.3 g (0.053 mole) of anhydrous aluminum chloride was added. The system was flushed with acetylene for 3 min. The gas inlet was replaced with an addition funnel and 8.3 g (0.053 mole) of spiro[3.3]heptane-3-carboxylic acid chloride was added slowly over a 10 min. period. The addition funnel was replaced with the gas inlet tube and acetylene was bubbled through the mixture for 4 hr. The mixture was poured into 100 ml of crushed ice and 150 ml of saturated sodium chloride solution. The phases were separated and the aqueous material was extracted with 195 ml (3×65 ml) of ether. The combined organic extracts were washed with 150 ml (3×50 ml) of 10% (v/v) aqueous hydrochloric acid solution, 150 ml (3×50 ml) of saturated sodium bicarbonate solution and 100 ml of saturated sodium chloride solution. The material was dried over anhydrous magnesium sulfate, filtered and the solvents were removed in vacuo. The material was distilled at reduced pressure to yield 7.3 g (75.7%) of 1-chloro-3-(spiro[3.3]hept-2-yl)-1E-propen-3-one.
Analysis -- b.p.65°-68° C/0.2 mm.
NMR(CDCl 3 ): δ1.5-2.5, multiplet, 10H; δ3.3, multiplet, 1H; δ6.4, doublet, 1H J=14HZ; δ7.2 ppm, doublet, 1H J=14Hz.
H. Preparation of 1-Iodo-3-(spiro[3.3]hept-2-yl)-1E-propen-3-one
1-Chloro-3-(spiro[3.3]hept-2-yl)-1E-propen-3-one (7.3 g, 0.042 mole) was mixed with 25.2 g (0.168 mole) of sodium iodide and 45 ml of dry acetone (distilled from anhydrous potassium carbonate, b.p. 56° C). The mixture was refluxed with rapid stirring overnight. The mixture was cooled and the solvent was removed in vacuo. The solid residue was taken up in 75 ml of water and the products were extracted with 150 ml (3×50 ml) of ether. The organic material was washed with 50 ml of saturated sodium bicarbonate solution, 50 ml of aqueous sodium thiosulfate solution and 50 ml of saturated sodium chloride solution. The material was dried over anhydrous magnesium sulfate, filtered and the solvent was removed in vacuo to yield 6.9 g (62.2%) of crude 1-iodo-3-(spiro[3.3]hept-2-yl)-1E-propen-3-one.
Analysis -- NMR(CDCl 3 ): δ1.5-2.4, multiplet, 10H; δ3.3, multiplet, 1H; δ6.9, doublet, 1H, J=15HZ; δ7.5 ppm, doublet, 1H, J=15HZ.
I. Preparation of 1-Iodo-3-(spiro[3.3]hept-2-yl)-1E-propen-3RS-ol
1-Iodo-3-(spiro[3.3]hept-2-yl)-1E-propen-3-one (8.62 g, 0.0311 mole) was dissolved in 100 ml of absolute ethanol and the mixture cooled to -20° C. Sodium borohydride (4.71 g, 0.124 mole) was dissolved in 100 ml of absolute ethanol and added to the cooled mixture. The mixture was allowed to stir for 1 hr at 0° C. The solvent was removed in vacuo and the residue was taken up in 250 ml of water. The products were extracted with 300 ml (3×100 ml) of ether. The extracts were washed with 75 ml of saturated sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and the solvent removed in vacuo to yield 7.5 g of 1-iodo-3-(spiro[3.3]hept-2-yl)-1E-propen-3RS-ol.
Analysis -- NMR(CDCl 3 ): δ1.5-2.5, multiplet, 11H; δ3.8, multiplet, 1H; δ6.0-6.5 ppm, multiplet, 2H.
J. Preparation of 1-Iodo-3RS-(1-ethoxyethoxy)-3-(spiro[3.3]hept-2-yl)-1E-propene.
1-Iodo-3-(spiro[3.3]hept-2-yl)-1E-propen-3RS-ol (7.5 g, 0.027 mole) was mixed with 38.2 g (50 ml, 0.512 mole) of ethylvinyl ether. Phosphorous oxychloride (2 drops) was added and the mixture was allowed to stir overnight at room temperature. The mixture was poured into 75 ml of saturated sodium bicarbonate solution and the products were extracted with 100 ml (2×50 ml) of ether. The organic material was washed with 50 ml of saturated sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and the solvent was removed in vacuo. Chromatography was preformed on silica gel 60 (0.063-0.2 mm, 70-230 mesh, ASTM) using benzene elutant to yield 5.3 g (56.4%) of 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[3.3]hept-2-yl)-1E-propene.
Analysis -- NMR(CDCl 3 ): δ0.8-25, multiplet, 17H; δ3.5, multiplet, 3H; δ4.6, quartet, 1H, J=5HZ; δ6.3 ppm, multiplet, 2H.
EXAMPLE 10
This Example illustrates the preparation of the intermediate compound 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[5.5]undec-3-yl)-1E-propene using the following procedure.
A. Preparation of Spiro[5.5]undecane-3-carboxylic acid chloride
In a procedure as described in Example 9F, spiro[5.5]undecane-3-carboxylic acid chloride was prepared from thionyl chloride and spiro[5.5]undecane-3-carboxylic acid (preparation described in U.S. Pat. No. 3,350,442).
Analysis -- NMR(CDCl 3 ): δ0.6-2.4, multiplet, 18H.
B. Preparation of 1-Chloro-3-(spiro[5.5]undec-3-yl)-1E-propen-3-one
In a procedure as described in Example 9G, 1-chloro-3-(spiro[5.5]undec-3-yl)-1E-propen-3-one was prepared from anhydrous aluminum chloride, spiro[5.5]undecane-3-carboxylic acid chloride and acetylene. The compound was purified by column chromatography on silica gel 60 (0.063-0.2 mm, 70-230 mesh, ASTM) using chloroform as the solvent.
Analysis -- NMR(CDCl 3 ): δ0.6-2.6, multiplet, 19H; 6.5, doublet, 1H, J=15HZ; 7.3 ppm, doublet, 1H, J=15Hz.
C. Preparation of 1-Iodo-3-(spiro[5.5]undec-3-yl)-1E-propen-3-one
In a procedure as described in Example 9H, 1-chloro-3-(spiro[5.5]undec-3-yl)-1E-propen-3-one was reacted with sodium iodide in acetone to yield 1-iodo-3-(spiro[5.5]undec-3-yl)-1E-propen-3-one (70.9%).
Annalysis -- NMR(CDCl 3 ): δ0.8-2.5, multiplet, 19H; δ7.22, doublet, 1H, J=16HZ; δ7.85 ppm, doublet, 1H, J=16HZ.
D. Preparation of 1-Iodo-3-(spiro[5.5]undec-3-yl)-1E-propen-3RS-ol
In a procedure as described in Example 9I, 1-iodo-3-(spiro[5.5]undec-3-yl)-1E-propen-3-one was reduced with sodium borohydride in ethanol to yield 1-iodo-3-(spiro[5.5]undec-3-yl)-1E-propen-3RS-ol (98.5%).
Analysis -- NMR(CDCl 3 ): δ0.5-2.2, multiplet, 19H; δ3.95, multiplet, 1H; δ6.1-6.8 ppm, multiplet, 2H.
E. Preparation of 1-Iodo-3RS-(1-ethoxyethoxy)-3-(spiro[5.5]undec-3yl)-1E-propene.
In a procedure as described in Example 9J, 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[5.5]undec-3-yl)-1E-propene was prepared from 1-iodo-3-(spiro[5.5]undec-3-yl)-1E-propen-3RS-ol and ethylvinyl ether using phosphorous oxychloride as a catalyst. The compound was obtained in 76.9% yield.
Analysis -- NMR(CDCl 3 ): δ0.7-2.1, multiplet, 25H; δ3.6, multiplet, 3H; δ4.7, quartet, 1H, J = 6Hz; δ6.1-6.6 ppm, multiplet, 2H.
EXAMPLE 11
Preparation of Compounds TR-4758 and TR-4759
Repeating in a similar manner the procedure of Example 7, but replacing 1-tetrahydropyran-2-yloxy-7-{3R-(tetrahydropyran-2-yloxy)-5-oxocyclopent-1-enyl}heptane with methyl 7-(6-oxocyclohex-1-enyl)hept-5Z-enoate yields the 9a-homo prostaglandin E 2 analogues TR-4758 and TR-4759.
A. Compound TR-4759 had the following spectral properties;
Analysis -- IRλ max CHCl .sbsp.3 : 2.78, 2.85(broad), 3.4, 5.80, 5.85, 10.40μ.
NMR(CDCl 3 ): δ3.66, singlet, 3H; 3.92, multiplet, 1H; 5.40, multiplet, 4H.
Ms(70eV): m/e388(p); 370(p-H 2 O); 357(p-OCH 3 ); 352(p-2H 2 O).
B. Compound TR-4758 had the following spectral properties:
Analysis -- IR, NMR and Ms are essentially the same as compound TR-4759 above.
EXAMPLE 12
Preparation of compounds TR-4841 and TR-4852
Repeating in a similar manner the procedure of Example 7, but replacing 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[3.3]hept-2-yl)-1E-propene with 1-iodo-3RS-(tetrahydropyran-2-yloxy)-3-(2-methylspiro[3.3]hept-2-yl)-1E-propene yields the prostaglandin analogues TR-4841 and TR-4852.
A. Compound TR-4841 had the following spectral properties:
Analysis -- IRλ max CHCl .sbsp.3 : 2.78, 2.88(broad), 5.75, 10.4μ.
NMR(CDCl 3 ): δ1.00, singlet, 3H; 3.60, triplet, J=5.0Hz, 2H; 4.0, multiplet, 2H; 5.67, multiplet, 2H.
[α] D (CHCl 3 ,c0.89) -53.8°
Ms (70eV) m/e: 360(p-H 2 O); 342(p-2H 2 O); 269(p-C 8 H 13 ).
B. Compound TR-4852 had the following spectral properties:
Analysis -- IRλ max CHCl .sbsp.3 : 2.78, 2,94(broad), 10.4μ
NMR(CDCl 3 ): δ1.08, singlet, 3H; 3.10, broad singlet, 3H; 3.65, broad triplet, 2H; 3.90, multiplet, 2H; 5.60, multiplet, 2H.
[α] D (CHCl 3 ,c0.89) -43.8°
Ms (70eV) m/e: 360(p-H 2 O); 342(p-2H 2 O); 269(p-C 8 H 13 ); 251(p-C 8 H 13 -H 2 O).
EXAMPLE 13
Preparation of compounds TR-4842 and TR 4845
Repeating in a similar manner the procedure of Example 1, but replacing 1-iodo-3RS-(1-ethoxyethoxy)-3-(spiro[3.3]hept-2-yl)-1E-propene with 1-iodo-3RS-(tetrahydropyran-2-yloxy)-3-(2-methylspiro[3.3]hept-2-yl)-1E-propene yields prostaglandin analogues TR-4842 and TR-4845.
A. Compound TR-4842 had the following spectral properties:
Analysis -- IR: λ max CHCl .sbsp.3 : 2.78, 2.90, 5.75, 10.4μ.
NMR(CDCl 3 ): δ1.02, singlet, 3H; 3.66, singlet, 3H; 4.02, multiplet, 2H; 5.65, multiplet, 2H.
[α] D (c0.87,CHCl 3 ) -64.1°.
Ms (70eV) m/e:388(p-H 2 O); 339(p-2H 2 O--OCH 3 ); 317(p-OCH 3 --C 5 H 8 ); 297(p-C 8 H 13 ).
B. Compound TR-4845 had the following spectral properties:
Analysis -- IR, Ms spectra essentially the same as for compound TR-4842 above.
NMR (CDCl 3 ): δ1.08, singlet, 3H; 3.66, singlet, 3H; 3.96, multiplet, 2H; 5.60, multiplet, 2H.
[α] D (c0.86, CHCl 3 ) -44.8°.
EXAMPLE 14
This Example illustrates the preparation of the intermediate compound 1-iodo-3RS-(tetrahydropyran-2-yloxy)-3-(2-methylspiro[3.3]hept-2-yl)-1E-propene using the following procedure.
A. Preparation of 2-Methylspiro[3.3]heptane-2-carboxylic acid
A slurry of 2.15 g (44.2 mmol) of sodium hydride (50% in oil) in 45.0 ml of dry THF was stirred under argon at -20° C. A solution of 5.52 g (40.0 mmol) of spiro[3.3]heptane-2-carboxylic acid in 5.0 ml of dry THF was added dropwise. The reaction mixture was stirred for 0.5 hr at -20° C. A solution of 44.5 mmol of freshly-prepared, -20° C lithium diisopropylamide in 31.0 ml of THF was added to the reaction mixture. The reaction mixture was stirred for 0.3 hr at 0° C. Methyl iodide (2.80 ml, 44.5 mmol) was added, and the reaction mixture stirred an additional 2.0 hr at 25° C. The reaction mixture was cooled to -20° C and the reaction quenched by careful addition of cold 10% aqueous HCl. The mixture was extracted with 1:1 ethylacetate-ether. The extracts were washed with brine, then dried (MgSO 4 ), filtered, and solvents evaporated in vacuo. The residue was dissolved in 1 N NaOH and extacted three times with ether. The aqueous layer was acidified with 6 N HCl and extracted with 1:1 ethyl-acetate-ether. These extracts were washed with brine, dried (MgSO 4 ), filtered and evaporated in vacuo to yield 5.1 g of 2-methylspiro[3.3]heptane-2-carboxylic acid as a light yellow oil (82.5%).
Analysis -- NMR (CHCl 3 ): δ1.35, singlet, 3H; 11.4, broad singlet, 1H.
B. Preparation of 2-Methyl-2-acetylspiro[3.3]heptane.
A solution of 5.0 g (33.0 mmol) 2-methylspiro[3.3]heptane-2-carboxylic acid in 33.0 ml of dry ether was stirred under argon at 0° C and 47.6 ml (74.3 mmol) of 1.56 M methyl lithium in ether added dropwise. The reaction mixture was allowed to warm to 25° C and was stirred for 3.0 hr. The reaction mixture was cooled to -20° C and quenched by addition of 10% aqueous HCl. The layers were separated and the aqueous layer extracted with ether. The combined organic layers were washed with saturated aqueous sodium bicarbonate and brine, then dried (MgSO 4 ), filtered, and evaporated in vacuo to afford 2-methyl-2-acetylspiro[3.3]heptane as a light yellow oil (4.91 g 98%).
Analysis -- NMR (CDCl 3 ): δ1.35, singlet, 3H; 2.0, singlet, 3H.
IR: λ max CHCl .sbsp.3 3.85, 7.40, 8.80μ.
C. Preparation of (2-Methylspiro[3.3]hept-2-yl) (2-hydroxyvinyl)ketone
A solution of 7.8 g (130.0 mmol) methyl formate and 4.91 g (32.4 mmol) of 2-methyl-2-acetylspiro[3.3]heptane in 8.0 ml of dry ether was dropped into a slurry of 1.2 g of sodium hydride in 180 ml of ether. A few drops of MeOH were added and the reaction mixture stirred for 1.5 hr at 25° C. The reaction mixture was cooled to -10° C and the reaction quenched by slow addition of water. The layers were separated and the aqueous layer extracted twice with ether. The combined organic extracts were washed with water and 1 N NaOH. The combined aqueous layers were acidified with 6 N HCl and extracted with ether. The ether extracts were washed with brine, then dried (MgSO 4 ), filtered and evaporated in vacuo to yield 4.0 g of (2-methylspiro[3.3]hept-2-yl)(2-hydroxyvinyl)heptane as a yellow oil (69.5%).
Analysis -- IR: λ max CHCl .sbsp.3 : 3.85, 7.40, 8.80μ.
NMR (CDCl 3 ) δ 1.32, singlet, 3H; 5.5, doublet, J=4.0Hz, 1H; 7.90, doublet, J=4.0Hz, 1H; 8.05, singlet, 1H.
D. Preparation of 1-Chloro-3-(2-methylspiro[3.3]hept-2-yl)-1E-propen-3-one
A solution of 4.0 g of (2-methylspiro[3.3]hept-2-yl) (2-hydroxyvinyl) ketone in 25.0 ml of benzene was added dropwise with stirring to 3.95 g of thionyl chloride. The reaction mixture was allowed to stand for 18 hr at 25° C. The product was isolated by distillation (high vacuum) to afford 2.66 g 1-chloro-3-(2-methylspiro[3.3]hept-2-yl)-1E-propen-3-one as a yellow oil (40%).
Analysis -- bp 65°-75° C; R f (CHCl 3 ) 0.21.
E. Preparation of 1-Iodo-3-(2-methylspiro[3.3]hept-2-yl)-1E-propen-3-one
In a procedure as described in Example 9H, 1-chloro-3-(2-methylspiro[3.3]hept-2-yl)-1E-propen-3-one was reacted with sodium iodide in acetone to yield 1-iodo-3-(2-methyspiro[3.3]hept-2-yl)-1E-propen-3-one (87%).
Analysis -- NMR (CDCl 3 ) δ1.32, singlet, 3H; 7.22, doublet, J=14Hz, 1H; 7.85, doublet, J=14Hz, 1H.
F. Preparation of 1-Iodo-3RS-hydroxy-3-(2-methylspiro[3.3]hept-2-yl)-1E-propene
In a procedure as described in Example 9I, 1-iodo-3-(2-methylspiro[3.3]hept-2-yl)-1E-propen-3-one was reduced with sodium borohydride in ethanol to yield 1-iodo-3RS-hydroxy-3-(2-methylspiro[3.3]hept-2-yl)-1E-propene (100%).
Analysis -- NMR (CDCl 3 ): δ1.35, singlet, 3H; 3.3-4.0, multiplet, 2H; 6.35, multiplet, 2H.
IR: λ max CHCl .sbsp.3 2.78, 2.95(broad), 6.20, 7.25, 7.25, 10.3, 10.5μ.
G. Preparation of 1-Iodo-3RS-(tetrahydropyran-2-yloxy)-3-(2-methylspiro[3.3]hept-2-yl)-1E-propene.
Crude 1-iodo-3RS-hydroxy-3-(2-methylspiro[3.3]hept-2-yl-1E-propene (3.31 g) was dissolved in 12.0 ml dry ether and stirred under argon at 25° C. Distilled dihydropyran (1.25 ml) was added, followed by a small spatula of p-tolunesulfonic acid. The reaction mixture was allowed to stand for 2 hr at 25° C, then partitioned between ether and saturated aqueous NaHCO 3 . The organic layer was dried (MgSO 4 ), filtered, and evaporated in vacuo to afford 4.43 g crude 1-iodo-3RS-(tetrahydropyran-2-yloxy)-3-(2-methylspiro[3.3]hept-2-yl)-1E-propene as a crude orange oil. Purification by column chromatography on Silica Gel afforded 2.90 g of the compound as a clear oil.
Analysis -- NMR (CDCl 3 ): δ1.32, singlet, 3H; 3.50, multiplet, 1H; 3.75, multiplet, 2H; 4.60, broad singlet, 1H.
EXAMPLE 15
A. Evaluation of Inhibition of Human Platelet Aggregation by Analogues of Prostaglandins Structure III
The ability of test compounds to inhibit platelet aggregation was determined by a modification of the turbidometric technique of Born (Nature, 194:927 [1962]). Blood was collected from human volunteers who had not ingested aspirin or aspirin-containing products within the preceding two weeks in heparinized containers and was allowed to settle for one (1) hour. The platelet rich plasma (prp) supernates were collected and cooled. Siliconized glassware was used throughout.
In a representative assay 1.9 ml of PRP and 0.2 ml of test compound at the appropriate concentrations (0.001 to 100 mcgm), or 0.2 ml of distilled water (control procedure) were placed in sample cuvettes. The cuvettes were placed in a 37° C incubation block for 15 minutes, and then in a spectrophotometer linked to a strip chart recorder. After 30-60 seconds, 0.2 ml of a solution, prepared by diluting a calf-skin collagen solution 1:9 with Tyrodes' Solution, was added to each cuvette. Platelet aggregation was evidenced by a decrease in optical density.
Calculation of the degree of inhibition of platelet aggregation exhibited by each concentration of test compound was accomplished according to the method of Caprino et al., (Arzneim-Forsch., 23:1277 [1973]). An ED 50 value was then determined graphically. Activity of the compounds was scored as follows:
______________________________________ED.sub.50 (mcg/kg) Activity Value______________________________________No activity 0>1.0 1>0.1 ≦ 1.0 2>0.01 ≦ 0.1 3>0.001 ≦ 0.01 4≦0.001 5______________________________________
B. Evaluation of the Effects of Prostaglandin Analogues III on Gastric Secretion in the Rat
A procedure based on that described by Lipmann (J. Pharm. Pharmacol., 21:335 [1968]) was used to assess the influence of test compounds on gastric secretion. Rats of one sex weighing 150 to 200 g were randomly divided into groups of six animals each and fasted for 48 hours previously to the experiments, water being available adlibitum. The animals were anesthetized with ether, the abdomen was opened through a midline incision and the pylorus was ligated. Test compounds were diluted from stock solution so as to administer a dose of 1.5 mg/kg in a volume equivalent to 1 ml/kg. Subcutaneous injections were applied immediately after surgery and again 2 hours later, so that a total dose of 3.0 mg/kg was administered. Dilutions were made with phosphate buffer (pH 7.38) as recommended by Lee et al. (Prostaglandins 3:29 [1973]), in order to insure adequate stability of drugs at the subcutaneous depot. Each compound was tested in one group of rats; an additional control group received only the vehicle.
Four hours after pyloric ligation the animals were killed with ether, the cardias ligated and the stomachs removed. The volume of gastric secretion was measured and the contents centrifuged at 500 rpm for 10 minutes. Total acid in the supernatant was titrated against a 0.1 N sodium hydroxide solution and the amount expressed in mEq.
Volume and total acid values of the treated group were compared with those of the controls by the "T" test. Antisecretory activity was scored according to the following scale:
______________________________________% decrease in acidity Activity Value______________________________________ <26 026-50, not significant 126-50, significant 251-75 3 76-100 4______________________________________
C. Evaluation of the Effects of Prostaglandin Analogues III on Femoral Blood Flow in the Dog
The peripheral vasodilator or constrictor effects of these compounds were determined in mongrel dogs of either sex, weighing between 10 and 20 kg anesthestized intravenously with 35 mg/kg of sodium pentobarbital. An external iliac artery was dissected immediately above the femoral arch for a length of approximately 5 cm and a previously calibrated, non-connulating electromagnetic flowmeter sensor with a lumen between 2.5 and 3.5 mm was placed snugly around the vessel. Cannulas were placed in a branch of the artery arising distally to the location of the flowmeter sensor for intraarterial drug administrations, in the contralateral femoral artery for systemic blood pressure recordings and in the trachea for artificial respiration with room air. Femoral blood flow and systemic blood pressure were continously recorded with an electromagnetic flowmeter and pressure tranducer, respectively.
After an adequate control period, test compounds were injected intraarterially at one log-spaced doses ranging from 0.001 to 10 mcg., in a volume of 0.5 ml and at 5 to 10 minute intervals. Maximum changes in bloodflow, as well as any variations in blood pressure, were tabulated for each dose in absolute values (ml/min. and mmHg). The calculations were made taking as control values those existing immediately before administration of each dose. The direction of the observed change (plus for increase and minus for decrease) was also noted. The dose changing bloodflow by 100 ml/min (ED 100 ml/min) was calculated graphically and was used for scoring activity as follows:
______________________________________ED.sub.100 ml/min, mcg Activity Value______________________________________>10.0 01.01 - 10.0 10.11 - 1.0 20.01 - 0.1 3______________________________________
D. Evaluation of the Effects of Prostaglandin Analogues III on Blood Pressure and Heart Rate in the Anesthetized Cat
The acute effects of test compounds on blood pressure and heart rate were determined in cats of either sex anesthetized with a mixture of pentobarbital sodium (35 mg/kg, i.v.) and barbital sodium (100 mg/kg, i.v.). Cannulas were placed in the trachea to allow adequate spontaneous ventilation, in a femoral artery for blood pressure recording with a strain gage transducer, and in a saphenous vein for drug administration. Heart rate was recorded by means of a cardiotachometer driven by the R wave of the electrocardiogram. After a period of 10 minutes of stable recordings of blood pressure and heart rate, the test compound was administered intravenously at doses increasing from 0.01 to 10.0 mcg/kg, spaced one log and injected at 10 minutes intervals. All doses were injected in a volume of 0.1 ml/kg. Modifications of blood pressure and heart rate induced by the test compound were expressed both in absolute units (mmHg and beats/minutes) and as percent of values recorded immediately before administration of each dose. Biphasic responses were tabulated in the order in which they occur. The direction of the observed changes was also noted (+ for increases and - for decreases).
Activity of compounds in this test was judged only on the basis of the degree of hypotension observed. Thus, the ED 50 mmHg (dose decreasing blood pressure by 50 mmHg) was calculated graphically and the compound scored according to the following scale:
______________________________________ED.sub.50 mmHg, mcg/kg Activity Value______________________________________>10.0 01.01 - 10.0 10.11 - 1.0 20.01 - 0.1 3______________________________________
Table D summarizes the results of the preceding assays A to D utilizing the preferred examples.
TABLE D
Summary of Activity of Prostaglandin Analogues III in; Test A: Inhibition of Human Platelet Aggregation; Test B: Inhibition of Rodent Gastric Secretion; Test C: Increase in Canidae Femoral Blood Flow; and Test D: Decrease in Normal Feline Blood Pressure and Heart Rate
TABLE D______________________________________TR Example Activity ValueNo. No. Test A Test B Test C Test D______________________________________4126 2A 1 NT NT 04127 2B 1 NT NT 04120 1A 3 2 0 04121 1B 1 1 2 04020 5A 1 0 0 04021 5B 1 0 0 04136 4A 1 1 0 04137 4B 1 3 3 24146 6A 1 0 0 04147 6B 1 0 0 24139 3A 1 0 0 04138 3B 1 NT NT 04713 7A 1 4 NT NT4714 7B 1 0 NT NT4841 12A 1 0 NT NT4852 12B 1 2 NT NT4842 13A 1 0 NT NT4845 13B 3 3 NT NT4726 8A 1 0 NT NT4727 8B 1 0 NT NT4758 11B 1 0 NT NT4759 11A 1 0 NT NT______________________________________ NT: Not tested
E. Evaluation of Cascade Assay Effects by Analogues of Prostaglandin Structure III
The smooth muscle stimulant effects of test compounds were determined simultaneously in four different tissues that are known to be reactive to naturally occurring prostaglandins. Segments of rat stomach fundus, rat colon, chick rectum and rabbit aortic strip were obtained as described by: Vane, J. R., Brit. J. Pharmacol., 12: 344 (1957); Regoli, D. and Vane, J. R., Brit. J. Pharmacol., 23: 351 (1964); Mann, M. and West, G. B., Brit. J. Pharmacol., 5: 173 (1950); and Furchgott, R. F. and Bhadrakom, R., J. Pharmacol. Exper. Ther., 108: 129 (1953). One end of each preparation was tied to the bottom of a 10 ml tissue chamber and the other to a force displacement transducer (Grass FT-03) for continuous tension recording. The stomach, colon, and rectum segments were stretched to an initial tension of 1 g, while the aortic strip was subjected to 4 g. All preparations were left undisturbed for 1 hour prior to testing. The chambers were equipped with an external jacket through which water, maintained at 40° C, was circulated. Preparations were arranged one beneath the other in descending order (aorta, stomach, colon and rectum). Provision was made for bathing the four tissues successively so that they were superfused with the same fluid (Gaddum, H. J., Brit. J. Pharmacol., 6: 321 [1953]. The bathing fluid consisted of: Krebs bicarbonate solution aerated with a mixture of 95% O 2 and 5% CO 2 and warmed at 37° C; atropine sulphate (0.1 mcg/ml), phenoxybenzamine hydrochloride (0.1 mcg/ml), propranolol hydrochloride (3.0 mcg/ml), methysergide maleate (0.2 mcg/ml) and brompheniramine maleate (0.1 mcg/ml) were added to eliminate the possibility of smooth muscle responses being due to stimulation of cholinergic, adrenergic, serotonin or histamine receptors. The fluid was circulated by means of a roller pump and was allowed to drip over the preparations at a rate of 10 ml/minute.
Test compounds were diluted from stock solutions so as to administer quantities ranging from 0.001 100,000 ng in a volume of 0.5 ml. The compounds were applied by dripping on the uppermost tissue, at intervals of 10 to 20 minutes. Maximal increases in tension after each dose were measured and the results were used to plot dose-response curves. ED 50 data (doses necessary to produce a response 50% of maximum) were then calculated graphically for each tissue. Maximum responses utilized were those elicited by PGE 1 in gastric and rectal tissue, by PGF 2 α in colonic tissue, and by PGA 2 in aortic tissue.
Activity in each tissue was scored according to the following scale:
______________________________________ED.sub.50, ng Activity Value______________________________________>10000 01001 - 10000 1 101 - 1000 2 10 - 100 3<10 4______________________________________
F. Evaluation of the Effects on the Rat Uterus in Vitro by Analogues of Prostaglandin Structure III
The uterine stimulant effect of test compounds was determined in segments of uterus obtained from rats (140-160 g) pretreated subcutaneously with 1 mg/kg of diethyl-stilbesterol 18 hours before the experiment. The tissues were placed in 10 ml chambers filled with de-Jalon solution at 29° C, were aerated and bubbled with 95% O 2 and 5% CO 2 , and were prepared for isometric recording with force displacement transducers. Preparations were stretched to an initial tension of 1 g and were left undisturbed for 30 minutes. Carbachol (1 mcg/ml) was then added to the bath and a response was recorded. After a 10 minute interval the carbachol procedure was repeated. Responses to increasing concentrations of a test compound (0.001 to 10 mcg/ml with one log intervals) were then recorded every 10 minutes. Preparations were washed four times after each response. All doses of compounds were administered in a 0.1 ml volume. Because it has been observed that the magnitude of the second response to carbachol (approximately 10% greater than the first) is close to the maximal response of the tissue, such value was taken as a measure of the sensitivity of a particular segment. Responses to each concentration of the test compound were expressed in terms of percentage of the second response to carbachol and the ED 50 (dose producing a response 50% that of carbachol) was calculated graphically. Activity was scored according to the following scale:
______________________________________ED.sub.50 (mcg/ml) Activity Value______________________________________>10 01.001 - 10 10.101 - 1.0 2 0.01 - 0.1 3<0.01 4______________________________________
G. Evaluation of the Effects on the Guinea Pig Trachea in Vitro by Analogues of Prostaglandin Structure III
A male guinea pig weighing 200-500 g was killed by a blow on the head. A 20 mm length of the trachea was dissected from the animal, transferred to a petri dish containing Krebs' solution (aerated with 95% O 2 and 5% CO 2 at 37° C), and cut longitudinally opposite the tracheal muscle. The tissue was then cut transversely three quarters of the distance across, a second cut in the opposite direction (again three quarters of the distance across the tissue) was made and the procedure was continued for the whole tissue. The ends of the trachea were pulled to form a zig-zag shaped strip. The tracheal strip used in the experiment was approximately 30 mm when extended under 0.25-0.5 g load in the tissue bath. Cotton thread was tied to one end of the tissue, and linen thread to the other. It was attached via the linen thread to a glass hook in a 5 ml isolated tissue bath containing Krebs' solution (37° C, aerated with a mixture of 95 % O 2 and 5% CO 2 ). The opposite end was attached via cotton to an isotonic Harvard transducer (Model 386 Heart/Smooth Muscle Transducer, Harvard Apparatus). The load on the transducer lever was small, usually 0.3 g, with a range of 0.25-0.5 g, and the magnification high, 80 fold using an appropriate twin-channel pen recorder. A minimum of 30 minutes was allowed before applying a test compound to the tissue. Test compounds were then applied (in volumes of 0.5 ml) at 30 minute intervals, being in contact with the tissue for 5 minutes followed by an overflow washout time of 20 seconds.
Prostaglandin E 1 , at a bath concentration of 0.1 mcg/ml, was then tested repeatedly on two such strips, obtained from two different animals, until two responses (the values of which are recorded) differing by no more than 25% occur. A test compound was then added to the same two strips at bath concentrations of 0.01, 0.1, 1.0, and 10.0 mcg/ml and the effects of the compound were recorded. After the test compound had been evaluated at the highest concentration, PGE 1 was retested at 0.1 mcg/ml (and the value of the response recorded) to insure that the viability of the strips was retained during the experiment. The mean of the effects of the test compound on the two strips was then calculated for each concentration, and, based on the resulting values, an activity value was assigned as follows:
______________________________________Response Activity Value______________________________________More relaxation at 0.01 mcg/mlthan that elicited by PGE.sub. 1 R4More relaxation at 0.1 mcg/mlthan that elicited by PGE.sub.1 R3More relaxation at 1.0 mcg/mlthan that elicited by PGE.sub.1 R2More relaxation at 10.0 mcg/mlthan that elicited by PGE.sub.1 R1No effect at any concentrationgreater than that elicitedby PGE.sub.1 0More contraction at 10.0 mcg/mlthan the degree of relaxationelicited by PGE.sub.1 C1More contraction at 1.0 mcg/ml thanthe degree of relaxationelicited by PGE.sub.1 C2More contraction at 0.1 mcg/ml thanthe degree of relaxationelicited by PGE.sub.1 C3More contraction at 0.01 mcg/ml thanthe degree of relaxationelicited by PGE.sub.1 C4______________________________________
H. Evaluation of Antagonistic Effects on the Guinea Pig Ileum in Vitro by Analogues of Prostaglandin Structure III
The degree and specificity of antagonism of test compounds to the smooth muscle stimulant effects of prostaglandins were assessed in segments of terminal guinea pig ileum. Preparations were placed in tissue chambers filled with Ringer-Tyrode solution at 37° C, bubbled with a mixture of 95% O 2 and 5% CO 2 , and arranged for isometric recording with force displacement transducers. The segments were stretched to an initial tension of 1 g, and responses to a test concentration of acetylcholine (0.1 mcg/ml) were obtained every 5 minutes until two similar responses were observed (usually after four administrations). Responses to acetylcholine (0.1 mcg/ml), PGE 1 (0.1 mcg/ml), BaCl 2 (100 mcg/ml) and PGF 2 α (1 mcg/ml) were obtained (and recorded) in that order at 5 minute intervals before and after 100 seconds of incubation with 0.1 and 1.0 mcg/ml of the test compound. Any direct contractile effect of the test compound was recorded and evaluated in terms of mean values in grams of tension developed at each concentration. Responses to the different agonists observed after incubation with the test compound were expressed as percent of control responses. All drugs were administered in a volume of 0.1 ml.
Antagonism to prostaglandins was scored independently for PGE 1 and PGF 2 α according to the following criteria:
______________________________________Response Activity Value______________________________________Less than 50% blockade of PG response 0More than 50% blockade of PG responsesand more than 10% antagonism of Achand/or BaCl.sub.2, or production of directcontraction 1More than 50% blockade of PG responsesat 1 mcg/ml with less than 11% antagonismof Ach and BaCl.sub.2 without production ofdirect contraction______________________________________
Table E summarizes the results of the preceding assays E to H utilizing the preferred examples.
TABLE E__________________________________________________________________________Summary of Activity of Prostaglandin Analogues III in:Test E: Cascade AssayTest F: Rat UterusTest G: Guinea Pig TracheaTest H: Antagonistic Effects on Guinea Pig Ilcum Test HTR Ex. Test E Test Test AntagonismNo. No. Stomach Colon Rectum Aorta F G PGE.sub.1 PGF.sub.2α__________________________________________________________________________4126 2A 0 O 0 0 NT Cl 0 14127 2B 0 0 0 0 0 C1 0 14120 1A 0 0 1 0 0 C4 0 04121 1B 0 0 0 0 0 C1 0 04020 5A 2 0 0 0 0 R0 0 04021 5B 4 0 0 0 0 C0 0 04136 4A 2 0 1 0 0 C2 0 04137 4B 1 0 NT 0 0 C1 0 04146 6A 1 2 NT 0 0 C0 0 04147 6B 2 0 2 1 0 R0 0 14139 3A 0 0 0 0 0 C1 0 04138 3B 0 0 0 0 0 C1 0 04713 7A 0 0 1 0 0 C1 0 04714 7B 0 0 0 0 0 Cl 0 04841 12A 0 0 0 0 0 C0 0 04852 12B 0 0 0 0 2 C0 0 04842 13A 0 0 0 0 0 R0 0 04845 13B 0 0 0 0 0 C4 1 04726 8A 0 0 0 0 0 C4 1 04727 8B 0 0 0 0 0 C2 0 04758 11B 0 0 0 0 0 C1 0 04759 11A 0 0 0 0 0 C4 0 0__________________________________________________________________________ NT:not tested RWW:ml | Novel monospiroalkyl analogues or derivatives of prostaglandin A, E and F are useful modifiers of smooth muscle activity. The compounds have valuable pharmacalogical properties as platelet antiaggregating agents and gastric antisecretory agents. The compounds are also valuable pharmacological agents for increasing femoral blood flow and decreasing blood pressure and heart rate. | 2 |
TECHNICAL FIELD
[0001] The invention described herein pertains generally to the use of alkylphenol-free polymeric polyphosphites and polymeric copolyphosphites to stabilize rubber, during its production and rubber compounds during processing and use.
BACKGROUND OF THE INVENTION
[0002] At least one purpose associated with the addition of a stabilizer to a rubber is to prevent deterioration of the rubber during processing at high temperatures and also to permit the manufacture of products with increased intrinsic quality attributable at least in part to increased resistance to thermal and light degradation during their intended use.
[0003] Many organic phosphites have been used as stabilizers, and most are based on alkylphenols. Among them are the commercially significant phosphites, tris (nonylphenyl) phosphite (TNPP) and tris (2,4-di-t-butylphenyl) (TTBP) phosphite. Historically, TNPP has been the primary low cost liquid phosphite stabilizer used in the plastic and rubber industry. Recently, however, plastic and rubber manufactures have been reluctant to use TNPP in their formulation due to concerns that one of the degradation products of TNPP (nonylphenol) may be xenoestrogenic.
[0004] Due to this concern about alkylphenols, it is advantageous to use a phosphite containing no alkylphenols. U.S. Pat. No. 8,563,637, U.S. Pat. No. 8,981,042, US published patent application US 2014/0378590 and US published patent application US2013/0190434 as well as applications claiming priority thereto and therefrom, all disclose polymeric polyphosphites and copolymeric polyphosphites, that are good polymer stabilizers and do not contain any alkylphenols. Such polymeric polyphosphites are unique since they have very low migration from polymer films, are good color stabilizers for polymers, exhibit good color stability towards gamma irradiation of polymers, and in general are a good overall stabilizer for polymers especially LLDPE and all polyolefins. This invention will illustrate the use of alkylphenol-free polymeric polyphosphites that show enhanced stabilizing performance in rubbers, e.g., polybutadiene rubber.
[0005] It has been found that using these polymeric phosphites containing no alkylphenols has some unexpected performance benefits in rubber compounds. These polyphosphites offer superior color protection during high temperature processing and long term heat aging. In addition to these color benefits they provide superior protection against gel formation.
SUMMARY OF THE INVENTION
[0006] The present invention is directed to novel liquid polymeric polyphosphites of the general structure (I) as stabilizers for rubbers during processing.
[0000]
[0007] wherein
each R 1 , R 2 , R 3 and R 4 are the same or different and are independently are selected from the group consisting of C 12-20 alkyl, C 12-22 alkenyl, C 12-40 cycloalkyl, C 12-40 cycloalkylene, C 12-20 alkyl glycol ethers and Y—OH as an end-capping group; each Y is independently selected from the group consisting of C 2-40 alkylene, C 7-40 cycloalkylene, C 3-20 alkyl glycol ethers, C 3-40 alkyl lactone, and —R 7 —N(R 8 )—R 9 —; R 7 , R 8 and R 9 are independently selected from the group consisting of C 1-20 alkyl, C 2-22 alkenyl, C 6-40 cycloalkyl, C 7-40 cycloalkylene and H; m is an integral value ranging from 1 to 100 inclusive; x is an integral value ranging from 2 to 1,000 with the proviso that when —O—Y is a C 3-20 alkyl glycol ether, x is an integral value no less than 7; and further wherein no more than two of R 1 , R 2 , R 3 and R 4 are terminated with an hydroxyl group.
[0014] The present invention is also directed to novel copolymeric polyphosphites of the general structure (II) as stabilizers for polymers during processing.
[0000]
[0015] wherein
each R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and are independently selected from the group consisting of C 12-20 alkyl, C 12-22 alkenyl, C 12-40 cycloalkyl, C 12-40 cycloalkenyl, C 12-20 alkyl glycol ethers and A-OH and B—OH as an end-capping groups; each A and B are different and independently selected from the group consisting of C 2-40 alkylene, C 7-40 cycloalkylene, C 3-20 alkyl glycol ethers, C 3-40 alkyl lactone, and —R 7 —N(R 8 )—R 9 — wherein R 7 , R 8 and R 9 are independently selected from the group C 1-20 alkyl, C 2-22 alkenyl, C 6-40 cycloalkyl, C 7-40 cycloalkylene and H; m and n are integral values ranging from 1 to 100 inclusive; x and y are integral values ranging from 1 to 1,000 wherein x+y sum to at least 3, with the proviso that when —O-A or —O—B are C 3-20 alkyl glycol ethers, at least one of x or y is an integral value no less than 7; and further wherein no more than two of R 1 , R 2 , R 3 , R 4 and R 5 are terminated with an hydroxyl group.
[0021] The present invention is also directed to the novel cycloaliphatic polyphosphite and copolyphosphites of U.S. Pat. No. 8,981,042 and patent application US 2014/0378590 and have the general Structure (Ill).
[0000]
where each R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and are independently selected from the group consisting of C 1-20 alkyl, C 2-22 alkenyl, C 6-40 cycloalkyl, C 7-40 cycloalkylene, C 3-20 methoxy alkyl glycol ethers, C 3-20 alkyl glycol ethers or Y—OH (serving as an end capping moiety) for R 1 , R 2 , R 3 , R 4 , R 5 and R 6 ;
Y is selected from the group consisting of C 2-40 alkylene, C 2-40 alkyl lactone, and C 2-40 cycloalkyl and further comprises C 2-20 alkyl glycol ethers when Y is in the polyphosphite backbone (e.g., ethylene, propylene, caprylactone, polyalkylene glycol);
x is an integral value ranging from 8 to 1,000;
z is an integral value ranging from 0 to 1,000 with the proviso that when z is 8 or greater, then x is an integral value ranging from 1 to 1,000;
m is an integral value ranging from 1 to 20;
w is an integral value ranging from 1 to 1,000.
[0028] The novel, polymeric polyphosphites and copolymeric polyphosphites of the general Structures (I) or (II) or (Ill), as disclosed in above referenced patents and patent applications are especially suitable for stabilization of rubber and rubber compounds. The advantages of high molecular weight polymeric phosphites are very low volatility, low migration out of the rubber being stabilized, low gel counts, and improved resistance to NOx gas. These advantages can translate into desirable properties for rubber compounds when the polymeric polyphosphites are added either singly or in combination.
[0029] This invention therefore relates to a composition that is prepared by processing a rubber compound with one of the polymeric polyphosphites disclosed in the above patents and/or applications and the process for preparing a film or molded article from said composition. The polymeric polyphosphite may be used alone or in combination with other antioxidants and polymer additives.
DETAILED DESCRIPTION OF THE INVENTION
[0030] The best mode for carrying out the invention will now be described for the purposes of illustrating the best mode known to the applicant at the time of the filing of this invention. The examples and figures are illustrative only and not meant to limit the invention, as measured by the scope and spirit of the claims.
[0031] Unless the context clearly indicates otherwise: the word “and” indicates the conjunctive; the word “or” indicates the disjunctive; when the article is phrased in the disjunctive, followed by the words “or both” or “combinations thereof” both the conjunctive and disjunctive are intended.
[0032] As used in this application, the term “approximately” is within 10% of the stated value, except where noted.
[0033] As further used in this application, the term “rubber” or “rubbers” or “rubber compound” includes both natural and synthetic rubbers. Natural rubber, coming from latex of Hevea brasiliensis , is mainly poly-cis-isoprene containing traces of impurities like protein, dirt etc. Although it exhibits many excellent properties in terms of mechanical performance, natural rubber is often inferior to certain synthetic rubbers, especially with respect to its thermal stability and its compatibility with petroleum products.
[0034] Synthetic rubber is made by the polymerization of a variety of petroleum-based precursors called monomers. The most prevalent synthetic rubbers are styrene-butadiene rubbers (SBR) derived from the copolymerization of styrene and 1,3-butadiene. Other synthetic rubbers are prepared from isoprene (2-methyl-1,3-butadiene), chloroprene (2-chloro-1,3-butadiene), and isobutylene (methylpropene) with a small percentage of isoprene for cross-linking. These and other monomers can be mixed in various proportions to be copolymerized to produce products with a range of physical, mechanical, and chemical properties. The monomers can be produced pure and the addition of impurities or additives can be controlled by design to give optimal properties. Polymerization of pure monomers can be better controlled to give a desired proportion of cis and trans double bonds.
[0035] As used herein, synthetic rubbers includes, but is not limited to polyacrylate rubbers, ethylene-acrylate rubbers, polyester urethanes, bromo isobutylene isoprene rubbers, polybutadiene rubbers, chloro isobutylene isoprene elastomers, polychloroprene, chlorosulfonated polyethylene, epichlorohydrin, ethylene propylene elastomers, ethylene propylene diene monomers (“EPDM”), polyether urethane rubbers, perfluorocarbon rubbers, fluorinated hydrocarbons, fluoro silicone rubbers, fluorocarbon rubbers, hydrogenated nitrile butadiene rubbers, polyisoprene, isobutylene isoprene butyl rubbers, acrylonitrile butadiene, polyurethane, styrene butadiene rubbers, styrene ethylene butylene styrene copolymers, polysiloxane, vinyl methyl silicone, acrylonitrile butadiene carboxy monomer, styrene butadiene carboxy monomer, thermoplastic polyether-esters, styrene butadiene block copolymers, styrene butadiene carboxy block copolymers.
[0036] As further used in the application, synthetic rubbers includes the use of at least one rubber as an impact modifier for other polymer systems, particularly such as polystyrene. Rubber may be added to polystyrene at levels of about 10% to produce High Impact Polystryene (HIPS). The improved properties of the neat rubber will also translate into the final product when used as an impact modifier. For example the improved color and mechanical properties of the rubber stabilized by the polymeric polyphosphites of the current invention will translate into improve color and mechanical properties of the High Impact Polystrene.
[0037] In addition, the term “gum rubber” is sometimes used to describe the tree-derived natural rubber and to distinguish it from synthetic natural rubber.
[0038] The invention provides for improved rubber compositions prepared by a standard rubber processing processes. The rubber may be any of the commercially produced rubbers and/or compositions containing rubbers or rubber compounds.
[0039] The rubbers may contain polymers of monoolefins and diolefins such as polyethylene, polypropylene, polyoisobutylene, poly-1-butene, poly-4-methylpentene, polyisoprene, polybutadiene, for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and polymers of cycloolefins such as cyclopentene and norbornene, and blends of the polymers described above.
[0040] The rubbers may contain copolymers of monoolefins and diolefins with each other or with other vinyl monomers such as ethylene/propylene, propylene/1-butene, propylene/isobutene, propylene/butadiene, ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, isobutylene/isoprene, ethylene/alkylacrylates, ethylene/alkylmethacrylates, ethylene/vinyl acetate, ethylene/acrylic acid (and salts, ionomers, thereof), terpolymers of ethylene, propylene, and dienes such as hexadiene, dicyclopentadiene, and ethylene-norbornene.
[0041] In general the polymeric polyphosphites of this invention are added to the organic material to be stabilized in amounts from about 0.001 wt % to about 5 wt % of the weight of the organic material to be stabilized. A more preferred range is from about 0.01% to 2.0%. The most preferred range is from 0.025% to 1%.
[0042] The stabilizers of this invention may be incorporated into the organic materials at any convenient stage prior to manufacture of the film using techniques known in the art.
[0043] The stabilized polymer compositions of the invention may also contain from about 0.001% to 5%, preferably from 0.01% to 2%, and most preferably from 0.025% to 1% of other conventional stabilizers listed below or in Vanderbilt Chemicals, “Antioxidants for Rubber Selection Guide ”, by Vanderbilt Chemicals, published 2013, (hereinafter “Vanderbilt Selection Guide”).
[0044] Hindered phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol; octadecyl 3,5-di-tert-butyl-4-hydroxy-hydrocinnamate; tetrakis methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane; and tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate. Other phenolic antioxidants are listed in Vanderbilt Selection Guide.
[0045] Thioesters such as dilauryl thiodipropionate and distearyl thiodipropionate.
[0046] Aromatic amine stabilizers such as N, N′-diphenyl-p-phenylene-diamine. Other aromatic amine stabilizers are listed in the Vanderbilt Selection Guide.
[0047] UV absorbers such as 2-hydroxy-4-n-octyloxybenzophenone, 2(2′-hydroxy-5′-methylphenyl)-benzotriazole, and 2(2′-hydroxy-5-t-octylphenyl)-benzotriazole.
[0048] Phosphites such as tris(2,4-di-tert-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, and 2,4-dicumylphenyl pentaerythritol diphosphite.
[0049] Acid neutralizers such as calcium stearate, zinc stearate, calcium lactate, calcium stearyl lactate, epoxidized soybean oil, and hydrotalcite (natural and synthetic).
[0050] Other additives such as lubricants, antistatic agents, antiblocking agents, slip agents, fire retardants, nucleating agents, impact modifiers, blowing agents, plasticizers, fillers, dyes, and pigments may be used in an amount appropriate and in combination of the invented polymeric phosphites to modify a selected property of the polymer.
[0051] Alkanol amines such as but not limited to triethanolamine and triisopropanolamine.
[0052] The polymeric phosphites (generally a liquid) of this invention are generally much more compatible with the rubber polymer than other commercially available mono-phosphites such as tris(2,4-di-t-buytlyphenol)phosphite (TTBP) and tris(nonylphenol)phosphite (TNPP). The high molecular weight and the improved compatibility offers several distinct advantages over traditional monophosphites or diphosphites. Solid phosphites such as TTBP are known to exude from polymer films and must be used at lower concentrations to minimize buildup on processing equipment. Additionally such solid monophosphites may exude to the surface of the polymer post-processing forming a layer of dust on the surface of the film.
[0053] Liquid monophosphites such as TNPP do not typically exude from the polymer during processing or post processing. However it is still desirable to have a more compatible polymeric phosphite since much of the rubber films and molded products produced are used for food packaging where the film may come into direct contact with food. It is known that whatever additives are contained in the polymer film have the potential to migrate from the polymer into the food it is in contact with. The polymeric polyphosphites of this invention exhibit far lower migration when in contact with food due to their high molecular weight.
[0054] Rubber compositions containing the polymeric polyphosphites also exhibit improved color stabilization in comparison to TNPP and TTBP. This is evident during melt processing as well as post processing. During melt processing the color, as measured by the Yellowness Index (YI) of the polymer may increase from the shear and heat degradation attributable to the extrusion or film production process. The polymeric polyphosphites produce a rubber compound of lower color (YI) when used at equal loading levels or even when used at lower loading levels.
[0055] There are many conditions post processing that the rubber compound may be exposed to that has the potential to increase the color of the polymer. Rubber compounds may be exposed to NO gases which are highly oxidative. Alkylphenols are oxidized by these gases forming color bodies in the polymer. Phosphites such as TNPP and TTBP are produced from alkylphenols and therefore contribute to the color increase of a rubber compound exposed to these gases. Since the polymeric polyphosphites of the current invention contain no alkylphenols, they do not contribute to the color increase thereby producing a product with lower color.
[0056] Rubber compounds may also be subject to gamma irradiation in medical applications to sterilize a medical device. The gamma irradiation can also decompose any alkylphenol groups in the polymer causing an increase in color. The polymer polyphosphites of this invention show far superior color hold when exposed to gamma irradiation since they are not composed of any alkylphenols.
[0057] Rubber compounds can also be exposed to elevated temperatures post processing. The elevated temperatures are very degradative to the polymer causing both color increase and loss of the polymer's mechanical properties. The polymeric polyphosphites offer equal or slightly better against the loss of mechanical properties and far superior protection against color increase.
[0058] During rubber processing it is common for small gels to form due to crosslinking of the rubber. The polymeric polyphosphites of this invention offer improved protection against the formation of these gels when compared to TNPP or TTBP.
[0059] Additionally the polymeric polyphosphites of the current invention offer a synergy with tocopherols (Vitamin E) when used in combination to stabilize a polymer. It is known in the art that Vitamin E is an excellent polymer stabilizer that can be used at a fraction of the loading level of many hindered phenol stabilizers. However it is not commonly used as a stabilizer in rubber compounds since it has the tendency to cause greatly increased color when used with traditional phosphites like TNPP and TTBP. The polymeric polyphosphites of this invention offer such improved color stability that they can be used with Vitamin E to produce a film with better color than traditional antioxidant packages using hindered phenols and TNPP or TTBP.
[0060] The Vitamin E/polymeric polyphosphite combinations are especially beneficial for protection against gas fade since the hindered phenolic may also contribute to color formation. This unique combination of Vitamin E and the polymeric polyphosphite can be used to make a rubber composition that is essentially completely resistant to gas fade.
[0061] The invention will now be described by a series of examples.
Example 1
[0062] PPG 400 (95 g, 0.237 mol), triphenyl phosphite (73 g, 0.235 mol), a mixture of lauryl and myristyl alcohol with a hydroxyl number of about 280, (47 g, 0.235 mol), and 0.8 grams of potassium hydroxide were added together. The mixture was mixed well and heated to 160-162° C. under nitrogen and held at the temperature for 1 hour. The pressure was then gradually reduced to 0.3 mmHg and the temperature was increased to 170-172° C. over the span of 1 hour. The reaction contents were held at 170-172° C. under vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to 50° C. The product was a clear, colorless liquid.
Example 2
[0063] PPG 400 (48 g, 0.12 mol), triphenyl phosphite (73 g, 0.235 mol), lauryl alcohol, (47 g, 0.235 mol), dipropylene glycol (16 g 0.12 mol) and 0.8 grams of potassium hydroxide were added together. The mixture was mixed well and heated to 160-162° C. under nitrogen and held at the temperature for 1 hour. The pressure was then gradually reduced to 0.3 mmHg and the temperature was increased to 170-172° C. over the span of 1 hour. The reaction contents were held at 170-172° C. under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to 50° C. The product was a clear, colorless liquid.
Example 3
[0064] 1,6 hexane diol (57 g, 0.48 mol), triphenyl phosphite (150 g, 0.48 mol), a mixture of lauryl and myristyl alcohol with a hydroxyl number of about 280, (97 g, 0.48 mol), and 0.8 grams of potassium hydroxide were added together. The mixture was mixed well and heated to 160-162° C. under nitrogen and held at temperature for 1 hour. The pressure was then gradually reduced to 0.3 mmHg and the temperature was increased to 170-172° C. over the span of 1 hour. The reaction contents were held at 170-172° C. under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to 50° C. The product was a hazy, colorless liquid.
Example 4
[0065] The apparatus in Example #1 was used. 100 grams (0.69 mol) of cyclohexane dimethanol, triphenyl phosphite (237 g, 0.76 mol), a mixture of lauryl and myristyl alcohol with a hydroxyl number of about 280, (190 g, 0.95 mol), and 0.4 grams of potassium hydroxide were added. The mixture was mixed well and heated to approximately 150° C. under nitrogen and held at temperature for 1 hour. The pressure was then gradually reduced to 0.3 mm Hg and the temperature was increased to 180° C. over the span of 1 hour. The reaction contents were held at 180° C. under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature. The product was a liquid.
Example 5
[0066] The apparatus in Example #1 was used. 20 grams (0.14 mol) of cyclohexane dimethanol, 7 g polypropylene glycol 400 (0.02 m), triphenyl phosphite (100 g, 0.32 mol), a mixture of lauryl and myristyl alcohol with a hydroxyl number of about 280 (136 g, 0.69 mol) and 0.4 grams of potassium hydroxide were added. The mixture was mixed well and heated to approximately 150° C. under nitrogen and held at temperature for 1 hour. The pressure was then gradually reduced to 0.3 mm Hg and the temperature was increased to 180° C. over the span of 1 hour. The reaction contents were held at 180° C. under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature. The product was a liquid.
[0067] Characteristics of the various synthesized additives may be characterized at least in part by the following tables.
[0000]
TABLE I
Example
#1
#2
#3
#4
#5
appearance
liquid
liquid.
liquid.
liquid
liquid.
Acid Value
0.01
0.05
0.01
0.01
0.01
(“AV”)
(initial)
% P
4.9
5.9
8.9
7.6
6.0
Avg. MW
9,111
7,250
31,515
13,957
1,651
[0068] The following examples are meant to illustrate the benefits of the current invention over convential phosphites. They are not intended to cover every single application which these could be used.
Example 6
High Temperature Oven Aging
[0069] High temperature aging is known to have oxidative effects on polymers and rubbers and often cause color and viscosity issues in polymers and rubbers when exposed to high temperatures. Alkylphenols such as those found in many phosphite stabilizers may also oxidize when exposed to higher temperatures and form color bodies in the polymer and/or rubber contributing to the color problem. This is equally applicable to phenolic primary antioxidants.
[0070] The polymeric polyphosphites of the current invention show a marked improvement in color hold in contrast to an alkylphenol containing phosphite such as TNPP as illustrated in Table II in which various samples were compounded and subjected to high temperature aging at 88° C. for various amounts of time as well as viscosity testing (measured in Mooney units).
[0000]
TABLE II
Formulation*
Sample #1
Sample #2
Sample #3
Unstablized cis-polybutadiene rubber
99.2
99.2
99.2
TNPP
0.5
Example #1
0.5
Example #4
0.5
Irganox ® 1076
0.3
0.3
0.3
Color
Initial
12.0
12.9
12.8
24 hrs
49.9
13.2
13.0
48 hrs
52.0
45.7
44.1
72 hrs
58.0
47.3
45.3
96 hrs
65.8
47.9
46.2
% increase
~448%
~271%
~261%
Mooney Viscosity**
Initial
36
36
36
24 hrs
30
36
37
48 hrs
31
36
37
72 hrs
45
40
39
96 hrs
69
39
39
% increase
~92%
~8%
~8%
*all percentages are by weight percent
**Studies performed on a Monsanto MV 2000 Viscometer @ 100° C.
[0071] As illustrated above, the use of a polymeric polyphosphite (e.g., Example #1 or Example #4) showed improved color control during heat aging and better viscosity control compared to the standard phosphite TNPP.
Example 7
NO x Oven Aging
[0072] NOx gases are known to have oxidative effects on polymers and often cause color issues in polymers exposed to them. Alkylphenols such as those found in many phosphite stabilizers may also oxidize when exposed to these gases and form color bodies contributing to the color problem.
[0073] The polymeric polyphosphites of the current invention show a marked improvement in color hold in comparison to an alkylphenol containing phosphite such as TNPP.
[0074] The following formulations using unstabilized styrene-butadiene rubber were compounded and pressed into 3×3 inch plaques at 150° C. for 3 minutes. The plaques were then cut in half for aging studies. The color of the samples was taken at periodic intervals. NO testing involved placing the plaques in a NO chamber at 65° C., the samples removed and color measuring by YI (yellowness index) in which the higher the number, the darker the color. The samples were also placed in a temperature controlled room (72° F. equivalently 22.2° C.) and samples removed and color tested similar to before.
[0000]
TABLE III
Formulation*
Sample #1
Sample #2
Sample #3
Unstablized SBR rubber
99.0
99.4
99.0
Irganox ® 1520
0.2
0.2
0.2
(2-methyl-4,6-
bis(octylsulfanylmethyl)phenol)
TNPP
0.8
Example #1
0.4
0.8
Color (YI) for NO x /Gas Fade Aging
Initial
9.9
9.7
10.0
Day 1
12.7
12.4
9.4
Day 4
18.2
17.6
14.8
Day 7
21.4
20.7
19.1
% increase
~116%
~113%
~91%
Color (YI) for Ambient Aging
Initial
10.2
10.1
10.1
Day 1
9.5
9.2
8.1
Day 4
10.5
9.2
7.7
Day 7
10.7
9.4
7.7
% increase
~5%
~−7%
~−24%
[0075] The formulations with the polymeric polyphosphite of example #1 performed better when compared to the more traditional TNPP even at lower concentrations.
[0076] The best mode for carrying out the invention has been described for purposes of illustrating the best mode known to the applicant at the time. The examples are illustrative only and not meant to limit the invention, as measured by the scope and merit of the claims. The invention has been described with reference to preferred and alternate embodiments. Obviously, modifications and alterations will occur to others upon the reading and understanding of the specification. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof. | The invention pertains generally to an improved polymer composition which contains at least one polymeric polyphosphite or copolymeric polyphosphite additive containing no alkylphenols. Alkylphenol-free polymeric polyphosphites offer distinct advantages over conventional phosphite technology in rubbers and rubber compounds. Polymeric polyphosphites offer improved performance in regards to the prevention of color formation during high temperature processing and NOx aging. | 2 |
[0001] This application claims priority to United Kingdom Patent Application No. 1516028.6 filed on Sep. 10, 2015 which is hereby incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The invention relates to door looking device that restrict the level to which a door can be opened, particularly for use with front doors to buildings.
BACKGROUND TO THE INVENTION
[0003] Door locking devices, which allow secure limited opening of a door for permitted inspection of a caller but prevent unwanted entry, are generally referred to as “door chains”. These devices usually comprise a short length of chain; a first end of which is secured to a door frame the second end of the chain is releasably secured to a guard plate, with the guard plate being fixedly attached to a door associated with the door frame. When the second end of the chain engages the guard plate, the door chain allows the door to be opened a small amount to confirm the identity of the caller, but prevents unwanted entry, after inspecting the caller, the second end of the chain may be disengaged from the door guard plate allowing the door to be opened fully.
[0004] There are shortfalls associated with the most commonly used, conventional door chains of this type. For example, the door chains:
1) do not provide for varying degrees of limited opening of a door; 2) they do not provide adequate protection for the edge of the door against damage caused by contact with the chain; and 3) the chain may to inadvertently disengage the door guard plate when the door vibrates as it is kicked violently by a would-be intruder, thereby compromising security.
SUMMARY OF THE INVENTION
[0008] Accordingly, the present invention is directed to a door chain assembly comprising a chain and a guard plate, wherein:
[0009] the guard plate comprises a back plate and a chain-receiving plate, wherein the chain-receiving plate extends from the back plate and the chain-receiving plate is provided with an aperture and/or a chain-holding slot;
[0010] and wherein the chain comprises a plurality of links with adjacent links being rotationally offset with respect to one another.
[0011] The present invention positions the chain-receiving aperture and/or slot in a position that is non-parallel with the door. As a result, when the chain engages the aperture and/or slot of the guard plate, gravity assists with seating the chain within the aperture and/or slot. Thus, it becomes more difficult for the chain to inadvertently disengage because to do so, the chain has to move away from the floor, rather than simply away from a vertical slot.
[0012] Preferably, the chain receiving plate extends away from the back plate at an angle between 45° and 135° from the back plate and, more preferably, the chain-receiving plate extends substantially perpendicularly from the back plate. Again, by positioning the slot to be non-parallel with the door, and preferably substantially parallel with the ground, the likelihood of the chain inadvertently disengaging is reduced.
[0013] Advantageously, the aperture and/or the chain-holding slot is provided with removable blocking means and, more advantageously, the removable blocking means is connected to the guard plate and is able to be temporarily displaced from the aperture and/or the chain-holding slot. By providing blocking means that can be inserted and removed from the chain-holding aperture and/or slot, the chain can be prevented from being unintentionally removed from the chain-holding slot.
[0014] In a preferable arrangement, the blocking means is biased so that in a rest position it extends at least partially into the aperture and/or the chain-holding slot and it can be at least partially temporarily displaced against the bias to reduce the amount it extends into the aperture and/or the chain-holding slot. Providing bias means, the blocking member has to be actively retracted to engage or disengage the chain. As a result, the chain cannot be inadvertently disengaged, thereby resulting in a more secure arrangement, particularly as the chain is also arranged to be held in the aperture and/or slot by gravity.
[0015] In one arrangement, the aperture is in communication with a second slot extending in a different direction from the chain-holding slot and the blocking means engages the second slot and biasing means comprises a compression spring positioned in or adjacent to the second slot to resist movement of the blocking means from the aperture and/or the chain-holding slot. A second slot may be provided to hold the biasing means for the blocking member. This allows for the use of a compression spring, or similar, to be employed to bias the blocking member in a position wherein it blocks the aperture and/or slot.
[0016] Advantageously, the blocking member comprises a pivotable cap that is adapted to be received within the aperture. The cap may be connected to the guard plate or the back plate and is able to pivot into, and out of, the aperture and/or slot, thereby blocking the chain from engaging or disengaging the guard plate.
[0017] Alternatively, the blocking member comprises a spring member attached to the guard plate, which, in a rest position, extends into the aperture and/or the chain-holding slot and is adapted to be temporarily displaced such that, when in the displaced position, it is clear of the aperture and/or the chain-holding slot. The use of a spring member provided a biasing to the device, which then allows the aperture and/or slot to be blocked and unblocked as required.
[0018] It may be desirable that the chain-holding slot comprises at least one angled section. By providing an angle in the chain-holding slot, for example the slot being “V” or “W” shaped, the channel in which the chain is held becomes more complex and makes inadvertent disengaging more difficult. Whilst the slot might be provided with curves, an angle is more difficult for the chain to traverse.
[0019] It is advantageous that the longitudinal axis of the links of the chain are substantially perpendicular to one another. Having the links of the chain arranged to be substantially perpendicular to one another allows for the length of the chain to be adjusted by feeding a link into the chain-holding slot in a particular orientation, wherein the adjacent links cannot pass through the chain-holding slot due to their orientation.
[0020] The assembly may be provided with a chain anchor plate, which is fixedly attached to a door frame for securing one end of the chain to the door frame. Alternatively, the chain may be connected directly to the door frame.
[0021] Preferably, the arrangement between the guard plate and the back plate forms what may be described as a ‘T’ bar as, when viewed from its end, it is generally in the form of a ‘T’ shaped elongate bracket in which the guard chain is engaged in the substantially horizontal limb of the door guard plate.
[0022] The central rib of the ‘T’ bar or ‘T’ shaped bracket may define an aperture close to one end and centrally therein, from which a pair of opposing long narrow slots respectively, extend outwardly from the aperture centrally and transversely of the central rib to slot ends adjacent each end of the central rib. Alternatively, a keyhole shaped aperture may be provided in the central rib of the ‘T’ bar with the keyhole aperture adjacent one end of the central rib and a long narrow slot leading from the aperture, centrally of the central rib to a slot end adjacent the other end of the central rib of the ‘T’ bar door guard plate.
[0023] The slot in the device may be a closed slot, that is, a slot that has a close periphery.
[0024] The back plate may be integral with the guard plate or they may be separate parts that are fixedly connected to one another.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] The invention will now be described further by way of example, with reference to the accompanying drawings, in which:
[0026] FIG. 1 is a front view of a door chain assembly in accordance with the present invention;
[0027] FIG. 2 is a perspective view of the assembly of FIG. 1 in a first position;
[0028] FIG. 3 is a top view of the assembly of FIG. 1 in a second position;
[0029] FIG. 4 is a top view of the door guard plate of FIG. 1 ;
[0030] FIG. 5 is another top view of the assembly FIG. 1 ;
[0031] FIG. 6 is a perspective view of part of the assembly of FIG. 1 ;
[0032] FIG. 7 shows parts of the assembly of FIG. 1 ;
[0033] FIG. 8 is a top view of a second assembly in accordance with the present invention;
[0034] FIG. 9 shows a chain for use with the assemblies of the present invention;
[0035] FIG. 10 is a front view of the part of the chain of FIG. 9 ;
[0036] FIG. 11 is a perspective view of part of a third assembly in accordance with the present invention;
[0037] FIG. 12 is a top view of the third assembly in a first position;
[0038] FIG. 13 is a top view of the assembly of FIG. 12 in a second position;
[0039] FIG. 14 shows a fourth assembly in accordance with the present invention;
[0040] FIG. 15 illustrates a further view of the assembly of FIG. 14 ;
[0041] FIG. 16 is a top view of a fifth assembly in accordance with the present invention;
[0042] FIG. 17 is a top view of a sixth assembly in accordance with the present invention;
[0043] FIG. 18 is a top view of a seventh assembly in accordance with the present invention;
[0044] FIG. 19 shows an eighth assembly in accordance with the present invention;
[0045] FIG. 20 shows a ninth assembly in accordance with the present invention;
[0046] FIG. 21 shows a tenth assembly in accordance with the present invention;
[0047] FIG. 22 shows an eleventh assembly in accordance with the present invention;
[0048] FIG. 23 shows a first part for use in a twelfth assembly in accordance with the present invention;
[0049] FIG. 24 shows a second part for use with the part of FIG. 23 ;
[0050] FIG. 25 shows an alternative second part for use with the part of FIG. 23 ;
[0051] FIG. 26 is a perspective view of a thirteenth assembly in accordance with the present invention;
[0052] FIG. 27 is a perspective view of a further part for use in the assembly of FIG. 26 ;
[0053] FIG. 28 is a perspective view of parts shown in FIGS. 27 and 28 in an assembled arrangement;
[0054] FIG. 29 is a further view of the assembly of FIG. 26 ;
[0055] FIG. 30 is a perspective view of a fourteenth assembly in accordance with the present invention;
[0056] FIG. 31 is a perspective view of a fifteenth assembly in accordance with the present invention in a first position;
[0057] FIG. 32 is a perspective view of the assembly of FIG. 31 in a second position;
[0058] FIG. 33 is a perspective view of a sixteenth assembly in accordance with the present invention;
[0059] FIG. 34 is a perspective view of a seventeenth assembly in accordance with the present invention;
[0060] FIG. 35 is a top view of a eighteenth assembly in accordance with the present invention; and
[0061] FIG. 36 is a perspective view of part of the assembly shown in FIG. 35 .
DETAILED DESCRIPTION
[0062] FIGS. 1 to 7 show a first example of a door chain according to the present invention, in which a door chain assembly 1 is provided. The illustration of FIG. 1 shows the assembly fixedly secured to a door and door frame, with the door chain is in its operative or standby condition, wherein one end of the guard chain 30 is secured to the door frame anchor plate 50 by means of its end link 31 a . The end link 31 a engages the metal loop 52 which forms part of the anchor plate 50 , with the anchor plate 50 fixedly secured to the door frame with screws 15 . The free end of the guard chain 30 is releasably secured in the narrow slot portion 27 in the door guard plate 20 , the guard chain 30 having gained entry to the narrow slot 27 by means of the slot aperture 26 , which has a diameter that allows passage of the guard chain 30 . The slot aperture 26 is closed, blocked or covered by a handle 40 which is spring biased to the closed position, as shown in FIGS. 2 and 3 . It is necessary to move the handle 40 transversely on the guard plate 20 against the force of a small compression spring 36 to provide chain access to the slot aperture 26 . The free end of the guard chain 30 may then be lowered through the slot aperture 26 and a chain link 31 selected for engagement in the narrow slot 27 , the selected link 31 is then moved to abut the slot end 27 a of the narrow slot 27 . The slot 27 is a closed slot that has solid periphery.
[0063] In the illustration of FIG. 1 , the third link 31 from the free end of the guard chain 30 is engaged in the narrow slot 27 , engaging the second link on the free end of the chain in the slot 27 will allow the door to be opened the maximum amount allowed by the guard chain. In this manner link selection determines the amount a door may be opened for inspection of a caller, allowing for varying degrees of limited opening of a door. After inspection of a caller the door must be closed to permit removal of the chain 30 from the door guard plate 20 to allow the door to be opened fully.
[0064] The door guard plate 20 is in the form of a “T” bar, which comprises a chain-receiving plate in the form of a central rib 23 and a back plate in the form of extended flanges 22 . Back plate of the ‘T’ bar provides a pair of extended flanges 22 and 22 a that are provided respectively with several spaced screw fixing apertures 14 by means of which the guard plate 20 is fixedly secured to a door. The central rib 23 of the ‘T’ bar extends beyond the end of the extended flanges in the direction distal from the door frame. The extension portion 29 of the central rib 23 is also reduced in width and acts to support a handle 40 .
[0065] The central rib 23 comprises a slot aperture 26 centrally therein, from which a pair of opposing narrow slots 27 and 28 respectively extend outwardly from the slot aperture 26 . The slots 27 and 28 extend centrally and transversely in the central rib to their respective slot ends 27 a and 28 a, which are adjacent each end of the central rib 23 . The long narrow slot 27 which extends towards the front of the guard plate 20 , in use, is engaged by the guard chain 30 , the short narrow slot 28 accommodates a small compression spring 36 which acts to bias the guard plate handle 40 .
[0066] The slot aperture 26 facilitates entry of the free end of the guard chain 30 into the door guard plate 20 . A link 31 of the guard chain 30 is selected for engagement in the narrow slot 27 and the chain 30 is inserted into the aperture. The selected link 30 is then positioned in, and moved along, the slot 27 towards the front of the door guard plate until the link 31 abuts the slot end 27 a. The slot 27 is slightly wider than the diameter of wire from which the chain links are formed, to ensure that a chain link can only pass sideways through the narrow slot 27 . Thus, the adjacent link of the chain acts as a stop, thereby providing an interlock between the guard chain 30 and the door guard plate 20 . A number of different links on the free end of the guard chain 30 may be engaged within the slot 27 to releasably secure the guard chain 30 to the door guard plate 20 . Individual links of the chain 30 directly engaging the door guard plate 20 provide varying degrees of selective and secure limited opening of the door for inspection purposes and the length of the chain 30 restricts the amount by which the door may be opened. The slot aperture 26 and narrow slot 27 being located on the horizontal plane, facilitates easy engagement of the free end of the guard chain 30 and thereby a selected link 31 , in the door guard plate 20 .
[0067] The rear narrow slot 28 in the extended portion 29 of the central rib 23 of the door guard plate 20 is arranged to house a short compression spring 36 the spring 36 comprises a closed loop 37 at one end to receive a retaining pin 39 . The spring 36 acts to bias the door guard plate handle 40 to its closed position, in which position it blocks access to the slot aperture 26 .
[0068] A handle 40 is provided, which may be fabricated from metal or plastic, the external profile of that handle 40 is generally rectangular and is provided with a transverse recess 42 which allows that handle 40 to be mounted on the narrow portion 29 of the central rib 23 and to be a snug, slidable fit thereon. A portion of the sides 43 and 43 a of the handle 40 are been removed, indicated by numeral 45 to allow the front end of the handle 40 to project onto the central rib 23 to cover the slot aperture 26 when the handle 40 is in its closed position, as shown in FIGS. 2 and 3 . Stop faces 46 on the handle 40 engage the pair of stop faces 25 on the back end of the central rib 23 to limit inward travel of the handle 40 . A pair of pin receiving apertures 44 and 44 a are defined centrally and adjacent the front of the handle 40 and gripping corrugations 47 or the like may be provided on the top and bottom surfaces of the handle 40 .
[0069] In order to assemble the handle 40 on the door guard plate 20 the spring 36 is first loaded into the short rear slot 28 of the central rib 29 , as shown in FIG. 5 , and the handle 40 is then slidably mounted on the narrow portion 29 of the central rib 23 captivating the compression spring 36 on the door guard plate 20 . The spring 36 is then compressed against the slot end 28 a to align the loop 37 on the end of the spring 36 with the pair of apertures 44 and 44 a in the handle 40 . The retaining pin 39 is inserted to locate in and bridge the apertures 44 and 44 a and be engaged in the loop 37 of the spring 36 . The handle 40 is secured on the door guard plate 20 and spring biased transversely thereon to its closed position, in which position it blocks access to the slot aperture 26 .
[0070] In order to engage the guard chain 30 in the door guard plate 20 the handle 40 is first moved transversely on the central rib 23 against the force of the spring 36 sufficient to expose the slot aperture 26 . At this point the spring 36 may have “bottomed”, whilst holding the handle 40 in its open position with one hand the free end of the guard chain 30 is lowered through the slot aperture 26 . A link 31 is selected for engagement in the narrow slot 27 and the selected link 31 is moved to abut the slot end 27 a, as shown in FIG. 4 , after which the handle 40 is then released to automatically close the slot aperture 26 . Thus, the guard chain 30 is releasably secured in the door guard plate 20 and cannot be accidentally or inadvertently disengaged from the door guard plate 20 . In one construction, when the handle 40 is moved to its open position against the force of the spring 36 , it will remain in the open position unaided while the guard chain 30 is being engaged in the door guard plate 20 . The handle 40 may then be manually released to close the slot aperture 26 .
[0071] To disengage the guard chain 30 from the door guard plate 20 the handle 40 is moved transversely on the guard plate 20 against the force of the spring 36 to its open position, exposing the slot aperture 26 . With the handle 40 in its open position, the guard chain 30 is moved transversely in the narrow slot 27 and into the slot aperture 26 and the free end of the guard chain 30 can be lifted out of the door guard plate 20 .
[0072] FIGS. 8 to 10 show a door frame anchor plate 50 described in the previous embodiment and illustrated in FIG. 1 in conjunction with a door guard plate 20 a . The door guard plate 20 a comprises a short length of metal, generally in the form of a ‘T’ section. The main body 21 of the door guard plate 20 a provides a pair of extending flanges 22 and 22 a. The flanges 22 and 22 a are provided, respectively, with several spaced screw fixing apertures 14 by means of which the door guard plate 20 a is fixedly secured to a door. The main central rib 23 of the door guard plate 20 a extends past the flanges 22 and 22 a on the end of the door guard plate that, in use, is furthest away from the door jamb.
[0073] The central rib 23 defines a keyhole slot which comprises a slot aperture 26 , dimensioned to permit passage of the guard chain 30 , which is provided centrally and adjacent the back end of the central rib 23 . A narrow slot 27 extends outwardly from the slot aperture 26 centrally and transversely in the central rib 23 to a slot end 27 a adjacent the front end of the door guard plate 20 a. In use, the free end of the guard chain 30 is releasably secured in the narrow slot 27 .
[0074] A chain handle 60 is provided and is secured in the last link 31 b on the free end of the guard chain 30 . The handle 60 , which is in the form of a generally oval metal or plastic disc is stepped 63 to provide a primary body portion 61 and a secondary body portion 62 . The primary body portion 61 is dimensioned such that it cannot pass through the narrow slot 27 and can only pass sideways through the slot aperture 26 . The width of the secondary body portion 62 of the handle 60 is dimensioned to allow it to pass through the narrow slot 27 thus the handle 60 can only pass sideways through the slot aperture 26 and narrow slot 27 and therefore requires manipulation. An elongated slot 64 is defined centrally in the secondary body portion 62 the aperture 64 extends from the step 63 to adjacent the top of the handle 60 . The last link 31 b on the free end of the guard chain 30 is fixedly secured in the slot 64 in the guard chain handle 60 , the other end of the guard chain 30 is secured to the door frame anchor plate 50 by means of its end link 31 a.
[0075] The chain handle 60 facilitates engagement and disengagement of the free end of the guard chain 30 in the door guard plate 20 a. Requiring that the handle 60 be manipulated in order for the guard chain 30 to be removed from the door guard plate 20 a ensures that the guard chain 30 cannot accidentally or inadvertently disengage the door guard plate 20 .
[0076] In order to engage the guard chain 30 in the door guard plate 20 a, the handle 60 is held on its side and partially entered into the narrow slot 27 and slot aperture 26 , releasing the handle 60 will cause it to swivel through the narrow slot 27 and aperture 26 on the link 31 b which is straddling the narrow slot 27 . The link 31 b is then moved transversely using the free end of the guard chain 30 to be positioned over the slot aperture 26 , at which time the free end of the guard chain 30 may be lowered through the slot aperture 26 . A link 31 is then selected and engages in the narrow slot 27 and is moved transversely therein to abut the slot end 27 a. The guard chain 30 is now releasably secured in the door guard plate 20 a.
[0077] To disengage the guard chain 30 from the door guard plate 20 a, the free end of the guard chain 30 is moved transversely to disengage the narrow slot 27 and locate in the slot aperture 26 . The guard chain 30 may then be drawn upwards through the slot aperture 26 until the handle 60 abuts the side of the aperture 26 . When the guard chain 30 is moved transversely so that the link 31 b straddles the narrow slot 27 , the handle 60 on the link 31 b is swiveled and the handle 60 is pushed upwards and through the narrow slot 27 and slot aperture 26 .
[0078] FIGS. 11 to 15 show door guard plates which employ a plastic or metal closure to shield the slot aperture 26 . The closures are required to be moved manually between open and closed positions and are provided to prevent the guard chain 30 inadvertently disengaging the door guard plate.
[0079] FIGS. 11 to 13 show a door guard plate 20 b, which has a closure 70 that is swivelably mounted on the extension 29 a of the central rib 23 by means of the swivel pin 39 a. The swivel pin 39 a extends through a pair of apertures 75 on the closure 70 and the pin aperture 26 a (not shown) in the central rib extension 29 a. The closure 70 defines a large open, through slot 74 in one side that is dimensioned to receive the central rib 23 . In this manner the closure 70 can cover the slot aperture 26 on both sides of the central rib 23 . FIG. 11 is a perspective view of the closure 70 .
[0080] FIG. 12 shows the closure 70 secured to the central rib 23 on the door guard plate 20 b, by means of the swivel pin 39 a. The closure 70 , in its closed position, blocks access to the slot aperture 26 preventing removal of the guard chain 30 from the door guard plate 20 b. FIG. 13 shows the closure 70 in its open position, after being swivelled on the pin 39 a, allowing access to the slot aperture 26 for removal or insertion of the free end of the guard chain 30 . A handle 60 is not required on the free end of a guard chain 30 if the door guard plate has a slot aperture 26 closure. Any available link 31 will act as an interlock between the guard chain 30 and the door guard plate 20 b.
[0081] FIG. 14 illustrates a door guard plate 20 c that supports a plastic or metal closure 80 , which is in the form of a disc having a peg 82 depending outward from its underside. The peg 82 is close to the periphery of the body 81 . A small annular bead 83 is provided on the end of the peg 82 which is a push fit into the aperture 26 a (not shown) in the central rib extension 29 a. In FIG. 14 , the closure 80 is shown in its closed position in which position it blocks access to the slot aperture 26 , the closure is 80 is swivalable between its two positions on the peg 82 . As doors may be hinged on their left or right sides, the closure 80 can be forced out of the central rib extension 29 a and inserted on either side thereof to change the orientation of the assembly.
[0082] FIG. 15 shows a door guard plate 20 d supporting a plastic closure 90 which has an annular stepped body 91 which is attached to a peg 94 by a hinge portion 93 , the peg 94 defines a small annular bead adjacent its free end and is a force fit into the aperture 26 a (not shown) in the central rib extension 29 a. The reduced diameter portion 92 of the main body 91 of the closure 90 is a snug fit in the slot aperture 26 when the closure 90 is in its closed position FIG. 15 shows the closure 90 in its open position, in which the free end of the guard chain 30 is able to access and engage the door guard plate 20 d. As with the previous example, the closure 90 can be engaged on either side of the central rib extension 29 a.
[0083] FIG. 16 shows a door guard plate 20 e comprising a slot aperture 26 that will not allow direct passage of the free end of the guard chain 30 . In order to releasably secure the guard chain 30 in the door guard plate 20 e each of the links 31 on the free end of the guard chain 30 are required to be singularly, manually manipulated. Each link 31 is required to be aligned sideways with the narrow slot 27 when it can be lowered through the slot aperture 26 and narrow slot 27 until the following link 31 abuts the side of the slot aperture 26 . The guard chain 30 is then rotated 90 degrees to align the adjacent link 31 with the narrow slot 27 , at which time it can be lowered until it abuts the side of the slot aperture 26 . In this manner the free end of the guard chain 30 is entered into the door guard plate 20 e.
[0084] When, for example, a person selects and loads the fourth link 31 from the free end of the guard chain 30 into the door guard plate 20 e, that fourth link is then moved transversely in the narrow slot 27 to abut the slot end 27 a and the guard chain 30 is then releasably secured in the guard plate 20 e. The guard chain 30 is quickly loaded into the door guard plate 20 e by alternating rotation i.e. 90 degrees clockwise then 90 degrees anticlockwise; rotating the guard chain 30 clockwise then anticlockwise, alternately, prevents twisting of the guard chain 30 .
[0085] To disengage the guard chain 30 from the door guard plate 20 e, the free end of the guard chain 30 is moved transversely in the narrow slot 27 and into the slot aperture 26 to the position illustrated in FIG. 16 . The guard chain 30 is then rotated alternately 90 degrees clockwise then 90 degrees anticlockwise until the guard chain 30 disengages the door guard plate 20 e. Requiring that the guard chain 30 be manipulated in this manner ensures that it cannot inadvertently or accidentally disengage the door guard plate 20 e.
[0086] FIGS. 17 and 18 show two door guard plates, 20 f and 20 g, which are almost identical to the door guard plate 20 a of FIG. 8 . The difference between the device of FIG. 8 and the one shown herein is that the narrow slot 27 in the door guard plates 20 f and 20 g has been modified or configured in order to reduce the risk of accidental or inadvertent disengagement of the guard chain 30 from the door guard plates 20 f and 20 g when the door chain 1 is operational.
[0087] FIG. 17 illustrates a door guard plate 20 f in which the narrow slot 27 b defines corrugations 27 c along its length. The corrugations 27 c provide a tortuous path for the selected link 31 to traverse. When the door chain 1 is operational and the link 31 abuts the slot end 27 a, should the door be violently kicked by a would-be intruder, the corrugations 27 c provide resistance to transverse movement of the guard chain 30 in the narrow slot 27 b. The door guard plate 20 g of FIG. 18 comprises a link enclosure 24 at its slot end which is configured to retain the selected link 31 at the slot end 27 a of the door guard plate 20 f, in order to prevent the guard chain 30 inadvertently disengaging the narrow slot 27 d.
[0088] FIGS. 19 to 22 , illustrate door guard plates that utilise resilient means to prevent inadvertent disengagement of the guard chain 30 from the door guard plates.
[0089] FIG. 19 shows a door guard plate 20 h that employs a torsion spring 100 to interfere with the passage of a selected link 31 in the narrow slot 27 . The torsion spring 100 is secured to the door guard plate 20 h by a fixing screw 15 which locates within the coils 101 . The head of the screw 15 grips a reduced diameter coil 103 at the fixed end of the spring 100 . The other free end of the spring 100 comprises a leg 102 , which is bent at 90 degrees to the spring body 101 and that is spring biased against the central rib 23 of the door guard plate 20 h. The leg 102 extends partially into over the narrow slot 27 so as to interfere with the passage of a selected link 31 engaged therein. A selected link 31 is required to be forced past the spring leg 102 as it is being moved to abut the slot end 27 a. To releasably secure the guard chain 30 in the door guard plate 20 h the free end of the guard chain 30 is lowered through the slot aperture 26 and it engages the selected link 31 in the narrow slot 27 . The chain 30 is then pulled sideways on the guard chain 30 . The link 31 will abut the spring leg 102 , then move the selected link 31 past the spring 100 , against the resistance of the spring leg 102 to abut the slot end 27 a.
[0090] FIG. 20 illustrates a door guard plate 20 i, which also utilises a torsion spring 100 b. In this embodiment, a loop 104 on the free end of the spring 100 a projects partially over the narrow slot 27 to obstruct passage of a selected link 31 therein. The spring loop 104 is spring biased against the surface of the central rib 23 . The extended leg potion 105 of the loop 104 is spring biased against the flange 22 . The method of engaging the guard chain 30 in the door guard plate 20 i is the same as the example of FIG. 19 .
[0091] FIG. 21 shows a door guard plate, 20 j, which incorporates a torsion spring, wherein the leg 106 on the free end of the spring 100 b interferes with the passage of the free end of the guard chain 30 in the slot aperture 26 to provide resistance to inadvertent removal of the guard chain 30 from the door guard plate 20 j. To releasably secure the free end of the guard chain 30 in the door guard plate 20 j, the first link 31 is entered into the slot aperture 26 and pulled down on until the ‘selected’ link 31 is aligned with the narrow slot 27 . The guard chain 30 is then moved sideways until the ‘selected’ link 31 abuts the slot end 27 a. To disengage the guard chain 30 from the door guard plate 20 j the engaged link 31 is moved transversely into the slot aperture 26 and the free end of the guard chain 30 is pulled out of the door guard plate 20 j, the spring leg 106 will flex as alternate links 31 are withdrawn.
[0092] FIG. 22 illustrates a door guard plate 20 k that employs a spring clip 100 c to provide resistance to passage of a selected link 31 in the narrow slot 27 . The spring wire clip 100 c has a main body 108 which is curved. The end 107 of the spring clip 100 c is bent at 180 degrees to form a hook 110 , which passes through an elongated slot 121 in the central rib 23 to anchor the end 107 of the spring clip 100 c to the central rib 23 , the other end 109 of the spring clip 100 c is bent to form a hook 111 which also passes through an elongated slot 120 in the central rib 23 to anchor the other end 109 of the spring clip 100 c to the central rib 23 . The main body 108 of the spring clip 100 c is spring biased against the surface of the central rib 23 and projects partially over the narrow slot 27 to provide resistance to passage of a selected link 31 therein. All other aspects of this example, including engaging and disengaging the guard chain 30 in the door guard plate 20 k, have been covered in relation to FIGS. 19 and 20 .
[0093] FIGS. 23 to 25 illustrate an example of a back plate and two chain-receiving plates according to the present invention. The plates are fabricated as a pressing from a flat metal strip or blank, although they may be produced by way of laser cutting a large sheet of metal.
[0094] FIG. 23 is a perspective view of the back plate, which comprises a number of spaced screw receiving apertures adjacent the sides thereof, along with three spaced elongated slots positioned centrally and transversely therein. The slots are dimensioned to receive three corresponding lugs that extend from the back side of the chain-receiving plates shown in FIGS. 24 and 25 . The back plate of FIG. 23 may be used with either of the chain-receiving plates shown in FIGS. 24 and 25 .
[0095] On assembly of the embodiment shown in FIGS. 23 to 25 , a chain-receiving plate ( FIG. 24 or 25 ) is engaged on the back plate of FIG. 23 by engaging the lugs of the chain-receiving plate into the respective apertures of the back plate. Once engaged, the two components are fixedly secured together by welding, which is applied from the back side (the side away from the chain-receiving plate) of the back plate. The welded surfaces may then be easily and quickly dressed on a grinding machine. Thus, when the door guard plate is secured to a door there are no visible signs of welding.
[0096] FIGS. 26 to 29 illustrate a further example of a door guard plate 20 p which may be formed as a pressing by piercing and folding a flat metal blank or strip. The door guard plate 20 p performs the same function as the guard plate 20 a of FIG. 8 . The door guard plate 20 p is generally a short ‘T’ profile bracket having two pairs of lugs 22 and 22 a respectively extending at 90 degrees outward of the central rib 23 and on either side thereof. Each of the lugs is provided with a screw receiving aperture 14 , by means of which the door guard plate 20 p is secured to a door. The lugs 22 and 22 a perform the same function as the extended flanges 22 and 23 of the previously discussed embodiments. A back plate 120 , which may be plastic or a metal die casting, is provided with the door guard plate 20 p. The back plate 120 acts as a door edge protector and to improve aesthetics. Recesses 122 and 122 a are provided in the front face 122 of the back plate 120 to receive the lugs 22 and 22 a respectively of the door guard plate 20 p in order that the lugs 22 and 22 a may be flush with the front surface 122 of the back plate 120 . Screw receiving apertures 14 in the back plate 120 are aligned with corresponding screw receiving apertures 14 in the lugs 22 and 22 a in the door guard plate 20 p. The operational aspects of this example of door guard plate are the same as those for the assemblies shown in FIGS. 8 and 16 .
[0097] FIG. 30 illustrates a door guard plate 20 q that is formed as a metal pressing or fabricated from a short length of 90 degree metal angle section. The door guard plate 20 q is provided with a metal or plastic back plate 130 which acts as a door edge protector. The door guard plate 20 q comprises a main body 23 a, which has a slightly shorter flange portion 22 extending therefrom at 90 degrees. The flange 22 is provided with several spaced screw receiving apertures 14 , by means of which it is secured to a door. The longer main body 23 a of the door guard plate 20 q defines a slot aperture 26 adjacent its back end and a narrow slot 27 extends outwards from the slot aperture 26 , centrally on the main body 23 a to a slot end 27 a which is close to the front end of the main body 23 a. The back plate 130 is the same length as the flange 22 and just over twice the width. Two sets of screw receiving apertures 14 are provided in the back plate 130 and align with corresponding screw receiving apertures 14 in the flange 22 . The operational aspects of the door guard plate 20 q are the same as those described in relation to the assemblies of FIG. 8 and FIG. 16 .
[0098] FIGS. 31 to 36 show a door guard plate 20 r that is generally in the form of a short length of metal ‘T’ section. Extended flanges 22 and 22 a, which extend substantially perpendicularly from each side of the main central rib 23 , are provided with spaced screw receiving apertures 14 for fixedly securing the door guard plate 20 r to a door. The main central rib 23 extends beyond the flanges 22 and 22 a on the end of the door guard plate that, in use, is furthest away from the door jamb. The central rib 23 defines a narrow entry slot 27 x located centrally and transversely therein, leading from the back end of the door guard plate 20 r to a slot end 27 a close to the front of the door guard plate 20 r. The slot 27 facilitates entry and engagement of a link 31 or links on the free end of the guard chain 30 in the door guard plate 20 r to releasably secure the guard chain 30 to the door guard plate 20 r.
[0099] The entry 27 x to the narrow slot 27 is at the end of the door guard plate 20 r that, in use, is furthest away from the door jamb. The slot 27 is on the horizontal plane and facilitates easy engagement of a selected link 31 therein. The links 31 can only pass sideways in the narrow slot 27 , thus the link adjacent a selected link 31 provides an interlock between the guard chain 30 and the door guard plate 20 r . A number of different links on the free end of the guard chain 30 may be engaged singularly in the narrow slot 27 to releasably secure the guard chain 30 to the door guard plate 20 r. Individual links 31 on the free end of the guard chain 30 directly engaging the door guard plate 20 r, provide varying degrees of selective and secure limited opening of a door for inspection of a caller. The last link 31 b on the free end of the guard chain 30 determines the maximum amount the door may be opened. The last link 31 b may be engaged on the flexible limb 23 a of the door guard plate 20 r, the inner surface of the link 31 b abutting the slot end 27 a.
[0100] An aperture 14 a is provided at the back end of the central rib 23 adjacent the entry 27 x on the flange side 23 b of the narrow slot 27 , the aperture 14 a is to receive a metal ring R 1 , the ring R 1 is captive in the aperture 14 a and swivelably moveable therein between an unlocked position, in which it permits access for the free end of the guard chain 30 to the narrow slot 27 , and a locking position, in which, it locks the free end of the guard chain 30 in the door guard plate 20 r, when the door guard plate 20 r is operational. An annular cut-out or holding recess 36 is provided in the edge of the resilient limb 23 a adjacent the free end of the resilient limb 23 a. The cut-out is provided to locate the one side of ring R 1 when the ring R 1 is in its locking position.
[0101] An angled lead or ramp 37 extends from the holding recess 36 to the end of the limb 23 a the lead 37 acts to guide the ring R 1 into the holding recess 36 as the ring R 1 is moved up the lead 37 against the force of the resilient limb 23 a to snap engage the holding recess 36 . The ring R 1 in its locking position, acts to support the flexible limb 23 a preventing it moving outward of the door guard plate 20 r. The ring R 1 prevents inadvertent removal of the guard chain 30 from the door guard plate 20 r.
[0102] FIG. 32 is a perspective view of the door guard plate 20 r which has a ring R 2 releasably secured in the narrow slot 27 . The last link 31 b on the free end of the guard chain 30 is fixedly secured to the ring R 2 and the ring R 2 is engaged on or over the flexible limb 23 a of the door guard plate 20 r and the inside surface of the ring R 2 is abutting the slot end aperture 27 a. The ring R 2 may be provided on the free end of the guard chain 30 as a handle for the chain. The rings R 1 and R 2 are, preferably, the same size. The guard chain links 31 and the end link 31 b which is attached to the ring R 2 are required to be engaged singularly and sideways in the narrow slot 27 to provide varying degrees of selective, limited opening of a door.
[0103] A small hump 38 may be provided adjacent the entry 27 x to the narrow slot 27 , the hump 38 projecting from the flange side 23 b of the central rib 23 into the narrow slot 27 , the small hump 38 will provide resilient resistance to removal of a selected link or ring R 2 from the narrow slot 27 in the door guard plate 20 r. The hump 38 would not be required if a locking ring R 1 or slot closure is provided. The slot entry 27 x may have curved or tapered entry leads 39 to assist in locating a selected link 31 on the free end of the guard chain 30 in the narrow slot 27 .
[0104] FIG. 33 is a perspective view of the door guard plate 20 r which has a closure 86 swivalably secured on the limb 32 b adjacent the narrow slot entry 27 x . The closure 86 is secured to the door guard plate 20 r by means of a swivel pin 39 a , which engages the apertures 88 defined in the body 87 of the closure 86 and the aperture 14 a in the limb 23 b. An indent 89 in the side of the closure 86 snap-engages the holding recess 36 in the resilient limb 23 a of the door guard plate 20 r when the closure 86 is swivelled to its closed position, in which position it prevents inadvertent disengagement of the guard chain 30 from the door guard plate 20 r . FIG. 33 shows the closure in its locking position. The flexible limb 23 a may be depressed inwards to relieve pressure between the flexible limb 23 and the indent 89 , when moving the closure 86 from its locked to its unlocked position, when the free end of the guard chain 30 may be released from the door guard plate 20 r.
[0105] FIG. 34 illustrates an alternative closure 96 for the door guard plate 20 r . The closure 96 comprises a short, thin walled rectangular sleeve, of which the back end 99 is closed and is preferably slightly curved. The internal bore 98 of the closure 96 is dimensioned to be a snug fit on the central rib limbs 23 a and 23 b. The resilient, flexible limb 23 a will provide that the closure 96 is firmly gripped when it is pushed onto the door guard plate 20 r to lock the free end of the guard chain 30 therein. In use, the closure 96 is stowed on the door guard plate 20 r and is only removed to allow the guard chain 30 to be releasably secured in the guard plate 20 r.
[0106] FIGS. 35 and 36 illustrate the door guard plate 20 r which has been modified to enable it to receive a thumb clip 130 as means to prevent the free end of the guard chain 30 inadvertently disengaging the door guard plate 20 r. The door guard plate 20 r is provided with a pair of spaced apertures 14 b adjacent the free ends of the limbs 23 a and 23 b respectively, the opposing apertures 14 b are to receive respective prongs 14 c on the double pronged thumb clip 130 . The thumb clip 130 is used to bridge the narrow slot 27 to prevent inadvertent disengagement of the free end of the guard chain 30 from the door guard plate 20 r when the door chain 1 is operational.
[0107] The thumb clip 130 comprises a short narrow body 131 , the sides 132 of which are dished to facilitate gripping and the back end 133 of the thumb clip 130 is curved. A pair of spaced prongs 14 c extend outwardly from the front end 134 of the thumb clip 130 . The prongs 14 c engage and locate respectively in the apertures 14 b in the door guard plate 20 r. The length of the prongs 14 c ensures that the thumb clip 130 is adequately engaged in the door guard plate 20 r. In use, the thumb clip 130 is stowed on the door guard plate 20 r and is only removed to allow the guard chain 30 to be releasably secured in the guard plate 20 r.
[0108] It is to be understood, that any suitable door frame anchor plate 50 or anchor means may be used in conjunction with the door guard plates illustrated and described in this specification, to fixedly secure one end of the guard chain 30 to a door frame.
[0109] The same numerals have been used throughout this specification to denote similar components. | A door chain assembly comprising a chain and an anchor plate. The anchor plate comprises a back plate and a chain-receiving plate and the chain-receiving plate extends from the back plate. The chain-receiving plate is provided with an aperture and/or a chain-holding slot. The chain comprises a plurality of links with adjacent links being rotationally offset with respect to one another. | 4 |
The invention relates to a process for fabricating a rechargeable non-aqueous cell and to cell produced by this process.
BACKGROUND OF THE INVENTION
Rapid increase in consumer interest in a variety of technologies such as portable power tools calculators, computers, cordless telephones, garden tools, portable televisions, radios, tape recorders, as well as back-up power sources in computer technology, memory devices, security systems, to name a few, has increased the demand for reliable, ligh-weight, high-energy power sources. Recent developments in high energy density cells have focused attention on anodes of alkali metal, non-aqueous electrolytes and cathode-active materials of nonstoichiometric compounds. Alkali metals, particularly lithium, are use as anode-active materials because they are highly electro-negative, thereby providing high energies per weight unit. Self-discharge of cells employing alkali metal as the anode-active material is minimized by employing non-aqueous solvents which are not reducible by the highly reactive anode mateials, thus enabling an exceptionally long shelf life.
Cathode active materials generally include transition metal chalcogenides such as NbSe 2 , NbSe 3 NbS 3 , MoS 2 , MoS 3 , TiS 2 , TiS 3 , TaSe 3 , TaS 2 , V 6 O 13 , CoO 2 and MoO 2 . These materials, especially niobium selenide, niobium triselenide, and niobium trisulfide, which are described in U.S. Pat. No. 3,864,167 issued to J. Broadhead et al. on Feb 4, 1975, have excellent capacities, good recycling properties and are very compatible with the alkali metals, especially lithium. The chalcogenide compounds are electronic conductor; however, their conductivity is not nearly as great as of metallic conductors. Therefore, the conductivity of the cathode structure is typically improved by admixing carbon black or particulate metal with the cathode-active material and/or supporting the cathode-active material on a metal grid or screen to improve current collection. Such metals may be selected from magnesium, aluminum titanium, zinc, lead, iron, nickel, copper, and alloys thereof.
U.S. Pat. No. 4.091,191 issued to Lewis H. Gaines on May 23, 1978 suggests the use of aluminum for incorporation in a particulate form (e.g. powder or fibers) into TiS 2 active material and for use as a screen or perforated sheet onto which a mixture of the cathode-active material and the particulate metal is molded or pressed. The particulate metal is added in amounts of up to 50 wt.%, preferably between 5 and 20 wt.% to the active material (TiS 2 ). Additionally, from 1 to 20 wt.% preferably from 2 to 10 wt.%, of a binder is admixed with the particulate metal and active material and the mixture is molded at pressure of up to 165 MPa (24000 psi) into a desired shape, e.g. about a perforated aluminum plate.
The disadvantages of this procedure lie in larger amounts of the particulate metal (powder or fiber) which, while adding strength and conductivity to the cathode structure, reduce the amount of cathode active material being included in a certain volume of a cathode electrode; addition of the binder further adds to the bulk of the molded material. Furthermore, expanded metal screens or grids, e.g. of nickel, cooper or thier alloys (commercially available from Exmet Corporation), rather than perforated sheet or screen of aluminum, have been typically used recently in the production of rechargeable non-aqueous alkali cells, primarily due to commercial availability and relative strength of the screen or grid made of such expanded metals. However, fibers of cathode-active material (e.g. niobium triselenide) on both sides of strands of a screen or grid of expanded metal such as nickel (e.g. 3Ni5.125) are more compressed relative to the fibers in the open areas. The compressed area exert more pressure on the separator during cycling enabling lithium to plate through the pores of the separator. The screen or grid also focuses the current at the intersection of the metal strands resulting in a nonuniform current distribution, thus increasing chances of forming an internal short. (Internal shorts are electric paths between the cathode (e.g. NbSe 3 ) and the alkali metal anode (e.g. Li) that develop through a separator during the charging phase.) The cells with these internal shorts manifest charge capacities which are larger than their discharge capacities. Their capacity will also fade faster with each cycle. These problems are not unique for the expanded metal grids or screens, but may occur also in cells with cathodes in which the current collector is in the form of a flat screen or perforated sheet.
Thus, a cell with a cathode which not only ameliorates the above shortcomings, but also is adaptable for mass-production use, is highly desirable.
SUMMARY OF THE INVENTION
The invention is a non-aqueous alkali metal e.g. lithium, cell in which the positve electrode (the cathode) has a unique laminated structure produced by conductively bonding mats (or sheets) of cathode-active material selected from transition-metal chalcogenides to a surface of a metal foil which acts as a current collector. Other structural features of the non-aqueous cell including negative electrode (anode), non-aqueous electrolyte and separator, are generally conventional. More specifically, the cathode is composed of a current collector consisting of an unperforated metal foil coated with a polymeric adhesive bonding mats (or sheets) of cathode active material to the foil. Conductive particles, such as carbon black, are used either as an additive to the polymer or as a thin coating on the cathode-active material facing the foil to provide an electronic bond between the foil and the mats. Some other conductive particles, such as an inert metal, may be used for the some purpose. Other structural feature of the non-aqueous cell including negative electrode (anode), non-aqueous electrolyte and separator, are generally conventional.
Cells with cathodes having the metal foil current collector provide performance and reliability which meets the cells with expanded metal current collector without added cost. In the preferred embodiment the metal foil is of aluminum, the active anode material is lithium and the active cathode material is NbSe 3 . Aluminum foil has advantages of lower cost, lighter weight, higher electrical and thermal conductivity. Aluminum foil is about five times cheaper than nickel expanded metal or aluminum expanded metal and about 50 percent lighter than nickel expanded metal. Cells with aluminum foil current collector have a lower cell impedance which results in significant improvement in both high rate discharge and low temperature performance. As a result of lower cell impedance, as well as more uniform current distribution, the cell can deliver more energy at low temperatures. For example, an AA size cell discharged at 4A, room temperature, shows a 33% improvement in energy and a cell discharged at 200mA, at -20° C., shows an 35% improvement as compared to the cell using a cathode with Ni expanded metal current collector. The softness as well as the absence of sharp edges and high spots in the aluminum foil tend to reduce the shorting frequency. Furthermore, because of the smooth surface of aluminum foil, the cathode can be compressed more uniformly to a thinner thickness without forming areas of a highly compressed NbSe 3 . The use of the invention described below permits production of these cells on a mass-production basis.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows schematically an exemplary rolled non-aqueous cylindrical cell made in accordance with the invention.
FIG. 2 shows the A.C. impedance of an uncycled cell with an aluminum foil current collector.
FIG. 3 shows an A.C. impedance of a cell with an aluminum foil current collector after 20 cycles.
FIG. 4 shows the A.C. impedance of an uncycled cell with the prior art expanded-metal Ni current collector.
FIG. 5 shows the A.C. impedance of a cell with the prior art expanded-metal Ni current collector after 20 cycles.
FIG. 6 shows comparisons of discharge voltage curves at different discharge currents for A1-foil current collector and prior art Ni expanded metal current collector.
FIG. 7 shows comparisons of discharge voltage curves at -20° C. for A1-foil current collector and prior art Ni expanded-metal current collector.
FIG. 8 shows the cycle life for A1-foil current collector and prior art Ni expanded metal current collector.
FIG. 9 shows the cycle life performance at 1000 mA discharge current for A1-foil current collector.
DETAILED DESCRIPTION
The present invention relates to a non-aqueous alkali metal recharageable cell with a unique cathode electrode. A non-aqueous alkali metal cell generally includes an anode, a separator, a cathode and an electrolyte which are enclosed within a suitable container. A great variety of cell structures may be used in the practice of the invention. Contemplated are cells of various sizes and shapes with varied amounts of electrolyte, as is well known in the art. Particularly attractive are rolled cylindrical cells.
FIG. 1 shows schematically a typical cell structure 10 useful in the practice of the invention. This type of structure is often called the rolled cylindrical cell structure produced by putting several, usually four, layers together and rolling them into a cylindrical shape. The four layers are a negative electrode (anode) 11, a separator 12, a positive electrode (cathode) 13, and another separator 14. The roll is generally enclosed within an enclosure or container (not shown) with suitable electrical connections (tabs) to the positive and negative electrodes. The container is filled with an appropriate electrolyte to permit electro-chemical action. Such rolled cells are described in U.S. Pat. No. 4,740,433 issued to W.P. Lu on Apr. 26, 1988 and U.S. Pat. No. 4,753,859 issued to L. E. Brand on Jun. 28, 1988. These patents are directed, respectively, to cells with an improved separator material and electrolyte system useful in the practice of this invention and are incorporated herein by reference. U.S. application Ser. No. 353,574 filed on May 18, 1989, in the name of S. M. Granstaff et al. (Case 4-5), also incorporated herein by reference, describes a lithium cell with an improved laminated negative electrode (anode) useful in practicing the present invention.
Active anode electrode materials useful in the practice of the invention include lithium, sodium, potassium, rubidium, cesium and combinations of these metals. Lithium is most preferred because of the high electrical potentials obtained with this material and excellent compatibility with various active positive electrode materials.
Electrolyte systems useful in the practice of the invention typically are made up of a solvent (often multicomponent) together with one or more current carrying species (e.g. salts) dissolved in the solvent. Particularly advantageous are solvents made up of such components as propylene carbonate, ethylene carbonate, dialkyl carbonates (e.g. diethyl carbonate) and various polyethylene glycol dialkyl ether (glymes) such as diglyme, triglyme and tetraglyme.
Salts useful as the current carrying species in the electrolyte system are well known in this art. Typical examples are LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiBF 4 , LiAlCl 4 , LiI and LiBr. Ammonium salts are also useful as current-carrying species in electrolytes for non-aqueous cells. Useful ammonium salts are tetraalkylammonium salts with anions such as hexafluoroarsenate, hexafluorophosphate, tetrafluoroborate, perchlorate and halides such as chlorine, bromine and iodine and alkyl groups with up to six carbon atoms. Tetrabutylammonium salts and tetraethylammonium salts are preferred because of availability, high solubility, stability and good conductivity exhibited by such electrolytes. Electrolytes with more than one salt (e.g., LiPF 6 and LiAsF 6 ) may also be used. Preferred is the mixture of lithium salt (preferably LiPF 6 and/or LiAsF 6 ) and tetraalkylammonium salts (e.g., one or more of the tetrabutylammonium salts and tetraethylammonium salts). Such a mixture of salts yields exceptionally high charge and discharge rates especially at low temperatures. The concentration of current-carrying species may vary over large limits, typically from 0.5 molar to saturation. Preferred concentrations are often determined by the concentration of maximum conductivity of the electrolyte solution, often around 0.25 to 0.75 of the saturation concentration. For example, for lithium salts, such as LiPF 6 and LiAsF 6 , typical concentration are 0.4 to 1.5 molar with 0.6 to 1.0 molar being preferred. For tetra-alkylammonium salts, concentration between 0.1 and 1.0 molar are typical. For mixtures of lithium salts and tetra-alkylammonium salts, lithium salt concentrations of 0.4 to 0.8 molar and tetra-alkylammonium salt concentrations of 0.2 to 0.4 molar are preferred.
Separator materials useful in the practice of the invention generally are polymer materials, such as polyethylene or polypropylene made in the form of microporous films. Preferred are various microporous polypropylene separators such as Celgard® 2400 and Celgard® 2402 made by the Celanese Corporation. Also useful are grafted separator materials such as the those described in U.S. Pat. No. 4,740,433 issued to Wen-Tong P. Lu on Apr. 26, 1988, incorporated herein by reference.
A variety of positive electrode active materials may be used, including transition - metal chalcogenides selected from NbSe 2 , NbSe 3 , NbS 3 , MoS 2 , MoS 3 , TiS 2 , TiS 3 , TaSe 3 , TaS 2 V 6 O 13 and MoO 2 . Niobium diselenide, niobium triselenide and niobium trisulfide, described in U.S. Pat. No. 3,864,167, which is incorporated herein by reference, are especially useful for use with lithium anode active material. Particularly good results are obtained when using niobium triselenide as the active positive electrode material. Such cells exhibit very high energy densities, long shelf life and long cycle life.
This invention is illustrated with reference to a rechargeable, non-aqueous alkali-metal cell in which the active-anode material is lithium and the active-cathode material is niobium triselenide. Nevertheless, the teachings presented for the illustrated embodiment are applicable to other rechargeable nonaqueous alkali-metal cells.
In the exemplary preferred embodiment, the cathode was fabricated by bonding NbSe 3 mats (or sheets) to aluminum foil. Commercial Reynolds Wrap® aluminum foil with a thickness ranging from 0.001 to 0.002 cm. (0.0004 to 0.0007 inches) was used for the current collector material without further processing. Mats of NbSe 3 may be prepared in a variety of ways. Typically, the mats are about 0.012 cm (0.0047 inches) in thickness. Thinner or thicker mats may be used as well. One especially suitable manner of fabrication NbSe 3 or (or NbS 3 ) mats is described in U.S. patent application Ser. No. 244,218, filed on Sept. 14, 1988 in the name of W. Fange and B. Vyas, entitled "Non-aqueous Cell Comprising Niobium Triselenide". Briefly, the mats (or sheets) are produced by a method that includes deposition of layer of a liquid suspension of niobium powder in an inert liquid, e.g. propylene glycol, on a suitable substrate e.g. alumina, removal of the liquid from the layer, and reaction of the niobium powder with vapor of selenium (or sulfur). In a specific embodiment using selenium, the reaction was conducted at temperatures ranging from 625° C. to 780° C. for a period of from 2 hours to 5 days. The process may include a first pre-reacting stage including heating at a temperature of from 520° C. to 625° C. from 4 to 24 hours, which may precede the reacting stage.
The mats (or sheets) were bonded to the aluminum foil using the following two procedure variants. Both cathode fabrication variants give similar cell performance; however, the second variant is cleaner, simpler and better adaptable to mass production.
The first variant includes applicant of a thin layer of carbon black (Cabot Vulcan XC72) on one side of NbSe 3 mats followed by placing the mats, with carbon-coated side facing the aluminum foil, on both sides of a polymer-coated aluminum foil, then passing the so-formed composite between rollers to compress the composite to a desirable thickness, typically to form 0.010 to 0.013 cm. (0.004 to 0.005 inches). Other compression techniques may be used as well. The polymer-coated aluminum foil was prepared by applying a thin layer of a solution of one weight percent (wt. %) EPDM in cyclohexane on the aluminum foil just before the carbon black coated NbSe 3 mats were placed on the foil to avoid solution drying out due to the volatile nature of cyclohexane. EPDM stands for a terpolymer of ethylene, propylene and diene and is commercially available from Exxon Chemical Company as Exxon V-4608 [chemical formula (C 2 H 4 ) x (C 3 H 6 ) y (C 9 H 12 ) z x=0.4-0.8, y=0.2-0.6, z=0- 0.1, by wt.] Other polymers, such as polyethylene oxide, silicone and polyurethane may be used in place of or in admixture with the EPDM.
The second variant comprises applying a well-mixed slurry of the EPDM, carbon black and cyclohexane on the aluminum foil, placing NbSe 3 mats upon both sides of the coated aluminum foil and then compressing the composite in the manner similar to that of the first variant. The slurry has an approximate composition of 2EPDM/4 carbon black/94 cyclohexane in wt.%.
Cathodes prepared by either variant were dried in a vacuum oven at about 70° C. for about 1/2 hour to remove residual solvent (cyclohexane) in the cathode. Other suitable temperatures and times may be used. In both method variants, the amount of carbon black in the finished cathode may be present within a range of from 0 to 20 wt.%, preferably from 0.5 to 5 wt.% with 1 to 3 wt.% being most preferred and the amount of the polymer may be present within a range of from 0.1 to 15 wt.%, preferred from 0.1 wt.% with from 0.3 to 0.5 wt.% being most preferred. The carbon black is desirable for providing an enhanced electronic conduction path between aluminum foil and NbSe 3 mats for electrochemical reactions. Other conductive particles, such as of inert metals mentioned above, may be used instead of or in combination with carbon black.
The so-formed cathodes were trimmed to a desirable dimension suitable for cell construction [for an AA size cell typically 3 cm. by 44.5 cm. (1.55" by 17.5")]. The leads of electrical connection of the cathode were made by pre-welding nickel or copper tabs to aluminum foil. The leads for electrical connection of the anode are also nickel or copper tabs pre-welded to the current collector of the anode.
The cycle behavior of cells with the aluminum foil cathode current collectors was obtained by testing cylindrical AA size cells filled with 0.8 M LiAsF 6 in a mixture containing 35 mol% propylene carbonate, 35 mol% ethylene carbonate and 30% mol triglyme. Similar AA cells with a nickel expanded metal cathode current collectors were used. The cells were tested by cycling at discharge currents ranging from 100 mA to 4000 mA; the cells were charged at 100 mA and 120 mA. The voltage range during cycling was from 1.4V to 2.4 V. The cycling was conducted at temperatures ranging from -20° C. to 45° C.
Impedance measurements and performance data of cells with the aluminum foil cathode current collector are presented below. The cell impedance was measured with a Schlumberger EMR 1170 Frequency Response Analyzer and a Solartron 1186 Electrochemical Interface (the cell's potential was held at the OCV value during the impedance measurement.) All cells, with the exception of fresh cells, were charged to 2.4 V before measuring their impedance. The cell impedance at 1 Hz is chosen for comparison because it is close to the DC resistance of the cell. Because there is a variation in cell capacities, the cell energies were multiplied by the ratio ACTUAL CAPACITY/1300; this factor normalizes all the cells' capacities around 1300 mAh and allows for a proper comparison of energies. In the cycle life data plots the capacities were normalized by the cell's first cycle capacity to 1.05 V.
The impedance measurements for cells with the aluminum foil current collector (FCC) and nickel expanded metal current collector (EMCC) are shown in FIGS. 2 and 3 and FIGS. 4 and 5, respectively. A fresh uncycled cell with the FCC cathode has a 1 Hz impedance of 0.3 ohms (FIG. 2) whereas an uncycled cell with the EMCC cathode has an impedance of 0.7 ohms at 1 Hz (FIG. 4). After twenty cycles the cell with the FCC cathode has 1 Hz impedance of 0.11 (FIG. 3) ohms and the cell with the EMCC cathode has a 1 Hz impedance of 0.17 ohms (FIG. 5). The lower impedance in the cell with the aluminum FCC cathode is the result of higher electronic conductivity (2.6 times that of nickel) and larger contact area (˜3.7 times that of the expanded metal). Although the presence of the polymer binder increases the contact resistance, the net effect is still about a 35% reduction in cell impedance.
The lower impedance in cells with the FCC cathodes results in overall higher voltage discharges. FIG. 6 shows discharge curves of cell voltages versus percent capacity for the 1A, 2A, 3A and 4A discharges of cells with the FCC cathode (solid line) and EMCC cathode (dotted line), respectively as measured at room temperature (˜25° C.). The cells were cycled twenty times before performing the 1A to 4A discharges. The curves show a significant improvement in capacity and mid-discharge voltage for the FCC cell at all four currents. The improvement in energy, as may be seen from Table I, for the cell with FCC over the cell with EMCC is small for the 1A and 2A cases, but becomes significant for the 3A and 4A cases with improvements of 10% and 33% respectively. The 200 mA discharges at -20° C. are shown in FIG. 7. The cell with FCC cathode has an energy of 1.179 Wh as compared to 0.945 Wh for the cell with EMCC cathode; this translates to a 25% energy improvement at -20° C. The voltage advantage of the cell with FCC cathode becomes larger at higher rates and at lower temperatures. There are no significant differences at moderate rates (˜400 mA) and temperature (˜25° C.).
Cells with the FCC cathodes and the cells with the EMCC cathodes were tested also for cycle life. FIG. 8 shows the cycle life for cells with FCC cathodes and EMCC cathodes tested at room temperature (˜25° C.). Both cells yield ˜150 cycles to a cutoff of 60% capacity; this is typical cycle life for an electrochemical cell when discharged at 400 mA and charged at 120 mA. At a higher discharge current of 1000 mA, cell with FCC cathode yielded 145 cycles at the 60% capacity cut off (FIG. 9). Both cells with FCC and with EMCC cathodes, at 45° C., shorted after about 120 cycles, respectively.
TABLE I______________________________________Energies At Different Discharge CurrentsFor Al Foil and Ni Expanded Metal SubstrateDischarge Al Foil Ni ExmetCurrent (FCC) (EMCC) % Improvement(Ampere) (Wh) (Wh) Over Ni Exmet______________________________________1A 1.872 1.855 0.92A 1.641 1.573 4.33A 1.410 1.280 10.24A 1.170 0.880 33.0______________________________________ | This invention relates to a process of fabricating a rechargeable non-aqueous cell and to a cell produced by the process. The cell includes a unique laminated cathode structure. Other structural features of the non-aqueous cell including anode, non-aqueous electrolyte and separator, are generally conventional. The novel cathode is composed of a current collector consisting of an unperforated metal foil to which are bonded mats of cathode active material, selected from transition-metal chalcogenides. In the process of forming the cathode, a non-perforated metal foil, such as aluminum, is coated with a layer of bonding polymer and after the mats of cathode-active material, such as niobium triselenide, are placed on both sides of the metal foil, the composite is compacted, preferably by passing between rollers. Electronic conduction is enhanced by either admixing carbon black with the polymer or coating that surface of the mats which is to be in contact with the metal foil, with a thin layer of carbon black. This design results in cells which show a distinct improvement in energy at higher rate discharges, e.g. at 3-4A, or at lower temperatures, e.g. -20° C., lower cost and weight than cells with conventional cathode collector having screen or grid of expanded metal, e.g. Ni, and are expected to ameliorate internal shorts resulting from the use of ex-met grids. | 8 |
FIELD OF THE INVENTION
The present invention relates to magnetic latches suitable for use on gates or doors where automatic latching is required when the gate or door is displaced to a position at which it is to be latched. An actuator is provided for unlatching so that the gate or door can be opened, usually pivotally, away from its latching position.
The present invention in various embodiments offers new and useful alternatives to previously available options and indeed lends itself to embodiments which may incorporate security locks such as quality cylinder locks.
BACKGROUND OF THE INVENTION
A significant development in magnetic latching and devices is the subject of the PCT International Publication WO92/03631 on the basis of which U.S. Pat. No. 5,362,116 was issued to David Doyle and Neil Dunne. This invention has been assigned to the assignees of the present invention. The Doyle and Dunne invention relates to a vertically operating magnetic latch particularly for a swimming pool gate with a lost motion arrangement so that a latching pin, after manual retraction and after opening the gate, is retained in an elevated retracted position by spring biasing and the actuating mechanism does not apply downward load-imposing forces against the biasing spring.
While this device has been successfully exploited, the present invention has been conceived to offer novel inventive and alternative embodiments for different applications in a different form. Indeed the present invention may be applied to provide magnetic latching as an alternative to conventional striker plates with spring door latches and the invention may lend itself to versions incorporating locks.
Embodiments of the present invention are envisaged as extending both to manually actuatable versions (such as embodiments having rotatable rotary knobs or rotatable handles) but also extends to actuation by other means such as solenoids or electric motors permits actuation from a remote location. Of particular significance in these embodiments is the inherent characteristics of magnetic latching as demonstrated by the Doyle and Dunne prior patent whereby when a gate or door is swung to its closed position, in contrast to conventional gate latches where force is required to displace a spring biased latch pin initially away from a latching position prior to it entering into latching engagement, with Doyle and Dunne there is no such resistance. This is especially valuable in installations having an automatic door closing device.
SUMMARY OF THE INVENTION
The present invention is embodied in a self-latching device for latching, in a predetermined position, two members which are otherwise moveable relative to one another, the device comprising a latch arm and a retaining element which in use provides a latching shoulder for the latch arm to prevent relative movement of the members, at least one of the latch arm and the retaining element providing a magnetic field and the other having magnetic properties, the latch arm being arranged to be displaceably mounted on a first of said members and the retaining element being arranged to be associated with the second of said members, the latch arm and retaining element undergoing relative movement into a latching position under the influence of the magnetic field when the members are in the predetermined position, and then relative movement of the two members is substantially prevented by an engagement portion of the latch arm and latching shoulder interengaging, and the latch arm being displaceable under applied force away from the retaining element to a retracted position so that the members may be moved apart, the device further comprises:
(a) a resilient biasing element associated with the latch arm to bias it towards the retracted position, but with a biasing force on the latch arm which is less than the force imparted on the latch arm by the magnetic field when the members are located in the predetermined position;
(b) an actuator movably mounted on the housing and extending from the housing transversely to the path of displacement of the latch portion for receiving a displacement force to displace the latch arm from its latching position to its retracted position, whereby the two members may be moved apart away from the predetermined position;
(c) a connector for connecting the actuator and the latch arm to displace the latch arm from its latching position to its retracted position and to leave the actuator free to move relative to the connector; and
(d) a second biasing element for returning the actuator to its initial position on removal of the displacement force leaving the biasing element to maintain the latch arm and connector substantially in its retracted position, whereby when in the predetermined position the latch arm is displaceable under the magnetic forces against the biasing means to re-establish its latching position.
Implementation of the invention may be by including a lost motion interconnection between the actuator and the latch arm whereby no significant load is applied to the latching arm and its biasing element when in the retracted position.
In the subject invention, the actuator may be designed so as to be movable in a rectilinear, arcuate or rotary manner either in or transverse to a plane in which the latch arm is to be displaced.
A particular embodiment is one wherein the latch arm is mounted for reciprocation in a housing and the housing also mounts the actuator in the form of a rotary actuator which may include a conventional rotatable handle, with the option of providing one handle on either side of the device, for example to be disposed on either sides of a gate. Each handle might incorporate a locking mechanism such as a wafer lock or cylinder lock for security reasons. The housing might incorporate an alternative locking mechanism.
One embodiment provides a carriage with spaced guides along which mounting elements of the latch arm can slide, the latch arm incorporating a pin around which a helical compression biasing spring is mounted as the biasing means. In such an embodiment a torsion spring can be provided as the restoring means for the rotary actuating means (such as the handles).
As described with reference to an illustrated embodiment, the latch arm can take the form of a generally C-shaped carriage which moves in guides in the housing and the C-shaped carriage has lobes at its open ends for engagement with corresponding projecting elements associated with a barrel connected to a rotatable handle.
An alternative approach, however, is to provide the latch arm with a drum-like structure around which a flexible connection element extends. The arrangement is such that the element is extended and perhaps tensioned when the latch arm is in the latching position and rotation of the drum by the actuator causes the latch arm to be retracted. The arrangement is such that after movement of a gate (or door) to an open position, the biasing means retains the latch arm in its retracted position and tension previously applied to the flexible element is relieved so that no or only negligible load is applied against the biasing means.
The device may include an actuator for displacing the latch arm by remote actuation for remote gate opening control. However, larger markets are thought to be for directly operated gate latches having handles.
Embodiments of the invention can be formed into a volume, shape and configuration consistent with conventional cylinder lock door locks, i.e. within an envelope of about 15 cm×10 cm×5 cm.
Embodiments may have the magnet material provided by a permanent magnet having a remanence (residual flux density) of about 12 kilogauss and the latch arm has a pin having magnetic properties and of transverse dimension of about 8 mm, preferably sealed within the body of the retaining element and the latch arm then has a steel pin providing the latching portion and of a suitable grade of steel having magnetic properties.
In place of a rotatable knob or rotatable handle for actuating means, the invention lends itself to embodiments which are remotely actuated, for example electrically by the use of a solenoid arrangement or motor to cause rotation of the actuator for retraction of the latching arm.
Generally arrangements incorporate a lost motion interconnection between the actuator and the latch arm such that little or preferably no load is applied to the latching arm and its biasing means when in the retracted position.
Although significant markets for embodiments of the invention are perceived to be for gate locks incorporating key actuated mechanisms such as wafer locks or cylinder locks, embodiments may be simply no-lock latch mechanisms, or embodiments having an egress button on one handle and a lock on the other.
Embodiments can provide a lost motion effect by having an eccentric drive pin to be displaced upon lock actuation to displace an internal element from a retracted position (where it rotates freely upon handle rotation) to an extended position in which it engages with a collar to rotate the collar and the collar in turn displaces a carriage to retract the latch arm.
The term “comprising” (and its grammatical variations) as used herein are used in the inclusive sense of “having” or “including” and not in the sense of “consisting only of.” Other features and advantages of the invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings which illustrate, by way of example, the features of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be further exemplified with reference to the accompanying drawings of which:
FIGS. 1A , 1 B and 1 C are respectively a plan view, a front elevation and an end elevation (in the direction of arrow A in FIG. 1A ) of an embodiment of the invention suitable for fitting to a gate;
FIG. 2 is an exploded view of the device of the embodiment of FIGS. 1A to 1C ;
FIG. 3 is an end view of an actuating barrel of the device on an enlarged scale;
FIG. 4 is an isometric view of the actuating barrel on an enlarged scale;
FIG. 5 is an end elevation of a sliding carriage of the latch arm on an enlarged scale;
FIG. 6 is an elevation of the sliding carriage of FIG. 5 ;
FIG. 7 is an elevation with the front housing removed and showing the latching configuration with a latch pin of the latch arm extended into latching engagement in a cavity of a latch block;
FIG. 8 corresponds to FIG. 7 but after rotation of an actuating handle to retract the latch pin to permit the associated gate to be swung open;
FIG. 9 is a view corresponding to FIG. 8 but after release of the handle to return to its normal position and with the latch pin retained in a retracted position;
FIG. 10 is a partly exploded isometric view of a second embodiment;
FIG. 11 is an isometric cross-sectional view of the embodiment of FIG. 10 when in the locked configuration and latch pin engaged by magnetic force into the receiving latch block;
FIG. 12 is an isometric view on an enlarged scale of the rotary actuating a mechanism of the second embodiment shown on an enlarged scale and in a locked configuration;
FIG. 13 is a view corresponding to FIG. 12 and showing an unlocked configuration;
FIG. 14 is an exploded view of a third embodiment;
FIG. 15 is an exploded view of a fourth embodiment;
FIG. 16 is a view of a fifth embodiment of the invention utilizing a flexible line to provide a lost motion system;
FIG. 17 is a view of the embodiment of FIG. 16 in which the handle has been depressed;
FIG. 18 is a view of the embodiment of FIGS. 16 and 17 in which the handle has returned to its neutral position after depression; and
FIG. 19 is a schematic view of the sixth embodiment modified for remote actuation.
FIG. 20 is a front part-sectional view of a seventh embodiment when actuated to retract a latch pin; and
FIG. 21 is a view of the embodiment of FIG. 20 when the actuator is released and the gate-closing position has been achieved and the latch pin magnetically displaced to a latching portion.
DETAILED DESCRIPTION OF THE INVENTION
The gate latch generally shown in FIGS. 1A to 1C is shown in assembled form and prior to installation. The latch 10 comprises a lockable latch module 11 to be mounted on a post of a gate and a receiving latch block 12 which is adapted to be mounted to a fixed gate post.
The latch module has a front casing 13 and a rear casing 14 adapted to be mounted on opposite sides of gate post. Front and rear handles 15 and 16 are provided and a security cylinder lock 17 is provided for each handle for independent locking purposes.
The components are shown in more detail in FIG. 2 . A mounting structure 20 is provided for attachment to a gate post of rectangular cross-section and to mount the components within the casings 13 and 14 and to mount the handles 15 and 16 . The mounting structure 20 includes a back plate 21 having spaced parallel grooves 22 to guide a latch pin assembly, and an integral end wall 23 having a small collar 24 around an aperture (not shown) through which a latching pin 25 can move. A helical compression spring 26 is mounted on the latching pin and the right hand end of the latching pin 25 upon assembly is attached by engagement in a cylindrical projection 30 of a generally C-shaped carriage 31 . The carriage 31 has integral parallel guide strips 32 extending from its rear face provided for sliding engagement in the grooves 22 in the back plate 21 .
An actuating barrel 33 (as shown in more detail in FIGS. 3 and 4 ) is to be rotated by the handles and displace the carriage axially relative to the latching pin 25 . The barrel engages with an end portion 34 of a front handle 15 after the end portion is assembled by passing through an aperture in the front casing 13 . An arcuate tab 40 projects from the end portion 34 to engage a slot in the barrel 33 so as to transmit rotation. The barrel 33 extends through an aperture in the back plate 21 to be connected to an end portion 35 of the rear handle 16 . An arcuate tab 40 also engages with a slot on the rear of the barrel 33 to transmit rotation.
As best seen in FIG. 3 , the actuating barrel 33 has a rectangular shaped through-aperture 38 for receiving a conventional actuating bar which extends from the rear of a cylinder lock 17 . The barrel has a structure which permits rotation of the barrel only when the key has been turned to unlock the lock 17 , as now described with reference to FIGS. 3 and 4 .
The rear end of the barrel 33 has a groove 33 B for accommodating the corresponding arcuate tab 40 from the rear handle so that rotary motion is transmitted to the barrel 33 when the latch is assembled and either handle is rotated. A similar groove 39 A is provided on the front of the barrel for the arcuate tab 40 of the front handle. The barrel assembly includes upper and lower ears 41 at the ends of pivotal arms 34 which are mounted on pivot pin 35 with a C-shaped spring clip 36 fitted over the arms 34 to bias them radially inwardly so that recess 37 in the inner periphery of each arm rest on lobes 39 A of a rotor 39 . The recess provides a detent function to define positively the position shown.
A middle portion of the barrel has an L-shaped bracket 43 for retaining end pins 64 of a torsion spring 66 (not shown in FIGS. 3 and 4 but shown in FIGS. 2 and 7 ). The L-shaped bracket has a mounting leg 44 and an arcuate base 45 with a groove 46 for accommodating the body of the torsion spring 66 .
FIGS. 5 and 6 show detail of the carriage 31 which has a central wall 31 A and the part cylindrical projection 30 accommodating a spring locking tag 31 B into which a groove 25 A near the rear of latching pin 25 is snap-fitted. The carriage 31 has inwardly directed lobes 63 for receiving a displacement force when either is engaged by an ear 41 of an arm 42 as described below.
FIG. 3 shows the configuration when the lock 17 has been unlocked so that the ears 41 project and upon rotation of the handle, as shown in FIG. 8 , upper ear 63 is engaged and the carriage moved rectilinearly to the right.
Referring now to FIG. 7 , the latching block 12 is shown mounted to a fixed gate post 60 and the latching module I 1 is shown mounted to an end post 61 of a gate. The latching block 12 is shown in part-sectional view and the latching module is shown with the front casing removed for clarity. In the configuration shown in FIG. 7 , the handles have been released and are arranged horizontally by the effect of a torsion spring 66 (shown in FIG. 2 ) and mounted on the barrel 33 . FIG. 7 shows the device in the predetermined position, i.e. the latching position at which the latch pin 25 has been magnetically attracted to extend so that the tip of the latch pin engages in the aperture 56 . The spring 26 is compressed between the interior of the end wall 23 and the carriage 31 . The carriage is thus drawn to the left and the lobes 63 of the carriage are adjacent to or engage with the ears 41 of the actuating barrel 33 , since in this configuration the lock is unlocked.
However, when the lock is locked, the rotor 39 is rotated and the lobes 39 A disengage the arms 34 which displace inwardly under the pressure of the spring clip 36 . If the handle 15 is displaced, the ears 41 do not engaged the lobes 63 of the carriage and the carriage does not move.
FIG. 7 also shows the end pins 64 of the torsion spring which engage of a location pin 65 which extends from the back plate 21 .
The components of the latching block 12 are more clearly shown in exploded view in FIG. 2 .
The components comprise an L-shaped mounting plate 50 adapted to be secured to a post by screws passing through apertures 51 on an end face. The mounting plate has dovetail section tracks 52 for engaging slidingly with complimentary shaped grooves on the rear of a latch body 53 . The latch body has a central cavity for accommodating a high strength magnet 54 which is held in position and the cavity sealed with suitable sealant when a cover element 55 is secured in place. The element 55 has a suitable shaped aperture 56 having a latching function when engaged with the tip of latching pin 25 .
Main fixing screws 67 (shown more clearly in FIG. 8 ) extend through the end wall 23 of the mounting structure 20 and into tapped receiving arms 68 of the rear housing 14 .
Although not shown in the drawing, the rear of the front housing 11 is provided with spaced mounting lugs having cylindrical bores through which the mounting screws 67 also extend to achieve assembly. FIG. 8 shows downward rotation of the handle 15 , typically after manual unlocking and depression of the handle. The actuating barrel 33 retracts the carriage 31 by virtue of engagement of the upper ear 41 with the upper lobe 63 of the carriage thereby displacing it to the right as shown in FIG. 8 . The pin 25 is thus retracted to the position shown in FIG. 8 and is removed from engagement with the cavity 56 of the receiving block. The gate can then be swung open and, when the handle is released, because there is no magnetic field influence, the carriage 31 remains in its position under biasing of the spring 26 and leaving the latch pin 25 retracted.
FIG. 9 shows the handle returned to its original position under influence of the torsion spring 66 with the carriage 32 in its right hand displaced position.
As and when the gate is returned to its closed position, the latch pin 25 again becomes aligned with the receiving cavity 56 and is then attracted under the strong magnetic field to move to the left thereby compressing the biasing spring 26 and sliding the carriage 32 to the left so that the configuration of FIG. 7 is attained.
Reference will now be made to FIG. 10 which shows a second embodiment of the disclosure which is similar to but a more practical version of the first embodiment. Like reference numerals have been used for like parts and only differences will be highlighted.
This embodiment shows the detail for mounting a conventional six pin cylinder lock 17 in each handle. The lock is inserted into the handle barrel with a lateral projection from each cylinder engaging in a corresponding cavity. A retaining plate 19 is inserted to close the cavity and secured by fixing screws 19 A. Each cylinder lock has a projecting tab 18 being of rectangular cross-sectional shape for conventional purposes and of a length to suit engagement in respective rotor elements 27 and 28 to be associated with the actuating barrel 33 as described in more detail below.
Each handle is secured to the respective casing by a spring clip 69 .
In this embodiment, the form of the mounting plate 20 is slightly different form, as illustrated, and the end wall 23 incorporates an integral security housing projection 28 .
In this embodiment, the barrel 33 , in place of the pivotal spring arms 34 of the first embodiment, has a moulded collar 29 . Within the collar is mounted a tongue 57 which is secured in cooperating relationship to the front and rear rotors 27 and 28 which are secured, as described below, by two plain roll pins 59 .
FIG. 10 shows in this embodiment that the handles have a pair of arcuate projecting tabs 40 for transmitting rotation. The front handle 40 has its tabs, on assembly, engaged in grooves 66 in a front portion of the barrel 33 whereas the rear handle 16 has its tabs 40 engaged in grooves 67 on the rear of the barrel 33 . Thus rotation of either handle will rotate the barrel. However the collar 29 does not rotate unless the tongue 57 has engaged in a recess 29 A in the collar. Engagement is achieved by unlocking. Unlocking the front lock turns the rotor 27 by virtue of engagement of the rectangular bar 18 in a central aperture in the rotor and, because of eccentric positioning of the pins 59 , the tongue is displaced to the left as shown in FIG. 10 so its leading end engages in the cavity 29 A in the collar. Thereafter rotation of the handle causes rotation of the collar 29 and upper or lower ear 41 then engages a lobe 63 of the C-shaped carriage to retract the latching pin.
Referring now to FIG. 11 , which is an oblique view through a vertical central plane of the assembled device in a locked configuration, the configuration of the tongue 57 will be better appreciated. The collar 29 is mounted on and freely rotatable on the barrel 33 with the torsion spring 66 , not shown in the drawing, located behind the collar 29 . This biases the barrel to its normal or rest position. The tongue 57 has a slightly elongate aperture 58 elongated in the vertical direction and receiving from each side thereof cylindrical projections, each having a through bore, from the respective rotors 27 and 28 . A first of the pins 59 A is inserted through rotor 27 through its cylindrical projection and into the complimentary cylindrical protection of the rotor 28 lying behind the tongue. The second pin 59 B is inserted through an aperture in the rotor 27 , through an arcuate slot 57 A in the tongue and into a corresponding aperture in the other rotor 28 .
The collar 29 is rotatably mounted around the barrel and in the position shown in FIG. 11 the tongue 57 is in a retracted position so that rotation of the barrel and tongue by a handle does not transmit any rotation to the collar 41 . The ears 41 lay adjacent the lobes 63 of the carriage. When the key mechanism is actuated to unlock the handle rotation of the rotor 27 occurs and the eccentrically disposed upper roll pin 59 occurs relative to the central pin 59 B in an anti-clockwise direction thereby displacing the tongue to the left is shown in FIG. 11 . This then causes the leading edge of the tongue to engage in the cavity 29 A whereby any rotation of the handle thereafter rotates the barrel, the tongue and the collar thereby retracting the carriage 31 and the latch pin 25 .
FIGS. 12 and 13 show an enlarged scale in isometric view the assembled components in the locked and unlocked configurations.
In place of the cylinder lock shown in FIG. 10 a wafer lock, which is less expensive and simpler, may be used. FIG. 14 is an exploded view of such an embodiment. A cylinder lock has an inherent lost motion effect but a wafer lock does not. Therefore when a wafer lock 117 is used, an adapter barrel 117 A or 117 B is utilised. Each adapter barrel has an eccentrically disposed arcuate slot facing the end of the wafer lock and accommodating and providing lost-motion for an eccentrically disposed cylindrical projection from the tip 117 C on the rear end of the wafer lock (see rear wafer lock 117 in FIG. 14 ). In the case of the front adapter barrel 117 A, it contains a short rectangular bar 117 D for engaging in and rotating the front rotor 27 and in the case of the rear adapter barrel 117 B there is a rectangular slot 117 E in the adapter barrel for accommodating the end of an elongate rectangular drive bar 18 which has the effect of driving the rear rotor 29 .
FIG. 15 is an exploded view of a third embodiment being a no-lock version wherein like parts have been given like reference numerals. Equivalent functionality applies without the complexity of locking options. In this embodiment an alternative form of non-adjustable latch block 112 is illustrated incorporating a cavity for the high performance magnet 54 which is retained by a cover plate 113 .
The barrel 33 is simplified as an integral moulding incorporating ears 41 and at a forward end region a pair of grooves 33 A for engaging with the projecting tabs 40 from the rear of the front handle for rotating the barrel. The rear portion of the barrel has further grooves 33 B for similar engagement with the projecting tabs 40 from the rear handle 16 . Upon assembly the barrel is located with the ears 41 located behind the lobes 63 of the carriage 31 and the embodiment operates by direct actuation of the carriage.
FIG. 15 also illustrates a square aperture 33 C extending through the barrel for accommodating a conventional square drive bar of a rotary door knob which is an alternative to the use of the handles shown.
Referring now to the fifth embodiment of FIGS. 16-18 , the drawings show an alternative connection system between the locking pin 25 and handle 15 to replace the actuating barrel 33 and the associated upper ear 41 and upper lobe 63 of the first embodiment. In this embodiment, there is provided a drum (not shown) around which is mounted a flexible line 70 . The line 70 is connected to a right hand end portion of the pin 25 . FIG. 16 shows the device in the same predetermined position as shown in FIG. 7 . The locking pin 25 is drawn to the left and the flexible line 70 is drawn off the drum and becomes taut. In this configuration the handles 15 and 16 are released and arranged horizontally by the effect of the torsion spring 66 .
Referring now to FIG. 17 , downward rotation of the handle 15 has occurred, typically after manual unlocking and depression of the handle 15 , causing the flexible line 70 to retract the locking pin 25 , displacing it to the right against the force of the magnet 54 . The pin 25 is thus retracted to the position shown in FIG. 17 and is removed from engagement with the cavity 56 of the receiving block. The gate can then be swung open, and when the handle is released, there is no magnetic field influence on the locking pin 25 . The pin 25 which is biased to the right by the biasing spring 26 . FIG. 18 shows the sagging of the flexible line 70 when the handle 15 is released and returns to its original position under the influence of the torsion spring 66 .
In a similar way to previous embodiments, when the door or gate is returned to its closed position, the configuration of FIG. 16 is attained once again.
Referring now to the adaptation of FIG. 19 , the parts are shown schematically with provision for a remote actuator 72 including an electrical actuator 72 having a set of connections 73 when it is to be hardwired to a circuit closing device or an aerial 74 where a wireless signal is to be received and interpreted to actuate the device. The circuit includes a source of electrical power such as a transistor radio battery sufficient to drive either a solenoid or a small motor 75 which drives the drum 70 A. Thus remote actuation can occur to remotely actuate the gate lock.
Referring now to the seventh embodiment of FIGS. 20 and 21 , like reference numerals have been used for like parts. This embodiment differs from the first embodiment by responding to rectilinear push-button operation which rotates a modified barrel 33 which otherwise functions as in the first embodiment.
Push button 118 has a gear rack 119 engaging a pinion 122 having a horizontal axis aligned with the axis of the latch pin 25 . The button 118 is slidably mounted in the housing of the device and is biased by a spring (not shown) to its outward or projecting position. When the button is depressed, rack 119 rotates pinion 122 which carries a crown gear 120 in constant mesh with a gear 121 on the barrel 33 so that the barrel rotates. Upper ear 41 engages the upper lobe 63 of the carriage 31 to retract it and the latch pin 25 to the position shown in FIG. 20 .
After opening of the gate on which the device is mounted, and upon release of the button, the barrel and button return to an initial position, corresponding to that shown in FIG. 21 , but with the carriage 31 and latch pins remaining in the displaced position shown in FIG. 20 .
When the gate is re-positioned to its closing position, the magnet in the receiving unit (not shown) attracts the latch pin to the latching position shown in FIG. 21 . | A magnetic self-latching device for a gate has a main body with handles on either side for operation or has an arrangement to be remotely actuated, for example electrically. A latching body has a high strength magnet usually provided at the bottom of a cavity which defines a latching shoulder. The latching body is adapted to be fixed to a gate post. The main body, with its housing, can be mounted on the gate frame and incorporates a latch pin which, in the door-closed position, is displaced by magnetic attraction to an extended latching position and against the biasing of a return spring. The gate cannot be opened until actuation of the mechanism occurs, for example by rotating a handle to retract the pin against the magnetic force; the gate can then be swung open. When the handle is released, the biasing spring retains the latch pin in a retracted position. A lost motion arrangement is provided so that there is substantially no load on the pin when the handles are released and the pin is supported in the retracted position by the return spring. A carriage and an associated actuator or a flexible/semi flexible line connection is provided in the housing for incorporating the lost motion arrangement. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/908,933, filed Mar. 29, 2007.
TECHNICAL FIELD
The present invention relates to leaching chambers for receiving and dispersing water and wastewater when buried in the soil, and more particularly, to such pre-molded leaching chambers as are corrugated and arch-shaped in cross-section with contiguously molded end walls, and lateral interior chambers having fluid communication openings at the chamber base.
BACKGROUND ART
The use of above-ground watering systems, particularly in dry climates such as the southwestern regions of the United States and in the Mediterranean regions of Europe, the Middle East, and Africa, brings with it a list of known problems. In addition to water loss through evaporation during the watering process, if watering is provided too lightly, shallow plant rooting results. Additionally, repeated surface applications of water tend to produce the buildup of mineral salts, which are detrimental to healthy plant growth.
As increasing population pressures result in greater demands upon fresh water supplies, the benefits of underground irrigation have become increasingly attractive. Such systems place water almost directly into the plant root zone and eliminate evaporative water losses. Their protected location also minimizes the risk of damage from surface activities.
The subsurface fluid distribution system described in my previous patent, Sipaila, U.S. Pat. No. 5,921,711, provides such a subterranean system with reserve fluid storage capacity to maintain soil dampness as well as replace water taken up by plants. As used in a passive subsurface irrigation system, capillary physics and gravity are relied upon to deliver water and nutrients to plants through an interconnected series of chambers and pans. Such systems are capable of reducing the amount of irrigation water required by 50-80% over the more traditional above-ground systems.
As is typical for such systems, the leaching chamber has sloped sidewalls that extend to a curved, arched top. When installed, such extended-arch chambers must resist both top and side loadings. The slots in the sidewalls permit the transport of water from within, but act to weaken the sidewall structure.
While thickening the sidewall would provide additional strength, it also results in an increase in the amount of material required—which is a polyolefin, and is thus tied to the rising cost of petrochemicals. In addition, the added weight of the resulting product adds to the cost of transporting the chambers to the installation site. Also, while it is vital that such chambers are able to efficiently stack for transport, the stacking of such bulked-up chamber walls must not result in forcing the sidewalls out, resulting in the overall flattening and weakening of the arch-shaped chamber.
It thus is desirable to provide additional solutions that increase the structural integrity of the arched chamber in a manner that enhances the operational efficiency and is not negated by increased transportation costs or product damage during shipment.
DISCLOSURE OF THE INVENTION
These and other objects are achieved by providing a pre-molded leaching chamber of arch-shaped cross-section, having a pair of contiguously molded, opposing end walls, alternating peak and valley corrugations along its length, and interior chambers formed at the base of the chamber at each peak corrugation providing fluid communication between the exterior and interior of the leaching chamber. The interior chambers are formed by an inner wall attached to an interior surface of the leaching chamber and extending substantially within the peak corrugation, spaced from the outer wall, to the base of the chamber. Vertically off-set apertures are formed in the inner wall and in the opposing outer wall, enabling fluid flow within the inner chamber.
A leaching chamber comprising: a corrugated outer shell extending along a longitudinal axis in a manner defining alternating peak corrugations and valley corrugations, said corrugated outer shell having an arch-shaped cross-section with a pair of opposed lateral end walls formed therein and no floor; and a plurality of inner walls attached to an interior wall of said corrugated outer shell, each at a location within a separate interior valley formed in said interior wall, with each of said interior valleys corresponding to a peak corrugation formed in said outer shell, said plurality of inner walls extending from a location of attachment to said interior wall to a terminus of a respective one of said interior valleys, each of said plurality of inner walls extending in a manner inwardly spaced from said corrugated outer shell to define a plurality of interior chambers, wherein each of the plurality of interior chambers has an inner wall aperture formed in said respective inner wall and an outer shell aperture formed in the corrugated outer shell.
A leaching chamber having an arch-shaped cross-section and alternating peak corrugations and valley corrugations along its length comprising: a pair of opposed end walls attached to said leaching chamber at opposite ends thereof, each of said pair of opposed end walls having a connecting pipe aperture formed therein; and a plurality of inner walls attached to an inner surface of said leaching chamber and extending towards a base of said leaching chamber, each of said plurality of inner walls extending in a spaced-apart manner from a separate one of such adjacent lateral wall segment of said leaching chamber as defines one of said alternating peak corrugations, each of said plurality of inner walls and each of said respective adjacent lateral wall segments define an individual interior chamber formed therebetween, each of said inner walls and said adjacent lateral wall segments have an aperture formed therein, whereby fluid communication between an interior of said leaching chamber and an outer environment of said leaching chamber may occur through each of said plurality of interior chambers.
These and various other advantages and features of the present invention are pointed out with particularity in the claims. Reference should also be had to the drawings which form a further part hereof, as well as to the accompanying descriptive matter in which are illustrated and described in various examples of with the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partial top perspective view of a leaching chamber in accordance with the present invention.
FIG. 2 is a partial bottom perspective view of the leach chamber of FIG. 1 .
FIG. 3 is a cross-sectional view, with portions shown in phantom, taken along line 3 - 3 of FIG. 1 .
FIG. 4 is a partial cross-sectional view taken along line 4 - 4 of FIG. 1 .
FIG. 5 is a partial cross-sectional view taken along line 5 - 5 of FIG. 1 .
FIG. 6 is a partially exploded cross-sectional view of a plurality of stacked leaching chambers, the cross-sectional views of each of the chambers taken along line 3 - 3 of FIG. 1 .
FIG. 7 is a partial cross-sectional view showing a connecting pipe enabling fluid communication between an adjacent pair of leaching chambers.
FIG. 8 is a cross-sectional view, similar to FIG. 3 , with portions shown in phantom, taken along line 3 - 3 of FIG. 1 showing an alternative embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference is now made to the drawings wherein like numerals refer to like parts throughout. In FIG. 1 , a leaching chamber 10 includes a corrugated outer shell 14 and an end wall 18 . A connecting pipe aperture 22 is centrally located in the end wall 18 , and is appropriately sized to receive a connector pipe that extends between and is used to connect adjacent leaching chambers (not shown in the Figures).
The end wall 18 also includes a pair of outer fluting extrusions 26 that are centrally located and extend between the connecting pipe aperture 22 and a base 24 of the end wall 18 . Functioning as stiffeners, the outer fluting extrusions 26 , together with a single inner fluting extrusion 28 (see FIG. 3 ), provide three-dimensional structural support to the end wall 18 without compromising the extrusion process of fabricating the leaching chamber 10 .
Additional structural support is provided by a footing flange 32 that is attached to and extends from the base 24 of the end wall 18 . A plurality of triangular braces 34 are arranged in a spaced-apart manner along the footing flange 32 to provide lateral rigidity to the flat end wall 18 . Each of these end wall reinforcement features may be fabricated as part of the extrusion process used to form the end wall and corrugated outer shell of the leaching chamber 10 .
A support footing 42 extends along each lateral terminus of the corrugated outer shell 14 , providing a stable support base when the leaching chamber 10 is positioned for use in an irrigation system or drainage system as well as when it is stacked for transport. In regard to the latter function, a stacking nub 46 is formed on and projects at a lateral location on the corrugated outer shell 14 . The stacking nubs 46 are positioned in a manner that provides support to the support footing 42 when a plurality of leaching chambers 10 are vertically stacked (see FIGS. 3 and 6 ).
The corrugated outer shell 14 exhibits a repeating outer pattern of peak corrugations and valley corrugations (ridges and grooves), with these outer peaks and valleys inversely corresponding to peaks and valleys from a perspective within the leaching chamber 10 (see FIG. 2 ). An inner wall 52 is formed within each of the interior valleys, and extends from the support footing 42 to a fused attachment seam 54 formed in the corrugated outer shell 14 .
The inner wall is inwardly spaced from the corrugated outer shell 14 at its location of attachment to the support footing 42 , forming an interior chamber 58 (see FIG. 4 ). A plurality of such interior chambers 58 are formed in, and laterally extend along, in a spaced-apart manner, both longitudinal sides of the leaching chamber 10 . Each of the interior chambers 58 is provided an inner wall aperture 62 formed in the inner wall 52 and an outer shell aperture 64 that is formed in the corrugated outer shell 14 .
In a presently preferred embodiment, the inner wall aperture 62 and the outer shell aperture 64 are vertically off-set, with the outer shell aperture 64 at a vertical location that is lower than the inner wall aperture 62 when the leaching chamber 10 is in operation. As is best shown in FIG. 4 , this vertical off-set inhibits the reverse flow of particulate matter from the outer environment through the interior chamber 58 , which would otherwise result in the fouling of the primary chamber of the leaching chamber 10 .
As discussed previously, most applications require a series of leaching chambers 10 that are connected together using discrete connecting pipes, with each pipe extending between opposing connecting pipe apertures to connect together adjoining leaching chambers 10 . It is essential that each leaching chamber 10 remain in fluid communication with any adjoining leaching chamber 10 with which it shares a connecting pipe 70 (see FIG. 7 ).
As is depicted in both FIGS. 5 and 7 , a stop nub 68 is formed in an interior wall of the corrugated outer shell 14 and extends downwardly to provide a surface against which an end of the connecting pipe 70 can rest. The stop nub 68 resists any further inward migration of the connecting pipe 70 after installation. Such longitudinal movement—in either direction, could result in the dislodgement of the connecting pipe 70 from an adjoining leaching chamber 10 , which in turn would abruptly end or severely impair the fluid communication therebetween. The distance between the adjacent, connected leaching chambers 10 can be as short as a few inches or as long as ten feet, depending upon the particular application. Separation in typical athletic fields is about one foot between the end walls 18 .
In an alternative embodiment of the present invention shown in FIG. 8 , the connecting pipe aperture 22 has been repositioned close to the base 24 of the end wall 18 . Under this embodiment drainage occurs at the bottom of the leaching chamber 10 , and no or only a very slight amount of water remains within the leaching chamber 10 —unlike the reservoir of water created within the leaching chamber 10 when the connecting pipe aperture 22 is positioned at a higher location on the end wall 18 (see FIG. 3 ).
The embodiment of FIG. 8 is also provided a lower profile, having a preferred height A of 4 inches instead of 6.3 inches, and a width B of 8.25 inches instead of the previous 13.25 inches. These dimensions provide a reduced profile having less cost in material, the ability to be placed at a shallower depth and with less fill—both lowering installation costs. The remaining dimensions are preferably much the same as in the previously discussed embodiment, the connecting pipe aperture 22 having a diameter C of 2.375 inches, the inner wall aperture 62 having a height D of 0.875 inches, and the outer shell aperture 64 having a height E of 1 inch (preferably reduced by one-half inch as compared to the previously-discussed embodiment).
The embodiment shown in FIG. 8 is best suited for applications in which drainage is the primary and/or only intended function. However, in flat arrays of the system, water backup can be obtained by utilizing an up-turned elbow as a terminating connecting pipe (not shown in the Figures). Such a terminus would create a pressure head, resulting in the flooding of the connector pipe and all intermediate leaching chambers—making irrigation a possible, but not preferred function of the alternative embodiment shown in FIG. 8 .
In a presently preferred embodiment, and recognizing that other dimensions are possible—and considered within the scope of the present invention, the leaching chamber 10 is fabricated by extruding a plastic such as high density polyethylene, polypropylene or other suitable polymers. By positioning all of the offset and connecting apertures in an injection mold cavity, all of the improvements can be monolithically molded to produce a one-piece leaching chamber without any other machining. The inner wall apertures and the outer shell apertures are spaced approximately one-and-a-half inches apart, on center, and are vertically offset approximately 1 to 1½ inches. The ½ inch stacking nub 46 and ¼ diameter and ½ inch-long stop nub 68 ; the ¼ inch by 3 inch-long fluting extrusions, the 2 inch height of the inner wall 52 ; the 1 inch width of the footing flange 32 , the ½ inch triangular braces 34 , and the 1 inch wide support footing 42 can all be incorporated in the same injection mold process to produce a single piece integrated chamber.
The installation of the leaching chambers in accordance with the present invention is initiated by the excavation of a series of trenches, fourteen to eighteen inches deep and eighteen to forty-eight inches wide. The length and width of the trenches will vary, depending upon the design requirements for the particular leaching bed, irrigation field or drainage tile. At a minimum, an excavated section of length four feet is leveled, and if downward leaching of water is not desired, water impermeable liners or enclosing boxes are installed in the leveled trench. Thereafter a series of leaching chambers are placed within the trench, and laid end-to-end so that the lateral leaching chamber water discharge apertures are substantially aligned. The leaching chambers are then connected to one another utilizing the end panel connector pipes.
A layer of sand or suitable fine gravel for drainage applications is then back-filled over the leaching chambers. Since the upward capillary draw of most sands exceeds a ten-inch vertical above the waterline, a preferred depth of the fill sand over the leaching chambers is approximately twelve inches from the trench bed. The present invention can make use of sands of varying coarseness, with a sand coarseness of 0.3 mm to 0.6 mm grain size being viewed as particularly appropriate.
Finally, the sand layer may be optionally covered with top soil to a depth of between approximately zero to four inches. Because of the arched cross-section of the outer shell 24 , the leaching chambers 10 are sufficiently strong to withstand the weight of vehicles on top of the replaced soil. Additionally, the individual settling of the leaching chambers within the trenches will not cause a break in the sand seal of the system, since the connector pipes 70 are self-adjusting with the apertures 22 in the end wall 18 .
Depending upon the slope of the particular terrain, several different arrangements of the leaching chamber arrays are possible. Since the leaching chamber units act independently throughout their (preferred) four foot length, on sloping terrain the trenches are preferably excavated level along the slope contours. The “adjacent” leaching chambers can then be connected perpendicularly across the slope contours, with such adjacent leaching chambers located on different vertical levels, utilizing longer connector pipes where required.
My invention has been disclosed in terms of a preferred embodiment thereof, which provides an improved half-pipe leaching chambers for subterranean fluid distribution that is of great novelty and utility. Various changes, modifications, and alterations in the teachings of the present invention may be contemplated by those skilled in the art without departing from the intended spirit and scope thereof. It is intended that the present invention encompass such changes and modifications. | A leaching chamber having an arch-shaped cross-section, a pair of contiguously molded, opposing end walls, and alternating peak and valley corrugations along its length, is provided interior chambers and fluid communication openings along the base on each extending side of the chamber. Formed within the chamber at locations corresponding to each peak corrugation, an inner wall is attached to an interior surface and extends substantially within the peak corrugation to the base of the chamber. An aperture is formed in both the inner wall and in the opposing outer wall of the chamber, enabling fluid communication through the interior chamber—and thus into and out from the interior of the leaching chamber itself. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION
This is a continuation application of application Ser. No. 09/442,500, filed Nov. 18, 1999, now U.S. Pat. No. 6,415,669, which is a continuation-in-part of application Ser. No. 09/056,880, filed Apr. 9, 1998, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention provides apparatus for aspirating and dispensing controlled amounts of liquid from a solid dispense block into receptacles, the apparatus including means for loading pipette tips designed for sealing on its outside diameter into internal cylinders within the dispense block head.
2. Description of the Related Art
U.S. Pat. No. 5,497,670 issued Mar. 12, 1996, the subject matter set forth therein invented by the inventor of the present invention, discloses an improved dispensing head apparatus including means for loading pipette tips carried by a pipette plate onto dispensing cylinders, the loading force being maintained during the apparatus operation cycle, thus ensuring a hermetic seal. The pipette tips are manually placed on the tip plate, the plate sliding within the dispensing apparatus.
Although the pipette tip plate holder described in the aforementioned patent provides many advantages when used with the apparatus described therein, there are certain disadvantages associated with its use. In particular, there is a possibility that the pipette tip slide plate may become contaminated. Most importantly, the pipette tip plate configuration is not easily adapted for robotics operation or automation.
U.S. patent application Ser. No. 08/751,859 filed Nov. 18, 1996, the subject matter set forth therein also invented by the inventor of the present invention, provides a self contained head dispensing apparatus similar to that disclosed in the aforementioned patent but modified to the extent that the pipette tip plate disclosed therein is replaced with a more conventional pipette tip carrier which is less expensive, is less likely to be contaminated and wherein the carrier is easily adapted for robotics operation or automation.
A microplate typically holding 96 wells with 9 mm on centers spacing in a 8 by 12 array is typically used with most dispense apparatus. The early prior art dispense devices started with one dispenser and moved in the X-Y direction 96 times to dispense into each of the 96 wells. Over time, dispense devices were added to include one row (8 or 12 wells per row) and then indexing either 8 or 12 times to fill the entire plate. A 96 dispense apparatus device to fill an entire plate at one time is disclosed, for example, in the '670 patent noted above.
The microplate has recently changed in design. Higher production speeds and larger storage libraries required higher density formats. The 96 well format with its 9 mm spacing has increased to 384 with 4.5 mm spacing. The 384 microplate has increased to 864 and now 1536 with 2.25 mm spacing. These different density plates have the same foot print (length, width).
In the dispensing method disclosed in the '859 application, a pipette that fits on the outside of a cylinder and tapers down to a small point is used. Most pipette dispensing systems are connected to the cylinder used in the dispensing head using an “O” ring to ensure a proper fluid seal from the pipette inside diameter (“ID”) to the cylinders outside diameter (“OD”). The typical pipette seals on its ID and therefore builds up the OD of the pipette. The typical OD is larger than 4.5 mm and therefore makes it difficult for use with higher density formats dispensing like 384 (4.5 mm spacing) since the 384 microplate has 4.5 mm spacing—therefore a pipette is to be used on the 384 format must have an OD that is smaller than 4.5 mm.
Prior art dispense devices, like the one disclosed in the '679 patent, use separate cylinders (one for each pipette), 96 total. This is the easiest way to connect to the pipettes ID. If a pipette is designed that seals on its OD, a new dispense head design is required. This would include sealing, loading, and stripping methods.
What is thus desired is to provide a new pipette design that allows sealing on its outside diameter with means of loading and stripping and to provide a new dispense apparatus that essentially comprises an integral solid block and which does not require discrete cylinders.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a self contained dispensing head apparatus wherein a pipette tip box tray carrier is utilized to furnish pipette tips, carried in a standard pipette tip box, to the head apparatus and wherein means are provided to engage the tray carrier in a manner whereby the pipette tips are loaded in corresponding internal cylinders (openings) in the apparatus. The dispense block head comprises a solid block of material having a plurality of internal cylinders to engage the pipette tips in a sealing arrangement.
The pipette tips are modified from the conventional design in that a disk-shaped ring portion is interposed adjacent to one end of the pipette, the upper tapered portion allowing the dispense head internal cylinders to form a seal therewith.
The present invention thus provides a dispensing head apparatus which enables liquid to be aspirated from a first microplate and dispensed into a second microplate using various array formats, the dispense block head being formed from one solid block, thus substantially reducing manufacturing costs. The dispense head also allows a tight array of internal cylinders to be provided thus accommodating higher density format microplates.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
For a better understanding of the invention as well as other objects and further features thereof, reference is made to the following description which is to be read in conjunction with the accompanying drawing wherein:
FIG. 1 is a side view of the dispense head apparatus with a pipette tip box to be loaded from the pipette tip box tray carrier;
FIG. 2 illustrates loading of pipette tips to the dispense head block;
FIG. 3 illustrates the removal of the pipette tips from the pipette tip box;
FIG. 4 is a sectional view of the tray carrier engaged with the tip box tray carrier loading plate;
FIG. 5 illustrates the tray carrier of FIG. 4 with the pipette tip box being removed from the tip box tray carrier loading plate;
FIG. 6 is an enlarged partial cross-sectional view of the dispense block head and a pipette tip positioned for sealing engagement;
FIG. 7 illustrates the pipette tip of FIG. 6 engaged in the dispense block head;
FIG. 8 illustrates the dispense head apparatus aspirating from a 384 well microplate;
FIG. 9 is a side view of the dispense head apparatus illustrating the dispense head apparatus stripping pipette tips back into the pipette tip box; and
FIGS. 10A and 10B illustrate the stages in stripping a single pipette tip from the dispense head apparatus.
DETAILED DESCRIPTION OF THE INVENTION
The basic liquid dispensing apparatus and in particular, the apparatus used to move the various components, such as the tip box tray carrier 22 , are described in U.S. patent application Ser. No. 08/751,859, filed Nov. 18, 1996, and will not be repeated herein for the sake of brevity. The discussion that follows will be directed to the new pipette tip design and the dispense head apparatus, both together allowing a 384 microplate (and multiples thereof) to be used for receiving and dispensing liquids.
The present invention is directed to a new pipette tip that is able to seal on the outside diameter (OD) and capable of automatic tip loading and stripping (unloading). In addition, the dispense head apparatus incorporates a new pipette dispense block head capable of dispensing or aspirating fluid at one time into a 384 microplate or, with multiple motions, into a 1536 microplate. A motion plate, not the subject of the present invention, can be used to index for 96 to 384 or 384 to 1536 microplate replication of transfer. The dispense block head is fabricated from a solid block rather than 384 separate cylinders as would be required by the design set forth in application Ser. No. 08/751,859 and thus, functions, in essence, as a cylinder head.
FIG. 1 is a simplified front view of the dispense head apparatus 10 of the present invention. The dispense head apparatus 10 is basically identical to the apparatus described in the '859 application except for the new dispense block head 26 and pipette tip 20 . In particular, dispense head apparatus 10 comprises piston plate 12 , horseshoe plate 14 , movable pipette tip box carrier loading plate 16 , 384 pipette tip box 18 , pipette tips 20 , pipette tip box tray carrier 22 , pipette tip box tray carrier loading pins 24 and dispense block head 26 . A floating stripper plate 30 , described in more detail hereinafter, is also new to dispense head apparatus 10 .
FIGS. 6 and 7 illustrate the upper tapered portion 2 of pipette tip 20 which is positioned to be loaded with the dispense block head 26 shown in FIG. 1 . Pipette tip 20 , formed of plastic material, comprises upper tapered portion 2 adapted to form a sealing interface 7 as shown in FIG. 7 when loaded into the dispense block head 26 . The upper tapered portion 2 also functions to center the pipette tip 20 into the internal cylinder 13 formed in dispense block head 26 (in the figure illustrated, dispense block head 26 comprises 384 internal cylinders; only one internal cylinder of the 384 holes is illustrated) during tip loading as shown in FIG. 2 . The centering function of upper tapered portion 2 also accommodates for pipette tip variations that normally occur in the molding process while still providing a useable hermetic seal for the 384 pipette tips used (the number of pipette tips used correspond to the number of internal cylinders in dispense block head 26 ). A disk-shaped ring portion 3 separates the upper tapered portion 2 from lower tapered portion 4 , the disk-shaped ring portion 3 having an upper surface 5 and lower surface 6 . During the tip loading sequence, lower surface 6 of disk-shaped ring portion 3 rests on the pipette tip box 18 and when the pipette tip box 18 is pulled up during the loading sequence (similar to the process in the aforementioned patent application), the pipette tips 20 are pneumatically forced into the dispense block head 26 to create a hermetic seal with upper tapered portion 2 and internal cylinder 13 . The axial loading force displaces the pipette tip 20 to ensure that the seal is made with the outside diameter of the upper tapered portion of the internal cylinder 13 and is frictionally held captive during aspirating and dispensing.
As illustrated in FIG. 6, the internal bore extends along the length of the pipette tip 20 . This shape is preferred because, as discussed herein, the pipette tip 20 is designed for precisely measuring fluids, and it distinguishes a measuring pipette tip from other types of pipette tips, such as centrifugable pipette tips. As generally understood in the art, a centrifugable pipette tip to function properly has a substantially tapered bore (i.e.—, tapered 20 degrees or more), and has multiple chambers for retaining the separated solids.
As illustrated in FIG. 6, and as readily appreciated geometrically, the bore is numerous orders of magnitude longer than it is in diameter.
The pipette tip loading sequence transfers pipette tips 20 from the pipette tip box 18 and with an upward force axially loads them into the dispensing block head 26 as shown. The mechanical method of loading the pipette tip 20 by moving the dispense block head 26 in x, y, z motions is the same as set forth in the aforementioned application with the addition of a floating stripper plate 30 incorporated into the dispense head apparatus 10 . As the loading sequence begins, the movable pipette tip box tray carrier loading plate 16 , with alignment provided by floating stripper plate guide pins 35 , raises (pulling with it) pipette tip box tray carrier 22 , and pipette tip box 18 with pipette tip 20 , up toward the dispense block head 26 to mate, compressing floating stripping plate return springs 32 against movable pipette tip box tray carrier loading plate 16 . This allows the free passage of the dispense block head 26 through the movable pipette tip box tray carrier loading plate 16 while at the same time creating a zero gap condition between the floating stripper plate 30 and the dispense block head 26 . The pipette tip box 18 continues upward, pushing the pipette tips 20 by applying force to the lower surface 6 of disk-shaped ring portion 3 , into the dispensing block head 26 and its sealing interface 7 as shown in FIG. 7 . Floating stripper plate 30 is now positioned between dispense block head 26 and the disk-shaped ring portion 3 . The pipette tip 20 is now seated and hermetically sealed within the internal cylinders 13 in dispense block head 26 . FIG. 4 illustrates the pipette tip box tray carrier 22 engaged with tip box tray carrier loading plate 16 therefor. FIG. 5 illustrates the pipette tip box tray carrier 22 with pipette tip box 18 being disengaged from the movable pipette tip box tray carrier loading plate 16 . The dispense block head 26 is now free to travel. When the pipette tips 20 are to be stripped, the opposite sequence is performed in the manner set forth in the aforementioned application.
In order to strip the pipette tips 20 from the dispense block head 26 , the following sequence occurs:
1. The dispense block head 26 is in a fixed position and the movable pipette tip box tray carrier loading plate 16 moves down (dispense block head 26 in essence, functions as a cylinder block).
2. The movable pipette tip box carrier loading plate 16 has an inclined surface pocket 51 at its bottom surface; inclined surface pocket 51 mates with the floating stripper plate 30 causing the floating stripper plate 30 to also be inclined in the downward movement. The floating stripper plate alignment pins 32 pass through a tapered hole in the movable pipette tip box tray carrier loading plate 16 . The taper allows the floating stripper plate 30 to conform to the inclined surface pocket 51 of movable pipette tip box tray carrier loading plate 16 .
3. The continuing downward motion of the floating stripper plate 30 eventually contacts the upper surface 5 of disk-shaped ring portion 3 .
4. Since the dispense block head 26 is in a fixed position, the motion of movable pipette tray carrier loading plate 16 and floating stripper plate 30 causes pipette tips 20 to be stripped in a sequential manner. FIG. 9 illustrates the floating stripper plate 30 and movable pipette tip box carrier loading plate 16 engaged and fully extended, and stripping pipette tips 20 from dispense block head 26 . FIGS. 10A and 10B illustrate two stages in the ejection of a single pipette tip 20 from the dispense block head 26 . In FIG. 10A, the movable tip box pipette carrier loading plate 16 is moving downwards towards floating stripper plate 30 ; in FIG. 10B, movable pipette tip box carrier plate 16 is in engagement with floating stripper plate 30 . A counterbore 33 is formed in floating stripper plate 30 to allow the disk-shaped ring portion 3 of pipette tips 20 to be seated therein when loaded into dispense block head 26 and, in turn, to be stripped by floating stripper plate 30 .
The inclined pocket 51 assures smooth operation by not forcing all of the pipette tips 20 from the dispense block head 26 at one time, allowing instead stripping of the tips one row at a time. The stripping function is provided by an axial force applied to the top surface 5 of disk-shaped ring portion 3 on the pipette tip 20 until all have fallen into pipette tip box 18 . Once the pipette tips 20 are loaded back into the pipette tip box 18 , the pipette tip box 18 and pipette tip box tray carrier 22 are lowered to a table using dispense head apparatus 10 “X”, “Y”, “Z” motions.
FIG. 8 illustrates the dispense apparatus being used to aspirate from a 384 microplate 60 .
The present invention thus provides an improved dispense head and associated pipette tips which is usable with the higher density microplates now available and wherein the manufacturing cost of the dispense head is substantially reduced.
While the invention has been described with a reference to its preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the invention. In addition, modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its essential teachings. | A self contained dispensing head apparatus wherein a modified pipette tip box tray carrier is utilized to furnish pipette tips, carried in a standard pipette tip box, by a pipette tip box tray carrier to the head apparatus and wherein means are provided to engage the pipette tip box tray carrier in a manner whereby the pipette tips are loaded into corresponding internal cylinders formed in the dispense block head. The dispense block head comprises a solid block of material having a plurality of internal cylinders to engage the pipette tips in a sealing arrangement. The pipettes are modified from the conventional design in that a disk-shaped ring portion is interposed adjacent one end of the pipette tip, a tapered end of the tip allowing a seal to be formed with the dispense block head internal cylinders. | 1 |
TECHNICAL FIELD
[0001] This application claims benefit from prior Provisional Application Ser. No. 60/135,290, filed May 21, 1999.
[0002] This invention relates to an apparatus and method for the construction and utilization of molecular deposition domains. More specifically, this invention is a method for the construction and utilization of molecular deposition domains into a high density molecular array for identifying and characterizing molecular interaction events.
BACKGROUND
[0003] Interactions between molecules is a central theme in living systems. These interactions are key to myriad biochemical and signal transduction pathways. Messages from outside a cell travel along signal transduction pathways into the cell's nucleus, where they trigger key cellular functions. Such pathways in turn dictate the status of the overall system. Slight changes or abnormalities in the interactions between biomolecules can effect the biochemical and signal transduction pathways, resulting in inappropriate development, cancer, a variety of disease states, and even cell senescence and death. On the other hand, it can be extremely beneficial to develop reagents and effectors that can inhibit, stimulate, or otherwise effect specific types of molecular interactions in biochemical systems; including biochemical and signal transduction pathways. Reagents and effectors that effect nucleus interactions may often become very powerful drugs which can be used to treat a variety of conditions.
[0004] Current Technology
[0005] Several recent studies have shown that a scanning probe microscope “SPM” may be used to study molecular interactions by making a number of measurements. The SPM measurements may include changes in height, friction, phase, frequency, amplitude, and elasticity. The SPM probe can even perform direct measurements of the forces present between molecules situated on the SPM probe and molecules immobilized on a surface. For example, see Lee, G. U., L. A. Chrisey, and R. J. Colton, Direct Measurement of the Forces Between Complementary Strands of DNA . Science, 1994. 266: p. 771-773; Hinterdorfer, P., W. Baumgartner, H. J. Gruber, and H. Schindler, Detection and Localization of individual Antibody-antigen Recognition Events by Atomic Force Microscopy , Proc. Natl. Acad. Sci., 1996. 93: p. 3477-3481; Dammer, U., O. Popescu, P. Wagner, D. Anselmetti, H. -J. Guntherodt, and G. N. Misevic, Binding Strength Between Cell Adhesion Poteoglycans Measured by Atomic Force Microscopy . Science, 1995. 267: p. 1173-1175; Jones, v. et al. Microminiaturized Immunoassays Using Atomic Force Microscopy and Compositionally Patterned Antigen Arrays , Analy. Chem., 1998 70(7): p. 1233-1241; and Rief, M., F. Oesterhelt, B. Heymann, and H. E. Gaub, Single Molecule Force Spectroscopy on Polysaccharides by Atomic Force Microscopy , Science, 1997. 275: p. 1295-1297. The above studies illustrate that it is possible to readily and directly measure the interaction between and within virtually all types of molecules by utilizing an SPM. Furthermore, recent studies have shown that it is possible to use direct force measurement to detect changes in molecular complex formation caused by the addition of a soluble molecular species. A direct force measurement may elucidate the effect of soluble molecular species on the interaction between a molecular species on an SPM probe and a surface.
[0006] Molecular Arrays
[0007] The ability to measure molecular events in patterned arrays is an emerging technology. The deposition material can be deposited on a solitary spot or in a variety of sizes and patterns on the surface. The arrays can be used to discover new compounds which may interact in a characterizable way with the deposited material. Arrays provide a large number of different test sites in a relatively small area. To form an array, one must be able to define a particular site at which a deposition sample can be placed in a defined and reproducible manner.
[0008] There are four approaches for building conventional molecular arrays known in the art. These prior art methods include 1) mechanical deposition, 2) in situ photochemical synthesis, 3) “ink jet” printing, and 4) electronically driven deposition. The size of the deposition spot (or “domain”) is of particular importance when utilizing an SPM to scan for molecular recognition events. Current SPM technology only allows a scan in a defined area. Placing more domains in this defined area allows for a wider variety of molecular interaction events to be simultaneously tested.
[0009] Mechanical deposition is commonly carried out using a “pin tool” device. Typically the pin tool is a metal or similar cylindrical shaft that may be split at the end to facilitate capillary take up of liquid. Typically the pin is dipped in the source and moved to the deposition location and touched to the surface to transfer material to that domain. In one design the pin tool is loaded by passing through a circular ring that contains a film of the desired sample held in the ring by surface tension. The pin tool is washed and this process repeated. Currently, pin tool approaches are limited to spot sizes of 25 to 100 microns or larger. The spot size puts a constraint on the maximum density for the molecular deposition sites constructed in this manner. A need exists for a method that allows for molecular domains of smaller dimensions to be deposited.
[0010] In situ photochemical procedures allow for the construction of arrays of molecular species at spatial addresses in the 1-10 micron size range and larger. In situ photochemical construction can be carried out by shining a light through a mask. Photochemical synthesis occurs only at those locations receiving the light. By changing the mask at each step, a variety of chemical reactions at specific addresses can be carried out. The photochemical approach is usually used for the synthesis of a nucleic acid or a peptide array. A significant limitation of this approach is that the size of the synthetic products is constrained by the coupling efficiency at each step. Practically, this results in appreciable synthesis of only a relatively short peptide and nucleic acid specimen. In addition, it becomes increasingly improbable that a molecule will fold into a biologically relevant higher order architecture as the synthetic species becomes larger. A need exists for an alternative method for deposition of macromolecular species that will preserve the molecular formation of interest in addition to avoiding the cost of constructing the multiple masks used in this method.
[0011] Ink jet printing is an alternative method for constructing a molecular array. Ink jet printing of molecular species produces spots in the 100 micron range. This approach is only useful for printing a relatively small number of species because of the need for extensive cleaning between printing events. A key issue with ink jet printing is maintenance of the structural/functional integrity of the sample being printed. The ejection rate of the material from the printer results in shear forces that may significantly compromise sample integrity. A need exists for a method that will retain the initial structure and functional aspects of the deposition material and that will form smaller spots than are possible with the above ink jet method.
[0012] Electronic deposition is yet another method known for the construction of molecular arrays. Electronic deposition may be accomplished by the independent charging of conductive pads, causing local electrochemical events which lead to the sample deposition. This approach has been used for deposition of DNA samples by drawing the DNA to specific addresses and holding them in a capture matrix above the address. The electronic nature of the address can be used to manipulate samples at that location, for example, to locally denature DNA samples. A disadvantage of this approach is that the address density and size is limited by the dimensions of the electronic array.
[0013] A need exists for a molecular deposition technique that will allow for smaller deposition spots (domains). Smaller deposition domains allow for an array to be constructed with a greater density of domains. More domains further allow for a wider variety in the deposition material to be placed on the same array, allowing a user to search for more molecular interaction events simultaneously.
[0014] A further need exists for the ability to place these spots at a defined spatial address. Placing the domains at defined spatial addresses allows the user to know exactly what deposition material the SPM is scanning at any given time.
[0015] Furthermore, a need exists for a method to make deposition domains with large molecular weight samples that also retains the desired chemical formation. Finally, a need exists for the efficient construction of these molecule domains into an array.
[0016] Molecular Detection
[0017] All of the above examples are further limited because they require some type of labeling of the deposition sample for testing. Typical labeling schemes may include fluorescent or other tags coupled to a probe molecule. In a typical molecular event experiment, an array of known samples, for example DNA sequences, will be incubated with a solution containing a fluorescent indicator. In the DNA example this would be fluorescently or otherwise labeled nucleic acids, most often a single stranded DNA of an unknown sequence. Specific sequence elements are identified in the DNA sample by virtue of the hybridization of the label to addresses containing known sequence elements. This process has been used to screen entire ensembles of expressed genes in a given population of cells at a particular time or under a particular set of conditions. Other labeling procedures have also been employed, including RF (radio frequency) labels and magnetic labels. These methods are less frequently used, however, than the fluorescent label methods desired above. All of these labels hinder experiments with extra steps, reagents, and in some cases, risk.
[0018] Other methods for the detection of the interactions of molecules on a molecular array include inverse cyclic voltametry, capacitance or other electronic changes, radioactivity (such as with isotopes of phosphorous), and chemical reactions. In virtually all cases, some form of labeling of the probe molecule that is added to the array is required. This is a significant limitation of current arrays. A need exists for a method that does not require this extra labeling step.
[0019] Scanning Probe Microscopy
[0020] A wide variety of SPM instruments are capable of detecting optical, electronic, conductive, and other properties. One form of SPM, the atomic force microscope (AFM), is an ultra-sensitive force transduction system. In the AFM, a sharp tip is situated at the end of a flexible cantilever and scanned over a sample surface. While scanning, the cantilever is deflected by the net sum of the attractive and repulsive forces between the tip and sample. If the spring constant of the cantilever is known, the net interaction force can be accurately determined from the deflection of the cantilever. The deflection of the cantilever is usually measured by the reflection of a focused laser beam from the back of the cantilever onto a split photodiode, constituting an “optical lever” or “beam deflection” mechanism. Other methods for the detection of cantilever deflection include interferometry and piezoelectric strain gauges.
[0021] The first AFMs recorded only the vertical displacements of the cantilever. More recent methods involve resonating the tip and allowing only transient contact, or in some cases no contact at all, between it and the sample. Plots of tip displacement or resonance changes as it traverses a sample surface are used to generate topographic images. Such images have revealed the three dimensional structure of a wide variety of sample types including material, chemical, and biological specimens. Some examples of the latter include DNA, proteins, chromatin, chromosomes, ion channels, and even living cells.
[0022] In addition to its imaging capabilities, the AFM can make extremely fine force measurements. The AFM can directly sense and measure forces in the microNetwon (10 −6 ) to picoNewton (10 −2 ) range. Thus, the AFM can measure forces between molecular pairs, and even within single molecules. Moreover, the AFM can measure a wide variety of other forces and phenomena, such as magnetic fields, thermal gradients and viscoelasticity. This ability can be exploited to map force fields on a sample surface, and reveal with high resolution the location and magnitude of these fields, as in, for example, localizing complexes of interest located on a specific surface.
[0023] Direct Force Measurement
[0024] To make molecular force measurements, the AFM probe is functionalized with a molecule of interest. This bio- or chemi-active probe is then scanned across the surface of interest. The molecule tethered to the probe interacts with the corresponding molecule or atoms of interest on the surface being studied. The interactions between the molecule functionalized on the probe and the molecules or atoms on the surface create minute forces that can be measured by displacement of the probe. The measurement is typically displayed as a force vs. distance curve (“force curve”).
[0025] To generate a force curve, the tip or sample is cycled through motions of vertical extension and retraction. Each cycle brings the tip into contact with the sample, then pulls the tip out of contact. The displacement of the cantilever is zero until the extension motion brings the tip into contact with the surface. Then the tip and sample are physically coupled as the extension continues. The physical coupling is the result of hard surface contact (Van der Waals interactions) between the probe and the surface. This interaction continues for the duration of the extension component of the cycle. When the cycle is reversed and the tip retracted, the physical contact is broken. If there is no attractive interaction between the tip and sample the tip separates from the sample at the same position in space at which they made contact during extension. However, if there is an adhesive interaction between the tip and sample during retraction, the cantilever will bend past its resting position and continue to bend until the restoring force of the cantilever is sufficient to rupture the adhesive force.
[0026] In the case of extendable molecular interactions, the distance between the tip and surface at which a rupture is observed corresponds to the extension length of the molecular complex. This information can be used to measure molecular lengths and to measure internal rupture forces within single molecules. In a force curve an adhesive interaction is represented by an “adhesion spike.” Since the spring constant of the probe is known, the adhesive force (the unbinding force) can be precisely determined. Upon careful inspection of a typical adhesion spike, many small quantal unbinding events are frequently seen. The smallest unbinding event that can be evenly divided into the larger events can be interpreted as representing the unbinding force for a single molecular pair.
[0027] The spectra produced by these binding events will contain information about the coupling contacts holding the molecules together. Thus, it is possible to interpret the signature generated by a mechanical denaturation experiment with regard to the internal structure of the molecule. An SPM can further utilize height, friction, and elasticity measurements to detect molecular recognition events. Molecular recognition events are when one molecule interacts with another molecule or atom in, for example, an ionic bond, a hydrophobic bond, electrostatic bond, a bridge through a third molecule such as water, or a combination of these methods.
[0028] In an alternative approach, the AFM probe is oscillated at or near its resonance frequency to enable the measurement of recognizance parameters, including amplitude, frequency and phase. Changes in the amplitude, phase, and frequency parameters are extremely sensitive to variations in the interaction between the probe and the surface. If the local elasticity or viscosity of the surface changes as a result of a molecular recognition event, there is a shift in one or more of these parameters.
[0029] Others have reported using AFMs and STMs for the deposition of materials. One report is from Chad Mirkin (Northwestern University) in which he used an AFM to write nanometer scale molecule features with short alkane chains. Hong, S., J. Zhu, and C. A. Mirkin, Multiple Ink Nanolithography: Toward A Multiple-Pen Nano-Plotter, Science. 1999, p. 523-525. A need exists, however, for a molecular domain deposition method that is not limited to short chain length molecules. A need exists for a method for depositing longer chain length macromolecules that does not change or hinder the formation of the deposited molecule.
[0030] A need exists for an improved apparatus and method for utilization in the detection of molecular interaction events. A need exists for a method for the creation of small, sub-micron scale molecular domains at defined spatial addresses. This apparatus should enable the user to test for a variety of different types of events in a spatially and materially efficient manner by facilitating the deposition, exposure, and scanning of molecular domains to detect a resultant molecular interaction event. Furthermore, an apparatus is needed that enables the placement of a large number of molecular domains in a relatively small area.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] [0031]FIG. 1 is a block diagram of the method of forming a deposition domain.
[0032] [0032]FIG. 2 is a block diagram of the method of forming an array and utilizing the same.
[0033] [0033]FIG. 3 is a side view of the deposition device used with the present invention.
[0034] [0034]FIG. 4 is a side view of the deposition device and the microspheres of the present invention.
[0035] [0035]FIG. 5 is a side view of a microsphere attached to a deposition device.
[0036] [0036]FIG. 6 is an alternative attachment of the microsphere to the deposition device.
[0037] [0037]FIG. 7 a is a side view of the deposition device before loading the deposition material on it.
[0038] [0038]FIG. 7 b is a side view of a capillary bridge between the deposition material and the microsphere during loading of the deposition material
[0039] [0039]FIG. 8 a is a side view of a microsphere with deposition material loaded on the microsphere.
[0040] [0040]FIG. 8 b is a side view of a capillary bridge between the microsphere and a surface during the deposition of a deposition domain.
[0041] [0041]FIG. 9 is a side view of a deposition domain on an array just after the microsphere has been withdrawn.
[0042] [0042]FIG. 10 is a perspective view of an array of the present invention.
[0043] [0043]FIG. 11 is an outline view of an example scan of an array after exposure to a target medium.
SUMMARY
[0044] A method for the construction of a molecular deposition domain on a surface, comprising, providing a surface, depositing a deposition material on a deposition device, and depositing the deposition material on the surface using said deposition device, forming a molecular deposition domain smaller than one micron in total area.
[0045] Another embodiment comprises method for constructing an array of molecular deposition domains including the steps of providing a surface, providing an at least one deposition material, depositing a first deposition material on a deposition device, depositing the first deposition material on the surface in a known position, forming a first molecular deposition domain smaller than one micron in total area, cleaning the deposition device, and repeating the above steps with an at least one other deposition material, creating an array of two or more deposition domains on said surface.
[0046] Yet another embodiment comprises a method for detecting a target sample, the method comprising, forming a molecular array on a surface, the molecular array including an at least one molecular deposition domain, said at least one molecular deposition domain smaller than one micron in total area, exposing the surface to a sample medium, the sample medium containing one or more target samples which cause a molecular interaction event in one or more of the at least one deposition domain, and scanning the surface using a scanning probe microscope to detect the occurrence of the molecular interaction event caused by the target sample.
[0047] A still further embodiment comprises a molecular array for characterizing molecular interaction events, comprising a surface, and an at least one molecular deposition domain deposited on said surface wherein the spatial address of the domain is less than one micron in area.
[0048] Another embodiment comprises a method for the processing of multiple arrays including forming an array in a substrate, the array comprising a plurality of deposition domains formed of a deposition material, exposing the array to one or more materials which contain an at least one sample molecule that causes a molecular interaction event with one or more of the deposition samples, and scanning the array utilizing a scanning probe microscope to characterize the molecular interaction events that have occurred between the target sample and the deposition material.
[0049] One object of this invention is the construction of relatively small molecular domains with large molecular species.
[0050] Another object of this invention is the construction of molecular arrays comprised of molecular domains, each containing as little as a solitary molecule.
[0051] Another object of the present invention is an apparatus and method for the creation of a molecular array comprised of one or more molecular domains, each with an area smaller than one micron.
[0052] Another object of this invention is the utilization of molecular domain arrays without having to perform a labeling step to allow for the detection of a molecular event.
[0053] Another object of this invention is a molecular deposition array that has an effective screening limit at the single molecule level.
[0054] Another object of the present invention is a method for using an AFM in a high throughput format to detect and evaluate interactions between molecules Another object of this invention is the placement of molecular deposition domains at a defined spatial address.
DETAILED DESCRIPTION
[0055] I. Definitions
[0056] The following are some definitions that may be helpful in understanding the description of the present invention. These are intended as general definitions and should in no way limit the scope of the present invention to those terms alone, but are put forth for a better understanding of the following description.
[0057] A. Deposition Material: This is a selected sample placed on a surface that can be recognized and/or reacted with by a target sample. The deposition material will ideally have a change inflicted upon it by one or more target samples that can be detected by later scanning with an SPM. This is the known material placed in the domain. Examples of deposition materials include, but are not limited to, biomolecules, proteins, a variety of chemicals, DNA, RNA, antibodies, or any other substance recognized by one skilled in the art which may have usefulness within the teaching of the present invention.
[0058] B. Deposition Domain: A deposition domain is a spot on a surface upon which a deposition material is placed. The domain may be of any size, shape, and pattern and may contain as little as one molecule of the deposition material. These deposition domains may alternatively be referred to as “spots” or “points.” The boundary of the domain is defined by the boundary of the material placed therein.
[0059] C. Array: Alternatively referred to using the term “array,” “bioarray,” “molecular array,” or “high density molecular array.” The term array will be used to describe the one or more molecular domains deposited on the surface.
[0060] D. Target Sample: A substance with a particular affinity for one or more deposition domains. These target samples may be natural or man-made substances. The target samples may be known or unknowns present in a solution, gas, or other medium. These target samples may bind to the deposition domain or simply alter the deposition in some other cognizable way. Examples of target samples may include, but are not limited to, antibodies, drugs, nucleic acids, proteins, cellular extracts, antibodies, etc. The target medium may likewise be artificially made or, in the alternative, a biologically produced product.
[0061] E. AFM: As noted above, AFM's are a type of scanning probe microscope. The AFM is utilized in the present invention as an example of an SPM. The invention, however, is not limited for use with one specific type of AFM, but can also be incorporated for use with SPM's of various makes, models, and technological improvements.
[0062] F. Deposition Device: The deposition device of the following description is a modified AFM probe and tip. The basic probe and tip of the AFM is well known to one reasonably skilled in the art. The modified probe and tip that is the deposition device of the present invention may alternatively be referred to herein as “tip,” “probe tip,” or “deposition device.” Other deposition devices can be substituted by one reasonably skilled in the art, including the use of a dedicated deposition device manufactured for the express purpose of sample deposition.
[0063] II. General
[0064] The apparatus and method of the present invention allows for the placement of an at least one deposition sample in an at least one molecular deposition domain forming an array. The method of creating the present invention deposition domain may result in deposition domains smaller than one micron in total area. Furthermore, this method allows the deposition of relatively large molecular species, as large as 1 kilodalton and larger, without shearing or changing the molecular formation. This array can be exposed to a sample medium that may contain a target sample, the presence of which may be ascertained and characterized by detecting molecular interaction events. The molecular interaction event detection may be performed utilizing an atomic force microscope.
[0065] The deposition domains of the present invention may be formed as small or smaller than one micron in area. The present invention allows the direct detection of molecular interaction events in the deposition domain of the array. The molecular interaction event is detected without the need for the labeling of the deposition material or of the target sample. While labeling may still be performed for use with the present invention, the present invention does not require labeling to be utilized.
[0066] The present invention utilizes a scanning probe microscope to interrogate the various deposition domains of the present invention array. As the probe is scanned over a surface the interaction between the probe and the surface is detected, recorded, and displayed. If the probe is small and kept very close to the surface, the resolution of the SPM can be very high, even on the atomic scale in some cases.
[0067] In the present embodiment, an AFM may be used as the deposition tool, but this does not exclude other types of SPM's being used in alternative embodiments. An unmodified AFM probe has a sharp point with a radius of curvature that may be between 5 and 40 nm The method herein uses a microfabricated deposition device with an apical radius on the order of 10-50 nm. Due to the small radius of curvature of the deposition device used herein, the spot size generated by the present method can range from larger spots to as small as 0.2 microns or smaller. The difficulties with the prior art method need for labeling, such as with radioactivity, fluorescence, enzymatic labeling, etc., are also avoided.
[0068] As one reasonably skilled in the art will appreciate, the molecular material deposited by the present invention may be of almost any size and type. The following materials and methods are not intended to exclude other materials that may be compatible with the present invention, however, the present example is given for better understanding of the scope of the present invention.
[0069] Surface Preparation
[0070] As shown in FIG. 1, block 10 , and FIG. 2, block 18 , a surface may first be provided. The deposition domains that form the array will be constructed on this surface. The surface used for the deposition of the present embodiment molecular domain should facilitate scanning by an AFM as well as facilitate the deposition of the deposition material. A surface which can accept and bind tenaciously to the deposition material may also be desired. The present embodiment utilizes a solid glass substrate. This solid glass substrate may be a glass slide well known to those reasonably skilled in the art. Other embodiments may use other substrates including, but not limited to, mica, silicon, and quartz. The present embodiment may further cover this surface with a freshly sputtered gold layer.
[0071] The ion beam sputtering of gold onto a surface is well known by those reasonably skilled in the art. Sputtering gold may produce an extremely smooth surface upon which a variety of chemistry and molecular binding may be performed. In other embodiments, the gold may be sputtered onto glass coverslips, smooth silicon, quartz or a similar flat surface. The smoothness required of the underlying substrate is a function of the sensitivity requirement of a particular test. For example, detection of a virus particle binding to antibodies on a surface requires only the smoothness of a typical glass coverslip. In contrast, detection of binding of a small ligand to a surface immobilized protein may require a supporting substrate with a surface roughness of one nanometer over an area of several microns.
[0072] In alternative embodiments, other surfaces besides that achieved by gold sputtering may be likewise utilized, such as, but not limited to, glass, Si, modified Si, (poly) tetrafluoroethylene, functionalized silanes, polystyrene, polycarbonate, polypropylene, or combinations thereof.
[0073] The gold of the present embodiment is sputtered onto the glass surface. This area of gold defines the boundary of the present embodiment array. The deposition material will be deposited in domains contained in this area.
[0074] Depositing the Deposition Sample on the Deposition Device
[0075] With reference to FIG. 1 block 12 , FIG. 2 block 20 , and FIG. 3, the deposition of the sample on the deposition device 40 will be described. The basic shape of the deposition device 40 is shown in FIG. 3. Before the deposition material is formed into a molecular domain on the above surface, the deposition material must first be placed onto the deposition device 40 . The deposition device 40 of the present embodiment may be a deposition device 40 and tip 42 commonly utilized by an AFM. The present embodiment starts with a standard silicon-nitride AFM probe under the tradename “DNP Tip” produced by Digital Instruments, Inc. These probes are generally available and well known in the art In the present embodiment, the deposition device 40 may be first placed on the deposition instrument. A Digital Instrument, Inc., Dimension 3100 may be used in the present embodiment, controlled by a standard computer and software package known in the art.
[0076] In the present embodiment, the deposition instrument may be modified with a microsphere 52 to facilitate the loading (depositing) of the deposition material 56 . While other embodiments may not utilize such a microsphere on the deposition device 40 , attaching a microsphere on the deposition device 40 allows the loading of a greater amount of deposition material upon the deposition device 40 , enabling a greater number of deposition domains 64 to be deposited before reloading with new material. Borosilicate glass spheres up to 25 microns or larger in diameter may be utilized in the present embodiment as the microspohere 52 .
[0077] First, a small amount of epoxy resin is placed upon a surface, usually glass. A standard ultraviolet activated epoxy resin, such as Norland Optical Adhesive #81, may be utilized, though those reasonably skilled in the art may fine other types of epoxies useful as well. The deposition device 40 is moved by the instrumentation and dipped slightly in the epoxy and withdrawn, retaining a small amount of the epoxy on the tip 42 . As shown in FIG. 4, on another surface 50 are placed a number of the microspheres 52 . Using the instrumentation controls, one or more of the borosilicate glass beads is touched by the end of the deposition device 40 . Because of the epoxy, the microsphere 52 sticks to the end of the deposition device 40 as it is pulled away. The deposition device 40 is then exposed to ultraviolet light to set the epoxy and permanently affix the microsphere glass bead 52 to the tip 42 of the deposition device 42 . As shown in FIG. 5 and 6 , the microsphere 52 may bind to the tip 42 of the deposition device 40 in various places without affecting the present invention The present embodiment places one microsphere 52 on the deposition device 40 . This microsphere 52 allows the deposition device 40 to retain more of the material to be deposited on the probe while still allowing the creation of deposition domains 64 on the sub-micron scale. As noted above, as little as one microsphere 52 may be deposited on the tip in the above process. Furthermore, the surface of the microsphere 52 allows for alternative types of surface chemistry to be performed when, in alternative embodiments, the deposition material is being bonded to the surface.
[0078] The microspheres 52 used in the present embodiment are commercially available and well known in the art, ranging in size to smaller than 0.05 microns. With a smaller the microsphere 52 , a smaller deposition domain 64 may be achieved, however less sample can be deposited on the tip at any one time, slowing down the construction of the array. Modification of the deposition device 40 may also be accomplished in a number of alternative ways, including spontaneous adsorption of molecular species, chemical derivitization of the AFM tip followed by covalent coupling of the probe molecule to the tip, or the addition of microspheres to the tip which may be coupled to molecules by standard chemistry. In additional embodiments, a laser may be used to locally heat the deposition device 40 and bond microspheres (such as polystyrene spheres) by a “spot welding” technique.
[0079] As shown in FIG. 1 block 12 , and FIG. 2 block 20 , after the microsphere 52 is placed on the deposition device 40 , the deposition material 56 may be loaded on the deposition device 40 by forming a capillary bridge 60 . The deposition material 56 may be placed on a surface as shown in FIG. 7 a . This large spot of deposition material 56 can be reused a number of times, depending on the number of domains 64 that are to be created. Though not drawn to scale, FIG. 7 a shows material that may have been micro-pipetted onto a surface for loading on the deposition device 40 .
[0080] In one embodiment, the deposition device 40 may be brought into direct contact with the material 56 on the surface. In alternative embodiments, the deposition device 40 and microsphere 52 may be brought into a near proximity to the deposition material 56 on the surface and achieve the same capillary action. The exact distance between the microsphere 52 and the deposition material 56 may vary and still have the formation of a capillary bridge 60 . This depends on conditions like relative humidity, microsphere 52 size, contaminants, etc. In the present embodiment, this distance may vary between touching to several nanometers or more.
[0081] The capillary bridge 60 , shown in FIG. 7 b , may be formed by controlling the humidity by timing a blast of humid gas. Longer bursts may result in a greater amount of material to be placed on the tip. Short bursts allow for less material to be used, but must be long enough to effectively transfer deposition material 56 from the surface 62 to the deposition device 40 . The optimal parameters are determined empirically, however a typical time of exposure to the humid gas is on the order of 500 milliseconds or longer. It has also been noted that a capillary bridge 60 may be spontaneously generated when the relative humidity of the air is more than approximately 30%. In cases such as this, it may be advantageous to have a controlled dry environment or to have a stream of dry air flowing over the surface which is interrupted by the humid blast of gas which forms the capillary bridge 60 . In other embodiments, this spontaneous capillary bridge 60 can be used to deposit the deposition material 56 , though less control of the process may result.
[0082] In the present invention the humidity may be controlled by several methods known to those reasonably skilled in the art. The present embodiment incorporates a small tube and argon gas source which creates the bridge by rapidly increasing the level of humidity around the probe and the deposition material. The tube of the present embodiment may be a flexible polymer material, such at “Tygon” tubing, with an inner diameter of 0.5 to 1.0 cm. This material is readily available, but other materials that will not introduce contaminants into the deposition material would likewise suffice. The small tube must first be filled with water.
[0083] The water used in the present embodiment should be of a highly purified nature, such as purified water with a resistance of 18 megaohms or more. It should be free of particulates by filtration and is usually sterilized by filtration and or autoclaving. Additionally, an argon gas source may be positioned at one end of the tube and may be controlled by the action of a needle valve and solenoid.
[0084] The water is then drained from the tube, leaving a humid gas in the tube. When the humidity blast is desired, the solenoid is activated to pulse a discrete amount of humidified argon through the tube and over the probe 40 , deposition material 56 , and surface 62 . As shown in FIG. 7 b , the capillary bridge 60 may be formed between the surface 62 and the deposition device 40 . The deposition device 40 is then moved away from the surface 62 , leaving a small amount of the deposition material 56 on the deposition device 40 , as shown in FIG. 8 a.
[0085] As shown in FIG. 8 a , the deposition material 56 is now on the deposition device 40 . Whether the deposition material 56 adsorbs onto the microsphere's 52 surface, the pores, or some other area, may vary depending on the type of microsphere 52 and the deposition material 54 . As shown in FIG. 1 block 14 , the deposition material 56 may now be dried on the deposition device 40 . The drying may be immediate and spontaneous due to the relatively little amount of wet material on the surface of the deposition device 40 . This is, of course, dependent on the relative humidity of the surrounding air. Drying the deposition material 56 on the microsphere 56 may facilitate the deposition of the material 56 on the surface 62 as laid out in the next step. For labile samples, drying could result in inactivation, and should be avoided, but this is not the case for robust samples such as antibodies, peptides and nucleic acids.
[0086] In an alternative embodiment, the deposition tip may be loaded with the deposition material 56 by direct immersion. The tip of the probe may be immersed in a solution containing up to 50% glycerol, 0.1-5 mg/ml of the deposition sample, and a buffer-electrolyte such as Tris-HCl at pH 7.5. A small amount of the above solution may be made by standard bench chemistry techniques known to those skilled in the art. Typically 1-10 microliters are made. Because of the nature of solutions, when the probe is dipped into the solution and withdrawn a small amount of the solution will cling to the surface of the tip in a manner known to those reasonably skilled in the art. In still further embodiments, other solutions, such as 10 mM NaCl and 1 mM MgCl 2 , phosphate buffered saline, or a sodium chloride solution, may be substituted by those reasonably skilled in the art. Alternative methods for loading the deposition material 56 on the deposition device 40 include spraying, chemically mediated adsorption and delivery, electronically mediated adsorption and delivery, and either passive or active capillary filling.
[0087] In still further embodiments, other probes may also be used, for example, AFM probes lacking a tip altogether (tipless levers), may also be used. The type of probe used may impact the spatial dimensions of the deposition domain 64 and may be influenced by the choice of the deposition sample.
[0088] Depositing the Sample on the Surface
[0089] The next step in creating the deposition domain 64 and array 66 is depositing hte sample on the surface. See FIG. 1 block 16 and FIG. 2 block 22 . Varying the humidity level surrounding the deposition device 40 and deposition material 56 may be taken advantage of to deposit the deposition material 56 onto the surface in a deposition domain 64 less than one micron in area. The capillary bridge 60 is illustrated by FIG. 8 b . This step may be performed in much the same way as depositing the deposition material 56 on the deposition device 40 . The degree of binding to the surface and the deposition device 40 is a function of the hydrophilicity and hydrophobicity of the two surfaces. Therefore, it may often be desirable to use deposition tools and surfaces that are free of oils and other hydrophobic contaminants to facilitate wetting of both surfaces.
[0090] Utilizing the AFM and the control computer and software, the deposition device 40 , with the deposition material 56 , may be brought into contact, or close proximity, with the deposition surface. The humid gas may then be released by activation of the solenoid. In the present embodiment the humidity is ramped up, and the capillary bridge 60 formed, for a time of approximately 400 milliseconds or less, depending on the amount of material the user wishes to deposit. The spots are on the sub-micron scale because the contact surfaces are on the order of microns or smaller and the degree of sample diffusion (which determines the final size of the deposition domain) is carefully controlled by regulating the amount and timing of the humid gas burst. When depositing the deposition sample 56 on the surface, in order to better control the length of time the capillary bridge 60 exists, a tube of dry air may be blown over the area by a solenoid in rapid succession after the humid air. This results in a very short burst of humid air, a capillary bridge 60 , and then the termination of the capillary bridge 60 , all in a very short time period As illustrated in FIG. 9, when the deposition device 40 is withdrawn, and the bridge 60 severed, a very small amount of the deposition material 56 has been deposited on the surface 62 in a deposition domain 64 . The transfer of large macromolecules may be achieved utilizing the burst of humid gas. As will be appreciated by one reasonably skilled in the art, the capillary bridge 60 may be broken by withdrawing the deposition device 40 or by the blast of dry air.
[0091] Because of the fine control of the deposition device 40 that may be possible with the AFM instrumentation, the exact surface spot in which the deposition takes place may be noted. Noting the surface point for each deposition domain 64 may ameliorate the detection of the molecular interaction event caused by the target sample. The pattern writing program can be one that is provided by an AFM manufacturer (e.g., the Nanolithography program provided by Digital Instruments, Inc.) or it can be created in-house. In the latter case, one example is to use a programming environment such as Lab View (National Instruments) with associated hardware to generate signal pulses which control the positioning of the deposition probe.
[0092] The steps laid out above produce the deposition domain 64 of the present embodiment. Repeating these steps with one or more deposition materials 56 , FIG. 2 block 26 , produces the array 66 of the present invention. This array is shown in FIG. 10. The number and size of the deposition domains 64 may be varied depending on the desire of the user.
[0093] One advantage to the present embodiment is the small size of the deposition domain 64 produced by the method. Furthermore, because of the manner in which the array 66 is produced, the user may be able to record and track the position of each of the particular deposition domains 64 . Finally, the above method allows the deposition of as little as a single macromolecule, which previous methods were unable to perform.
[0094] Once the array 66 has been formed, the user may desire to immediately utilize the array 66 on site, or may desire shipment of the array 66 for exposure to a sample medium at another location. The array 66 produced by the above steps may be ideal for shipment to a location, exposure, and return shipment for the scanning by an AFM.
[0095] Subsequent Depositions
[0096] In an alternative embodiment, the probe may be reloaded with a second deposition material 56 after one or more molecular domains are created with the first deposition material 56 . FIG. 2 block 26 . Using the probe with a variety of deposition materials 56 enables the creation of a number of deposition domains 64 on one surface. The different deposition materials 56 in the molecular domains that are deposited on the surface form the array 66 of the present invention. Because of the size of the molecular domain containing the deposition material 56 , the molecular domains can be placed on the surface in a an ultra high density array 66 , as shown in FIG. 10. In the present embodiment of this invention, the pitch (the distance from the center of one domain to the center of the next domain) of the molecular domains may be as small or smaller than one micron. The array 66 produced with these small molecular domains may be easily scanned by the AFM array 66 after the array 66 is exposed to the sample medium containing the target sample in the next step. Furthermore, the small sized array 66 requires exposure to a smaller amount of the sample medium of the next step, conserving both the deposition material 56 and the medium material.
[0097] The number of times the probe may be reloaded in this alternative embodiment may be only limited by the surface size and the number of samples the user desires to deposit. As will be appreciated by those skilled in the art, this ultra high density array 66 presents a unique advantage.
[0098] Cleaning the Probe
[0099] Before the probe is reloaded with subsequent deposition samples, the probe must be cleaned. FIG. 2 block 24 . The probe of the present embodiment AFM may be cleaned in several ways. In the present embodiment, the very tip of the probe is immersed in a small aliquot of a cleaning solution. The present embodiment cleaning step utilizes pure water as the solution. A few microliters of water is pipetted onto a surface and, using the instrumentation's piezo device (which is utilized to help the AFM scan surfaces), the tip is oscillated at up to 1000 Hz or more. Resonating the probe at 1000 hertz will effectively sonicate the tip, helping to effectuate reusing the tip to deposit other deposition materials 56 .
[0100] Exposing the Array to a Sample Medium
[0101] Once a high density array 66 is formed by the present invention, the array 66 may be exposed to a sample medium. FIG. 2 block 28 . The sample medium may contain a target sample that the user has placed therein. In other types of experiments, the user may be looking for the presence of an unknown target sample, utilizing the array 66 of the present invention to test for its presence. The usefulness of such arrays 66 are well known to those reasonably skilled in the art.
[0102] The array 66 may be dipped in a solution or exposed to a gas. The solution may include, but is not limited to, waste water, biological materials, organic or inorganic user prepared solutions, etc. The exposure time of the array 66 to the medium depends on what types of molecular interaction events the user may be studying. The target sample tested for should ideally cause a readable molecular change in one or more of the deposition materials 56 of the molecular domains placed on the array 66 . These molecular changes may include binding, changes in stereochemical orientation in morphology, dimensional changes in all directions, changes in elasticity, compressibility, or frictional coefficient, etc. The above changes are what the AFM scans and reads in the next step of the present embodiment.
[0103] Molecular Event Detection
[0104] After the molecular deposition array 66 is exposed to the test medium, it may be scanned by the AFM. See FIG. 2 block 30 . Use of an AFM in this manner to characterize a material deposited on a surface is well known to those reasonably skilled in the art. The present embodiment may utilize one scan for every deposition domain 64 of the array 66 to look for changes in the recorded features of the domains. Furthermore, the AFM may look at specific portions of the array 66 using site locators. As will be appreciated by one skilled in the art, various methods may be used to undertake the scanning of the array 66 of the present invention.
[0105] After the scan is taken, the scan must be analyzed. FIG. 2, block 32 . The present embodiment utilizes the detection of changes in height at defined spatial addresses, as described by Jones et al., supra. As shown in FIG. 11, height changes only occur at those addresses containing deposition material 56 to which the target sample is capable of binding. Since the identity of the molecules at each of the sample addresses is known, this process immediately identifies those deposition materials 56 capable of binding to the target sample. In FIG. 11, point 66 shows the normal height of the deposition domain 64 as scanned by the AFM. Point 68 shows how the AFM will recognize some feature that the molecular interaction event has affected in the deposition domain 64 .
[0106] In addition, the AFM can measure whether new materials have bonded to the deposition material 56 by testing for changes in shape (morphology) as well as changes in local mechanical properties (friction, elasticity, compressibility, etc.) by virtue of changes in the interaction between the probe and the surface. The typical parameters detected by an AFM include height, torsion, frequency (the oscillation frequency of the AFM probe in AC modes of operation), phase (the phase shift between the driving signal and the cantilever oscillation in AC modes) and amplitude (the amplitude of the oscillating cantilever in AC modes of operation).
[0107] The AFM scan may also be used to tell when the probe is interacting with different forces of adhesion (friction) at different domains on the surface. This interaction force is a consequence of the interaction between the molecules on the probe and on the surface. When there is a specific interaction, the force value is typically higher than for non-specific interactions, although this may not be universally true (since some non-specific interactions can be very strong). Therefore, it may be useful to include both known positive and negative control domains in the scan area to help distinguish between specific and non-specific force interactions. The target sample may affect the deposition material 56 that can be read by this scanning technique. A still further embodiment may directly measure the interaction forces between a molecular probe coupled to the AFM tip and the surface. The direct measurement of molecular unbonding forces has been well described in the art in addition to measuring changes in the elasticity.
[0108] In the screening methods described above, once it has been established that a molecular binding event has occurred, changes in the degree of binding upon introduction of additional sample molecules may also be analyzed. The potential for a third molecular species to enhance or inhibit a defined molecular interaction is of utility in locating new drugs and other important effectors of defined molecular interactions.
[0109] In the above examples an AFM is used for illustration purposes. The type of deposition instrumentation incorporated into the present invention is not limited to AFM's, or other types of SPM's. In one alternative embodiment, a dedicated deposition instrument may be used which may provide for extremely accurate control of the deposition probe. In this alternative embodiment, a DC stepper motor and a piezoelectric motion control device may be incorporated for sample and probe control. In still further embodiments, a force feedback system may be included to minimize the force exerted between the deposition tool and the surface.
[0110] One advantage to the present invention is the elimination of the labeling step required in other array 66 techniques. Radioactive and fluorescent labeling may be cost prohibitive and complex. The present invention eliminates the need for the labeling of molecular deposition domains 64 in an array 66 .
[0111] Another advantage to the present invention is the creation of molecular domains in an array 66 wherein each domain has a deposition area of less than one micron. Since the size of each domain is extremely small, a large number of domains may be placed in a small area, requiring less materials, a smaller medium sample for exposure, and the ability to perform a quicker scan.
[0112] Another advantage to the present invention array 66 is the ability to quickly scan for multiple molecular events in a reasonably short period of time.
[0113] III. Alternative Deposition Examples
[0114] The following are a few of the variations in the deposition method and array 66 apparatus that may be used within the scope of the present invention. These examples are given to show the scope and versatility of the present invention and are not intended to limit the invention to only those examples given herein. In each of these examples, the deposition material 56 may be deposited on the deposition device 40 and then to the surface utilizing the method described above, however the surface may be coated with other materials that will react in some way with the deposition material 56 , to bind the latter to the surface in the deposition domain 64 .
[0115] A. Surface Modification
[0116] One alternative embodiment for the covalent tethering of biomaterials to a surface for use in the present invention may be to use a chemically reactive surface. Such surfaces include, but are not limited to, surfaces with terminal succinimide groups, aldehyde groups, carboxyl groups, vinyl groups, and photoactivatable aryl azide groups. Other surfaces are known to those reasonably skilled in the art. Biomaterials may include primary amines and a catalyst such as the carbodiimide EDAC (1-ethyl-3-[3-dimethylaminopropyl]carbodiimide). Furthermore, the spontaneous coupling of succinimide, or in the alternative, aldehyde surface groups, to primary amines at a physiological pH may be incorporated for attaching molecules to the surface. In still another embodiment, photoactivatable surfaces, such as those containing aryl azides, may be utilized. These photoactivatable surfaces form highly reactive nitrenes that react promiscuously with a variety of chemical groups upon ultraviolet activation. Placing the deposition sample on the surface and then activating the material can create deposition domains 64 in spots or patterns, limited only by the light source activated.
[0117] Another embodiment for the tenacious and controlled binding of biomaterials to surfaces is to exploit the strong interactions between various biochemical moieties. For example, histidine binds tightly to nickel. Therefore, both nucleic acid and protein biomaterials may be modified using recombinant methods to produce runs of histidine, usually 6 to 10 amino acids long. This His-rich domain then allows these molecules to bind tightly to nickel coated surfaces. Alternatively, sulfhydryl groups can be introduced into protein and nucleic acid biomaterials, or preexist there, and can be used to bind the biomaterials to gold surfaces by virtue of extremely strong gold-sulfur interaction. It is well documented that gold binds to sulfur with a binding force comparable to that of a covalent bond. Therefore, gold-sulfur interactions have been widely exploited to tether molecules to surfaces. Jones, V. W., J. R. Kenseth, M. D. Porter, C. L. Mosher, and E. Henderson, Microminiaturized Immunoassays Using Atomic Force Microscopy and Compositionally Patterned Antigen Arrays 66, Anal Chem. 1998, p. 1233-41.
[0118] B. APTES
[0119] In this alternative embodiment, the surface may be treated with APTES (aminopropyl triethoxy silane). The APTES placed on the surface may present positively charged amino groups that can bind tightly to a negative charge. Materials such as DNA and RNA containing negatively charged groups may therefore bond to the surface after the APTES treatment. The details of the adsorption mechanism involved in this spontaneous attachment are not well defined. Therefore, in alternative embodiments, it may be advantageous to deposit biomaterials onto surfaces that can be covalently or otherwise tenaciously coupled to the target sample. DNA and RNA bind through interaction between their negative net charge and the net positive charge of the APTES surface.
[0120] C. Photochemical Sample Deposition
[0121] In this alternative embodiment, glass surfaces may be modified sequentially by two compounds, aminopropyltriethoxysilane (APTES) and N-5-azido-2-nitrobenzoyloxysuccinimide (ANB-NOS). The glass may first be treated with APTES to generate a surface with protruding amino groups (NH 2 ). These groups may be then reacted with the succinimide moiety of ANBNOS in the dark. These steps produce a surface with protruding nitrobenzene groups. The photosensitive surface may be then reacted with the first deposition material 56 in the dark, then a focused light source, like a laser, may be used to illuminate a portion of the surface. These acts result in localized covalent binding of the first deposition material 56 to the surface. The deposition material 56 not bonded to the surface may then be washed away and second deposition material 56 added by repeating the process. Reiteration of this process results in the creation of a biomolecular array 66 with address dimensions in the 1 micron size range. A limitation of this deposition method is that the sample size is dependent on the size of the illuminating light field.
[0122] A variation of the above embodiment may be to utilize the deposition device 40 and humidity ramping deposition technique described to place various molecular species at defined locations in the dark. After construction of the desired array 66 , the entire surface is exposed to light, thereby cross linking the molecular species at discrete spatial domains. This process may overcome the spatial limitation imposed by use of a far field laser or other type of light beam.
[0123] D. Photocoupling
[0124] In this embodiment a near field scanning optical microscope (NSOM) may be used to supply the light energy necessary to accomplish photocoupling of the sample molecule to a surface at a defined spatial address. The NSOM may overcome the diffraction limit which constrains the address size created by far field photocoupling as described in Example 2. The photoactive surface is prepared as described in Example II. The first molecule to be coupled is added to the surface and subjected to a nearfield evanescent wave emanating from the aperture of the NSOM. The evanescent wave energy may then activate the photosensitive surface and result in coupling of the sample molecules to a spatial address in the 10 to 100 nm size range. The first sample molecule is washed away and the process repeated with a second sample molecule. Reiteration of this process may result in the production of an array 66 of sample molecules coupled at spatial addresses with submicron dimensions.
[0125] An alternative approach may be to utilize both the sample manipulation and near field light delivery capabilities of the NSOM. In this approach, the NSOM probe may be first loaded with a molecular species as described in Example I. Then the same probe is used to provide the light energy to couple the molecule to the surface. The probe may then be washed and reused to create a spatial array 66 of molecular species covalently coupled to defined domains.
[0126] One advantage of coupling the deposition material 56 to the surface may be that the molecule may remain attached at a defined spatial domain even under stringent wash and manipulation conditions. Moreover, by coupling the molecule, the orientation of the molecules on the surface may be controlled by the careful selection of a tethering method.
[0127] Yet another advantage to coupling the molecule is that by controlling the coupling chemistry, the minimization of the chances of surface induced molecular denaturation may be achieved. Coupling the molecules to the surface may be especially advantageous when depositing biomolecules.
[0128] The information and examples described herein are for illustrative purposes and are not meant to exclude any derivations or alternative methods that are within the conceptual context of the invention. It is contemplated that various deviations can be made to this embodiment without deviating from the scope of the present invention. Accordingly, it is intended that the scope of the present invention be dictated by the appended claims rather than by the foregoing description of this embodiment.
[0129] All publications cited in this application are incorporated by reference in their entirety for all purposes. | The invention is a method for the formation and analysis of novel miniature deposition domains. These deposition domains are placed on a surface to form a molecular array. The molecular array is scanned with an AFM to analyze molecular recognition events and the effect of introduced agents on defined molecular interactions. This approach can be carried out in a high throughput format, allowing rapid screening of thousands of molecular species in a solid state array. The procedures described here have the added benefit of allowing the measurement of changes in molecular binding events resulting from changes in the analysis environment or introduction of additional effector molecules to the assay system. The processes described herein are extremely useful in the search for compounds such as new drugs for treatment of undesirable physiological conditions. The method and apparatus of the present invention does not require the labeling of the deposition material or the target sample and may also be used to deposit large size molecules without harming the same. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a National Phase of International Serial No. PCT/EP02/14417, filed Dec. 17, 2002.
FIELD OF THE INVENTION
This invention relates to a security paper for producing security documents, such as bank notes, identity cards or the like, having a through opening, and to a method and apparatus for producing such a security paper. The invention further relates to a value document, such as a bank note, identity card or the like, having a through opening.
DESCRIPTION OF THE BACKGROUND ART
WO 95/10420 describes a value document having a through opening punched thereinto after production thereof, said opening then being sealed on one side with a cover foil protruding beyond the opening on all sides. The cover foil is transparent at least in a partial area, so that upon an attempt to copy the value document the background will be visible and rendered accordingly by the copy machine. This permits forgeries to be easily recognized.
However, said known value document has the disadvantage that the opening produced by punching can likewise be produced by a forger. The color copy of an authentic value document no longer has the transparent area, but said area can subsequently be punched out analogously to the authentic value document and sealed again with a suitable cover foil. Forgeries are therefore difficult to recognize.
SUMMARY OF THE INVENTION
The invention is based on the problem of proposing a security paper and a value document having increased forgery-proofness in comparison with the prior art.
The basic idea of the invention is that by production of a “window opening” during sheet formation, i.e. during papermaking, the edge area of the opening will have characteristic irregularities which are not producible subsequently on the finished paper. The irregularities are expressed by the lack of a sharply cut edge or irregular accumulation of fibers in the edge area, and by individual fibers protruding into the opening. A rough check of this characteristic edge structure is already possible with the naked eye, while an exact check can be done with a magnifying glass.
The inventive edge structure ensures that the opening cannot be produced by subsequently punching a paper sheet. An opening produced in such a way therefore has a similar security value to a watermark produced during papermaking or a security thread embedded during papermaking.
Security paper is normally produced in broad webs with several copies disposed side by side. After completion, the webs are cut into sheets with e.g. 6×9 copies present thereon. Said sheets are printed and then cut into single copies.
If each single copy is to have a through opening, a corresponding number of elements are to be provided on the screen of the paper machine which prevent sheet formation exactly in the surface areas where the opening is needed. If the security paper is to have watermarks in addition, production is done as a rule on so-called “cylinder paper machines” wherein the screen is mounted on a rotating drum. In this case, the opening can be located in the area of the watermark.
The security paper according to the invention has at least one through opening produced during papermaking. To permit this opening to be produced, the screen of the paper machine must be provided with at least one water-impermeable, preferably elastic or movably mounted sealing element per copy. The sealing element prevents sheet formation in this area. To prevent fibers from being deposited on the sealing element during sheet formation, it is preferably formed so high that it protrudes clearly beyond the paper surface. Upon removal of the paper web by the take-off roll covered with pickup felt, however, it must be ensured that the sealing element does not hinder the contact between the moist and still very unstable paper web and the take-off roll, since the paper web will otherwise break in this area. For this reason the sealing element consists according to the invention of a highly elastic material which can be compressed by the take-off roll approximately to the level of the paper surface. Alternatively, the sealing element consists of a movably mounted, preferably rigid plastic or metal element which is lowered approximately to the level of the paper surface or therebelow either by the action of pressure of the take-off roll itself or by electronic control upon contact with the take-off roll.
Further possibilities for producing the opening are sealing the screen surface with a plastic material, such as a lacquer, whereby the plastic material is likewise to be understood as a sealing element according to the invention. Alternatively, rigid sealing elements in the size of the opening to be produced can be applied (e.g. soldered) to the screen surface, said elements having a thickness considerably greater than the thickness of the paper web.
In some cases it may be helpful to provide further drainage-reducing structures in the edge area of the sealing elements for producing a kind of rated breaking point in the paper web. This is because the cotton fibers principally used for security papers have the tendency to settle over the sealing elements unchecked, thereby preventing hole formation or at least making it more difficult.
The freeness-inhibiting structures can be for example special embossings in the papermaking screen, additional screen elements, possibly with a different mesh width from the original papermaking screen, or plastic structures. In principle, any conceivable structures can be used that delay freeness and thus form a bright corona around the opening to be produced. In some cases it is already sufficient to use only the freeness-inhibiting structures. For example, an annular embossing can be so designed that the inventive hole is produced upon removal of the paper web from the screen.
The paper web lying on the pickup felt and having the openings formed due to the sealing elements is then further processed into a self-supporting paper web in further method steps, such as calendering, sizing and drying. To improve hole formation one can, in addition or as an alternative to the freeness-inhibiting structures additionally used during papermaking, remove fibers protruding into the desired opening after paper formation, e.g. by punching or cutting, the fibers being removed only to the extent that the hole edge produced by papermaking is not destroyed or actually removed completely. For example, if a circular hole is to be produced but a fine web of fibers settles irregularly over the hole, the disturbing fiber web can be removed with a circular punching mold whose diameter is smaller than the desired hole. Then a hole edge produced by papermaking is always recognizable, possibly only in a partial area of the hole edge. The inventive security paper therefore has at least one opening whose edges are at least partly irregular and show a character similar to hand-made paper, unlike the sharp edges of a punched or cut opening.
The fibrous, irregular edge of the openings is visually recognizable and therefore serves as an authenticity feature that is easy to check. If forgery-proofness is to be increased further, at least one watermark can be formed in addition in the surroundings of the opening, or the opening produced in a watermark area. Depending on the type of watermark to be produced, this requires different measures on the papermaking screen. For producing two-level watermarks with a strong light/dark effect, metal wires or metal moldings (so-called electrotypes) are soldered to the papermaking screen. For producing multi-level watermarks, however, a three-dimensional relief is embossed into the papermaking screen. Combinations of screen embossing and other measures preventing sheet formation, such as electrotypes or the application of sealing compound, are also used in watermark production. The thereby obtained light/dark modulation in the security paper in the direct surroundings of the opening confronts the forger with hardly solvable problems.
The form of the watermark can be selected here so that it is meaningfully related to the outline contour of the opening, or the opening and the surrounding watermark form a connected motif.
The papermaking screen is preferably a cylinder. Since the sealing element is either elastic or at least movably mounted, however, the invention can also be readily used in fourdrinier paper machines.
The inventive goal of preventing or greatly hindering forgeries of value documents with an opening can also be obtained by producing a relatively large, thin area in the security paper by corresponding screen embossing and/or freeness hindrance with electrotypes and providing the inventive opening in said area, whereby the thin paper area protrudes beyond the opening at least on one side, preferably on all sides, so that upon transmissive viewing of the security paper the thin paper area stands out in contrast from the rest of the surrounding paper web. The opening can in this case be produced during papermaking, as described above. Subsequent punching or cutting, in particular laser cutting, of the security paper is likewise possible, however, since a forgery can be recognized by the lack of a thinner paper area in the immediate surroundings of the opening.
The thinner area in the security paper can have a uniform thickness or else be formed as a multi-level watermark. If the security paper consists of two-ply paper, it is also possible to provide one layer, preferably the thicker one, with a hole which is then covered by the second paper layer. In said second paper layer the inventive opening is finally incorporated subsequently, its dimensions being smaller than those of the hole produced in the first paper layer.
In the case of two-ply paper consisting of a thinner and a thicker layer, the inventive hole can of course also be located in the thinner layer.
The inventive opening can be composed of several partial openings separated from each other by paper bars. The partial openings can have any desired outline contours and are preferably used as an additional design element. For producing the particular partial openings all the above-mentioned methods for producing the inventive opening can be used analogously.
In accordance with a preferred embodiment of the invention, the opening is provided with a security element protruding beyond the opening at least on one surface of the security paper after production thereof. Said security element can consist of a simple transparent plastic film or else be executed as a multilayer security element having one or more visually and/or machine testable security features.
Said security feature can involve diffraction structures, such as reflection or transmission holograms, reflectively observable grating structures or volume holograms, thin-film elements or filter elements, such as polarizing filters or interference filters. Filter elements have in particular the advantage that they can be used for checking further security features provided on or in the security paper by making the opening congruent with said further security feature by folding the security paper. However, the security element disposed in the area of the opening can also carry a simple print or a moiré pattern as a security feature. The inks used for said print can have a substance with optically variable, luminescent, electrically conductive or magnetic properties. The optically variable substances can be in particular interference layer pigments or liquid crystal pigments.
The security feature can further consist of a metallization, whereby several different-colored metals can also be used. Rasterization of the metal layers or reflecting layers of diffraction structures is also possible. Any desired semitransparent layers can of course also be used. The security feature can furthermore consist of a perforation or a lens structure.
A sufficiently large area of the security element is preferably kept completely transparent to permit easy recognition of forgeries produced by a color copier. A copy does not have said transparent area.
The security element can be formed for example as a self-supporting label or embossed foil element protruding beyond the opening by a certain measure on all sides. With this solution it is advantageous if the security paper has a depression in the area of the bearing surface of the security element, so that the security paper has a continuous surface in said area. In extreme cases the security element can cover the security paper or value document all over. This solution can also be provided on both sides of the security paper or value document.
The depression can be produced by compressing the security paper in this area before application of the security element. However, it is particularly simple to already produce the depression during papermaking by hindering sheet formation in the direct surroundings of the opening and thus forming a thinner place in the paper.
In accordance with a further embodiment, the security element can also be formed in a strip shape and extend over the total length or width of the security paper. This variant makes sense particularly when the security element is applied to the as yet uncut security paper in endless form. In this case the security element can be laminated on the security paper by a hot stamping technique in a continuous process.
The outline contour of the security element can be chosen at will. It can for example match the contour of the opening or be meaningfully related to a watermark surrounding the opening. Security element and watermark can also form a connected motif. Thus, the security element or opening and the watermark can together convey the impression of a stylized sun if the security element or opening is of circular form and the watermark areas are disposed radially around the opening.
The same applies analogously to the security feature applied in the area of the security element. For example, the security element can carry a print repeated in form of the watermark as a security feature.
The opening and/or the security element can be circular, oval, rectangular, trapeziform or also star-shaped. Any other outline contour is of course also possible.
If both sides of the opening are provided with a security element, the same, or the same type of, security element can be applied to both sides, or else different ones. The following combinations are preferred:
Side 1
Side 2
Self-supporting plastic film, possibly with
Self-supporting plastic film, possibly with
one or more security features; in label or
one or more security features; in label or
strip form or all over
strip form or all over
Self-supporting plastic film, possibly with
Embossed foil element; in label or strip
one or more security features; in label or
form or all-over
strip form or all-over
Self-supporting plastic film, possibly with
Coating or print consisting of a resin or a
one or more security features in label or
printing ink containing visually and/or
strip form or all over
machine testable substances (e.g. liquid
crystal or interference layer pigments,
luminescent substances); in label or strip
form or all over
The inventive security paper can be further processed into any value documents, such as bank notes, shares, identity cards, credit cards, security labels, coupons, etc. It can also be used in the area of product protection for protecting any goods from forgery.
BRIEF DESCRIPTION OF THE DRAWINGS
Further advantages and embodiments will be explained with reference to the figures, in which:
FIG. 1 shows an inventive value document in a plan view,
FIG. 2 shows a section through said value document along A-A,
FIG. 3 shows an inventive apparatus for producing the inventive security paper,
FIG. 4 shows an inventive sealing element in accordance with detail B in FIG. 3 ,
FIG. 5 shows an alternative embodiment of the sealing element,
FIG. 6 shows detail B in accordance with FIG. 3 with additional screen embossing in the surroundings of the sealing element,
FIG. 7 shows a cross section through a security paper produced by the papermaking screen shown in FIG. 6 ,
FIG. 8 shows a plan view of the security paper section shown in FIG. 7 ,
FIG. 9 shows a further embodiment of the inventive security element in cross section along line A-A in FIG. 1 ,
FIG. 10 shows a further embodiment of the inventive security paper in cross section,
FIG. 11 shows a further embodiment of the inventive security paper in cross section,
FIG. 12 shows a further embodiment of the inventive value document.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows an inventive value document in a plan view. The shown example involves a bank note 1 . Said bank note 1 has a through opening 2 . Said opening was produced during production of the security paper used for the bank note 1 and therefore has a fibrous, irregular edge 14 . Said edge 14 arises during sheet formation of the paper used for the bank note and cannot be produced by subsequently punching or cutting the paper.
FIG. 2 shows the bank note 1 in cross section along line A-A. This makes it clear that the opening 2 is a through opening.
FIG. 3 shows the schematic representation of a cylinder paper machine 3 as is preferably used for producing the inventive security paper 10 . The apparatus 3 consists essentially of the papermaking screen 4 and the take-off roll 5 on which the pickup felt 6 is mounted.
The papermaking screen 4 has sealing elements 7 which prevent sheet formation when the papermaking screen is dipped into the paper pulp 8 and thus produce the inventive openings 2 . The sealing elements 7 are so formed that they do not hinder removal of the paper web 10 in the area of the take-off roll 5 . Since at this time the paper web 10 is still very unstable and has low strength, a contact without tension must be ensured between the paper web 10 and the pickup felt 6 .
FIG. 4 shows detail B of FIG. 3 in an enlarged form. The sealing element 7 shown here is fastened to the surface of the screen 4 . It consists of a pot-shaped element with a further pot-shaped element embedded therein. The two elements are urged apart by a spring 9 so that they abut with their edge areas.
FIG. 5 again shows the sealing element 7 in the depressed state. The sealing element 7 is urged against the pressure of the spring 9 under the level of the papermaking screen surface 4 . The pressure is preferably produced by the take-off roll 5 . That is, the sealing element 7 is urged downward upon contact with the take-off roll 5 , thus in no way hindering the distortion-free removal of the paper web 10 by the pickup felt 6 .
FIG. 6 shows a further embodiment of the inventive papermaking screen 4 with reference to an enlargement of detail B of FIG. 3 . In this case the papermaking screen 4 additionally has a watermark embossing 11 in the surroundings of the sealing element 7 . In the shown example the watermark embossing 11 is disposed symmetrically around the sealing element 7 . However, any other embodiment of the watermark embossing 11 is also possible. The watermark embossing 11 causes the deposit of paper fibers in different thicknesses during sheet formation, so that the finished paper web is modulated in this area and shows the reflected/transmitted light effect typical of watermarks.
FIG. 7 shows a paper web 10 produced with the help of the papermaking screen 4 shown in FIG. 6 . Said paper web 10 has an opening 2 produced by the sealing element 7 . The modulated paper areas 12 , however, were produced by the watermark embossing 11 . Said paper areas hereinafter designated “the watermark 12 ” can be directly related meaningfully to the opening 2 , or the opening 2 and the watermark 12 can together form a motif, as shown for example in a plan view in FIG. 8 . The opening 2 has a circular outline form and is surrounded by a radial watermark 12 , resulting in the motif of a sun.
FIG. 9 shows a further embodiment of the value document 1 shown in FIG. 1 in cross section along line A-A. In this case the opening 2 is sealed by a security element 13 on one side. Said security element 13 is preferably disposed in a depression 15 surrounding the opening. Said depression 15 can be produced by subsequent calendering of the paper web 10 , i.e. by compression of the paper fibers.
Alternatively, the depression 15 can also be produced by an actual reduction of the paper thickness in this area. This is most simply done directly during production of the paper web 10 by performing sheet formation thinner in said area through a corresponding formation of the screen. This can be done by corresponding embossings 16 in the papermaking screen 4 .
The sealing element 7 shown in FIGS. 4 and 5 can be realized in a great variety of ways. It is thus likewise conceivable to realize it by a foamlike plug which is compressed by the take-off roll 5 . This element is glued to the papermaking screen 4 and likewise prevents sheet formation in this area. However, it can also be realized by a pot-shaped, elastic element which is compressed by pressure and then returns to the original form.
The security element 13 can be of single- or multilayer form and has at least one paper or plastic layer. The security element 13 preferably has in the area of the opening 2 a relatively large transparent area which serves as copy protection, on the one hand, and makes the opening edge recognizable from both sides, on the other hand. Furthermore, the security element 13 can be provided with any desired security features.
FIG. 10 shows a further embodiment of the inventive security paper in cross section. The paper web 10 has an area 16 with a smaller paper thickness in comparison with the rest of the paper web. However, paper thickness is almost uniform throughout the area 16 . This thin area 16 can be produced by corresponding screen embossing or freeness hindrance during production of the paper web 10 . In said thinner area 16 the inventive opening 2 is subsequently provided. The edge contours 17 of the opening 2 are indicated by dashed lines in FIG. 10 . The opening 2 is preferably produced in this embodiment by subsequent punching or cutting of the paper web in the area 16 . It must at the same time be ensured that the area 16 protrudes beyond the opening 2 at least in a partial area to permit a corresponding check of the authenticity of the paper web 10 to be performed upon transmissive viewing.
FIG. 11 shows a further embodiment of the inventive security paper, whereby the security paper in this case consists of two paper layers 18 , 19 . The two paper layers 18 , 19 are produced on separate cylinders and combined directly after removal from the papermaking screen and then further processed jointly. In the first paper web 18 a hole 20 is produced with the above-explained aids during sheet formation on the cylinder. When the two paper webs 18 , 19 are combined, said hole 20 is sealed again on one side. After completion of the security paper the inventive opening 2 is provided in the second paper web 19 . The edges 17 of the opening 2 are also shown by dashed lines in this figure. The opening is produced here by cutting or punching, whereby it must be ensured analogously to the embodiment shown in FIG. 10 that the edges 17 or cut edges of the opening 2 are located in the area of the hole 20 .
FIG. 12 shows a further embodiment of the inventive value document 1 in a plan view. The opening 2 is composed in this example of several partial openings 21 , 22 , 23 separated from each other by paper bars 24 . Said partial openings 21 , 22 , 23 can be produced analogously to the above-described variants for the opening 2 . | A security paper for producing security documents, such as bank notes, identity cards or the like, having at least one opening, whereby the opening is produced during papermaking and does not have a sharp limiting edge in the edge area. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
The present invention is related to and claims priority from U.S. Provisional Application No. 60/681,948, entitled “INTEGRATED, CLOSELY SPACED, HIGH ISOLATION, PRINTED DIPOLES,” filed May 18, 2005, the contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates generally to wireless communications and more specifically to closely spaced antennas utilizing orthogonal polarization to reduce electromagnetic coupling.
BACKGROUND OF THE INVENTION
In certain circumstances, it becomes necessary to closely position multiple omni directional antennas, such as those used in repeaters, where the antennas for both the donor and subscriber sides of the repeater are placed in close proximity. For example, such closely spaced antennas can be embedded onto low cost printed circuit boards for use in various communications products and systems, such as in the WiDeFi™ TDD based repeater system. It is further desirable for such closely spaced antennas to maintain minimal antenna-to-antenna interaction while maintaining good gain characteristics, to be easily producible in high volume manufacturing using low cost packaging, and to be easy for a user to operate. Further, when the antenna is placed near a reflecting surface, such as a wall, that would otherwise change the free space isolation of the antennas, a mechanism is required to reduce or cancel the effect of the interaction.
Three key problems present themselves when attempting to achieve high isolation between multiple, closely-spaced antennas that are printed on a small PCB board with near omni-directional antenna patterns and that must work in close proximity to unknown structures such as walls, furniture, and the like. The problems are coupling of radiated energy, common mode coupling and multi-path or random coupling of in-band signal energy.
In dealing with the first problem of coupling of radiated energy from one antenna into the receiver section of another, the radiated fields emanating from the antenna structure must be cancelled somehow to increase isolation. The closer the antennas are in physical proximity, the more they will tend to couple energy, which coupling reduces isolation between the antennas. Additional problems can arise when attempting to maintain an omni or semi-omni directional antenna pattern.
Dealing with the second problem of common mode coupling involves a coupling mechanism that is difficult to cancel. Common mode coupling occurs due to a shared ground on a printed circuit board. Voltage perturbations on the ground plane associated with generating and transmitting a signal from one antenna circuit couple into an adjacent antenna circuit either electrically into input circuits through the ground plane or indirectly from energy induced into the ground plane or input circuits by the transmitted signal. The problem of common mode coupling is especially difficult when multiple antennas are integrated together on a very small ground plane.
The third problem of random coupling is often the most difficult coupling mechanism to address. With random coupling, energy from indeterminate reflections or interactions with objects that change the radiation patterns or sources of localized coupling are primarily the result of antenna placement. However, attempting to determine an exact antenna placement that reduces or removes the unwanted components while preserving the desired components and the directionality is not generally successful.
SUMMARY OF THE INVENTION
The present invention overcomes the above noted and other problems by providing an antenna configuration for a repeater in which two closely spaced antennas are orthogonally polarized to increase antenna isolation and reduce electromagnetic coupling. The two antennas may be fed in a balanced configuration to reduce common mode currents. The configuration is provided with a ground structure having various non-parallel and non-symmetrical shapes to reduce circulating currents and ground “hot spots” that can act as additional radiators thereby tending to increase coupling.
Alternatively, or in addition, to reducing shape symmetry and parallelism of the ground structure, an exemplary ground structure is provided with various printed structures that “choke” circulating ground currents by inducing opposite polarity currents that will generate electromagnetic (EM) fields with opposite, and thus canceling, polarities. The configuration may also be rotatable and capable of transmitting a sounding signal. By receiving the sounding signal during antenna rotation, the configuration is provided with feedback, which can be output to a user in the form of, for example, a sounding signal strength indicator or the like, providing information regarding antenna signal reflections to enable the user to directionally or spatially reposition the antenna configuration to maximize antenna operation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram illustrating a horizontally and a vertically polarized dipole antenna with resultant signals having respective horizontal and vertical polarization.
FIG. 2 is a diagram illustrating an exemplary dipole having undesirable circulating currents causing unwanted secondary radiation.
FIG. 3 is a diagram illustrating the exemplary dipole of FIG. 2 , having a Balun for eliminating undesirable circulating currents and associated radiation.
FIG. 4 is a diagram illustrating a top layer of a multi-layer printed circuit board having an orthogonally polarized antenna configuration.
FIG. 5 is a diagram illustrating a second layer of a multi-layer printed circuit board having an orthogonally polarized antenna configuration.
FIG. 6 is a diagram illustrating a third layer of a multi-layer printed circuit board having an orthogonally polarized antenna configuration.
FIG. 7 is a diagram illustrating a fourth layer of a multi-layer printed circuit board having an orthogonally polarized antenna configuration.
FIG. 8 is a diagram illustrating a fifth layer of a multi-layer printed circuit board having an orthogonally polarized antenna configuration.
FIG. 9A and FIG. 9B are diagrams illustrating a pair of perspective views of an exemplary embodiment of a packaged antenna configuration of the present invention that is adjustable/rotatable.
FIG. 10 is a diagram illustrating signals incident on an exemplary embodiment of an orthogonally polarized antenna configuration of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings in which like numerals reference like parts, several exemplary embodiments in accordance with the present invention will now be described. To address the above noted problems and other problems, an exemplary antenna configuration is provided where printed dipoles, or dipole elements, are positioned so as to be orthogonally polarized. The interference cause by a signal emanating from one radiating antenna into the adjacent antenna can be cancelled by establishing a polarity or orientation of the adjacent antenna having a natural tendency to cancel the signal energy which is produced with an electromagnetically opposite polarity or orientation from the radiating antenna.
It will be appreciated that the polarization of an antenna relates to the orientation of an electric field of a propagating signal radiated from the antenna and can be determined by the physical structure of the antenna and by its orientation. In contrast, the directionality of the antenna relates to the radiation pattern and is somewhat different from orientation. Polarization is typically referred to in terms of horizontal polarization, vertical polarization, circular polarization, and the like.
An example of polarization can be seen in FIG. 1 , where a configuration 100 is shown having a dipole element, or dipole, 101 having a vertical polarization and a dipole element, or dipole, 102 having a horizontal polarization. The dipole 101 and the dipole 102 are separated by a phase angle 120 , which will determine the phase difference between a reference signal propagated from each of the dipole 101 and the dipole 102 in a propagation direction 110 . It will be appreciated that an exemplary signal E y 103 transmitted, for example, from the dipole 101 , will be vertically polarized; that is, it will have an E field component propagating in a plane that is vertically oriented. Similarly, an exemplary signal E x 104 transmitted, for example, from the dipole 102 , will be horizontally polarized; that is, it will have an E field component propagating in a plane that is horizontally oriented. It will be appreciated that due to the orthogonal relationship between the polarization directions of the dipole 101 and the dipole 102 , the likelihood of interference between signals radiated from one of the antennas into the other is low. It will also be appreciated that a signal incident on one of the antennas having a polarization opposite to that of the antenna will not couple well into that antenna. As noted above, some problems arise due to signal reflection, which can change signal polarization. However, by establishing an orthogonal relationship between the polarization of each dipole, maximum cancellation can be achieved even for reflected signals since the polarization can be calculated as the sum of the E field orientations over time relative to an imaginary plane perpendicular to the propagation direction the signal. It should be noted that while the dipole 101 and the dipole 102 are orthogonal, they are separated by a phase 120 . In accordance with various exemplary embodiments, the dipole 101 and the dipole 102 are positioned in an orthogonal relationship on the surface of, for example, a printed circuit board, printed wiring board, or the like as will be described in greater detail hereinafter.
In placing exemplary dipoles on the surface of a printed circuit or wiring board, some problems may arise as shown in exemplary configuration 200 in FIG. 2 . A dipole antenna 201 is shown, for example, constructed of a coaxial cable with dipole elements 202 and 203 . In some instances unbalanced circulating currents in the dipole 201 from impedance mismatches or the like, can cause unwanted radiation 204 to emanate from portions of the dipole other than the radiating dipole elements 202 and 203 . The effect is greatest when a balanced configuration such as the symmetrical configuration of the dipole element 202 and the dipole element 203 meet the non-symmetrical or unbalanced portion of the dipole antenna 201 . In a circuit board environment, such radiation can cause interference by coupling into input stages of amplifiers, coupling into ground planes, or by coupling into other antenna present on the circuit board. To address the problem, as shown in exemplary configuration 300 in FIG. 3 , a balun 310 , sometimes referred to as a baluns, or a Marchand Balun, named after Nathan Marchand who described such a configuration in the 1940s for coaxial transmission lines, can be positioned near the dipole elements 202 and 203 of the dipole antenna 201 . It will be appreciated that the balun 301 preferably has a precise 180° phase shift, with minimum loss and equal balanced impedances. The balun 301 provides isolation from ground to eliminate parasitic oscillations.
The basic construction/design of the balun 310 consists of two 90° phasing lines that provide the required 180° split. This involves the use of wavelengths in the order of λ/4 and λ/2. It will be appreciated that in a general coaxial example, a wire-wound transformer provides a suitable balun. Miniature wirewound transformers are commercially available covering frequencies from low kHz to beyond 2 GHz. Such balun transformers are often configured with a center-tapped secondary winding. When the center tap is grounded, a short circuit is presented to even-mode, or common-mode signals providing isolation and rejection. Differential or odd-mode signals are passed without effect.
As will be described in greater detail hereinafter, wire-wound transformers are expensive and are comparatively unsuitable in form factor for the printed dipoles of the present invention. Thus, the printed or lumped element balun is preferable in practical application. It should be noted the lumped element or printed balun is preferably provided with a center-tapped ground to reject common mode or even mode signals. The Marchand Balun can be adapted for use in a printed circuit configuration to increase isolation and increase noise rejection in the printed dipoles of the present invention, to be described in greater detail hereinafter.
With reference to the previously noted first problem, the interaction of EM fields can be canceled by orienting the printed dipole antennas of the present invention such that the respective polarization of the EM fields of each of the antennas are orthogonal to each other, thereby reducing or canceling any coupling therebetween. To reduce other possible points of radiation from the PCB itself such as radiation which would likely emanate from the ground structure, the shape of physical areas of the printed ground structure in close proximity to the antennas can be adjusted such that the ground structure ordinarily situated in parallel relation to the antenna has perpendicular rectangular structures added such that re-radiation points such as corners are shifted away from antenna structures.
With reference to the previously noted second problem, generalized coupling through the board substrate can be reduced by driving each of the printed dipole antennas of the present invention in a balanced fashion ensuring better isolation. For example, if any portion one signal couples into the other antenna feed structure, it does so as a common mode signal to both traces of the balanced feed structure and is hence canceled. Further, current choke slots can be printed onto the outer edges of the ground layers to reduce any currents that would tend to circulate around the outside of the ground plane between the two antennas. The choke structures cause the circulating currents to flow in opposite directions thereby generating EM fields with in-turn induce counter currents tending to choke off and cancel the original currents.
With reference to the previously noted third problem, several methods including trial and error are possible. However, a preferable approach to dealing with antenna placement is by transmitting a sounding signal from one antenna and receiving or “listening” to the reflections as they propagate back into the other antenna. Based on the arrangement of structures surrounding the antennas, the strength of the signal reflections back into the receiving antenna will be either higher than desired or will be sufficiently low to allow proper system operation. An indication can be provided to a user, either through a visual indicator such as a lamp or an LED, or through a series of LEDs, an external monitoring device, or the like. If the strength of the reflections as indicated by the LEDs is higher than desirable, a user can be directed to move or reposition the antenna until the strength of the reflections are minimized to levels considered to be acceptable. As noted, the feedback to the user could take many forms and the readjustment of the antenna could be in any different direction and any distance.
To better appreciate the printed circuit configuration of the closely spaced dipoles, a top layer 400 of an exemplary multi-layer circuit board is shown in FIG. 4 . A first printed wiring board layer 401 being a top layer of a multi-layer printed orthogonally polarized antenna configuration includes a ground plane 402 occupying a portion of the first printed wiring board layer 401 . A horizontally positioned strip 410 and a vertically positioned strip 411 are portions of the orthogonally positioned printed dipoles. The area of the ground plane with a portion removed shown in a T configuration is a choke 420 , which can be used to reduce circulating currents in the ground plane as described above. Further, a rectangular area 403 can be added to the ground plane 402 in order to disrupt circulating current which could radiate and couple energy into dipole feed sections and other sensitive circuits such as amplifier inputs and the like.
A second layer 500 of a multi-layer printed orthogonally polarized antenna configuration is shown in FIG. 5 . A second printed wiring board layer 501 being a second layer of a multi layer printed orthogonally polarized antenna configuration includes a ground plane 502 occupying at least a portion of the second printed wiring board layer 501 . A horizontally positioned strip 510 and a vertically positioned strip 511 are portions of the orthogonally positioned printed dipoles. It will be appreciated that the dipole strips 510 and 511 are preferably connected through vias (not shown) to the dipole strips 410 and 411 shown in FIG. 4 . A rectangular area 503 can be added to the ground plane 502 in order to disrupt circulating current which could radiate and couple energy into dipole feed sections and other sensitive circuits such as amplifier inputs and the like. It will be appreciated that ground plane 502 further contains a feed channel 512 and a feed channel 513 for providing clear areas for reducing inductance from the ground planes into signal traces in adjacent layers associated with the feed paths that will couple to dipole sections such as the dipole strips 410 , 411 , 510 and 511 . In addition, achoke 520 can be provided corresponding to the choke 420 in the adjacent layer.
A third layer 600 of a multi-layer printed orthogonally polarized antenna configuration is shown in FIG. 6 . A third printed wiring board layer 601 being a third layer of a multi layer printed orthogonally polarized antenna configuration includes a ground plane 602 occupying at least a portion of the third printed wiring board layer 601 . It will be appreciated that the dipole strips 610 and 611 are preferably connected through vias (not shown) to the dipole strips 410 and 411 shown in FIG. 4 and to the dipole strips 510 and 511 shown in FIG. 5 . A rectangular area 603 can be added to the ground plane 602 in order to disrupt circulating current which could radiate and couple energy into dipole feed sections and other sensitive circuits such as amplifier inputs and the like. As previously noted a first printed dipole antenna, configured with dipole strips 410 , 510 and 610 and a second orthogonally positioned printed dipole antenna, configured with dipole strips 411 , 511 and 611 are fed, at least in part, through traces 612 and 613 respectively. It can be seen that only one portion of the dipole strips 410 , 510 and 610 and 411 , 511 , 611 are fed by the traces 612 and 613 . The other portions are connected to ground as will be described. Signals received and transmitted on first and second printed dipole antennas can be coupled to transceiver input or output circuits (not shown) as appropriate. A connector section 620 is also shown where various connections can be made from traces on the printed wiring board to pins associated with an external connector (not shown) that can be mounted in the area of connector section 620 .
A fourth layer 700 of a multi-layer printed orthogonally polarized antenna configuration is shown in FIG. 7 . A fourth printed wiring board layer 701 being a fourth layer of a multi layer printed orthogonally polarized antenna configuration includes a ground plane 702 occupying at least a portion of the third printed wiring board layer 701 . It will be appreciated that the dipole strips 710 and 711 are preferably connected through vias (not shown) to the dipole strips 410 and 411 shown in FIG. 4 , to the dipole strips 510 and 511 shown in FIG. 5 , and to the dipole strips 610 and 611 shown in FIG. 6 . A rectangular area 703 can be added to the ground plane 702 in order to disrupt circulating current which could radiate and couple energy into dipole feed sections and other sensitive circuits such as amplifier inputs and the like. In a manner similar to the signal portion of the first and second dipoles, for example as described above, a ground portion of the first printed dipole antenna, configured with dipole strips 410 , 510 , 610 and 710 and the second orthogonally positioned printed dipole antenna, configured with dipole strips 411 , 511 , 611 and 711 are coupled to ground through traces 712 and 713 respectively. A connector section 720 is also shown where various connections can be made from traces on the printed wiring board to pins associated with an external connector (not shown) that can be mounted in the area of connector section 720 . It will also be appreciated that a printed circuit trace for connection to the transceiver through a Marchand Balun can be provided for example, at traces 714 and 715 .
A fifth or bottom layer 800 of an exemplary multi-layer circuit board is shown in FIG. 8 . A fifth printed wiring board layer 801 being a bottom layer of a multi-layer printed orthogonally polarized antenna configuration includes a ground plane 802 occupying a portion of the fifth printed wiring board layer 801 . A horizontally positioned strip 810 and a vertically positioned strip 811 are portions of the orthogonally positioned printed dipoles. The area of the ground plane with a portion removed shown in a T configuration is a choke 820 , which can be used to reduce circulating currents in the ground plane as described above. Further, a rectangular area 803 can be added to the ground plane 802 in order to disrupt circulating current which could radiate and couple energy into dipole feed sections and other sensitive circuits such as amplifier inputs and the like.
In FIG. 9A and FIG. 9B , perspective views of an exemplary embodiment of a packaged antenna configuration 900 of the present invention are shown. The antenna package 901 is adjustable/rotatable about an axis or hinge which is located in the portion of the package surrounding plug 910 that can be plugged into a standard wall socket 920 . Such a configuration provides for potential positioning of the antenna package 901 for placement that reduces or eliminates interference. As depicted, the antenna package 901 , which could be associated with a WiDeFi™ TDD repeater, has an align LED 911 at the top of the antenna package 901 . Additionally the antenna package 901 can be rotated through an arc 902 such that the top of the antenna package 901 could be rotated down and away from a wall 903 . Such rotation would bring the antenna package 901 from a starting position parallel to the wall 903 to a position where one end of the dipole antennas is closer to the wall 903 and the other end is father away from the wall 903 , thereby providing a high degree of change in any coupling mechanisms that may be present due to the wall 903 . In such a configuration, the LED 911 will flash until the operation of sending and receiving the sounding signal as described above, while repositioning the antenna package 901 results in an acceptable position at which time it will stop, change color, or some other indicia that the interference between the sounding signal transmitter and receiver has been reduced to acceptable levels. When such an indication is provided, the user should stop rotating the antenna package 901 .
By placement of the first and second dipoles in orthogonal relation on a printed wiring board as described and illustrated herein, maximum isolation can be achieved. FIG. 10 shows a configuration 1000 where a first dipole 1001 and a second dipole 1002 are positioned in orthogonal relation, such as a 90° relation 1020 , on the surface of a printed wiring board. The first dipole 1001 can transmit signals 1010 with a corresponding polarization and optimally receive signals 1010 with the same polarization. Signals incident on the second dipole 1002 having the polarization of the first dipole 1001 , such as incident signal 1012 , will not be received, that is, will not effectively couple energy into the second dipole 1002 , since the polarization of the second dipole is directed orthogonally away from the polarization direction of the incident signal 1012 . Such signal rejection is true of incident signals 1012 incident from remote transmitters and from signal components associated with incident signals 1012 generated by the first dipole 1001 . Likewise, the second dipole 1002 can transmit signals 1011 with a corresponding polarization and optimally receive signals 1011 with the same polarization. Signals incident on the first dipole 1001 having the polarization of the second dipole 1002 , such as incident signal 1013 , will not be received, that is, will not effectively couple energy into the first dipole 1001 , since the polarization of the first dipole is directed orthogonally away from the polarization direction of the incident signal 1013 . Such signal rejection is true of incident signals 1013 incident from remote transmitters and from signal components associated with incident signals 1013 generated by the second dipole 1002 .
It should be noted that the respective first dipole 1001 and the second dipole 1002 can be coupled to a first transceiver/STA 1020 and a second transceiver/STA 1030 for providing a transmit signal and for receiving a signal received on the respective antenna. It will be appreciated that in various exemplary embodiments, the first transceiver/STA 1020 and a second transceiver/STA 1030 can be configured to operate by sending and receiving signals in various modes such as in a TDD mode using one or more frequency channels, in frequency division duplex (FDD) mode and the like, and can be configured to operated according to various standards under 802.11, 802.16, and the like.
The invention is described herein in detail with particular reference to presently preferred embodiments. However, it will be understood that variations and modifications can be effected within the scope and spirit of the invention. | An antenna configuration includes two closely spaced antennas each positioned so as to be orthogonally polarized with respect to the other. The antenna configuration increases antenna isolation and reduces electromagnetic coupling between donor side antenna and repeat side antenna. The antennas include printed dipoles connected to respective transceivers through respective baluns to balance the non-symmetrical portions of the antenna feed paths to reduce unwanted radiation therein. Printed features such as chokes and non-symmetrical and non-parallel structures are preferably included in the ground plane of a multi-layer circuit board to reduce or eliminate circulating ground currents. | 7 |
RELATED APPLICATION
[0001] This application is a continuation of application Ser. No. 10/084,592 filed Feb. 25, 2002, the entire disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] One of the most common diseases in newly received stocker and feedlot cattle is the Bovine Respiratory Disease (BRD) complex. BRD accounts for approximately 75% of morbidity and over 50% of mortality in feedlots (Edwards, A. 1996. Bovine Pract. 30:5). Studies have indicated that BRD manifests its economic losses cumulatively—through the cost of treatment, the cost of lost production and/or salvage, and the cost of death loss (Perino, L. J. 1992. Compend. Cont. Educ. Pract. Vet. 14 (Suppl.):3) These losses make BRD one of the most costly diseases affecting feedlot cattle. Respiratory tract lesions at slaughter correlate with feedlot and carcass performance (Gardner, B. A. et al. 1999. J. Anim. Sci. 77:3168).
[0003] In a recent study of the affects of BRD, heifers treated during the study period had lower average daily gain during the period. Heifers treated for BRD had lower marbling scores resulting in a 37.9% reduction in the percentage of carcasses grading U.S.D.A. Choice, or above. Heifers never treated produced a net return (carcass basis) that was $11.48/head more than heifers treated once for BRD, and $37.34/head more than those treated two or more times. (Stovall, T. C., et al. Impact of Bovine Respiratory Disease During the Receiving Period on Feedlot Performance and Carcass Traits, Animal Science Research Report. Oklahoma Agricultural Experiment Station, Oklahoma State University, Stillwater, Okla., USA, 2000.)
[0004] Other diseases are of equal or greater economic importance to the cattle industry, which has historically sought to protect livestock from disease, both for economic and public confidence reasons. Immunization of cattle as a means of preventing disease is a common and long-standing practice dating back to Jenner and Pasteur. Immunization is the practice wherein pathogenic biological agents (viruses, bacteria, fungus, rickettsia, protozoa, mycoplasma) have been inactivated, attenuated administered with or without immuno-modulating agents (adjuvants) to animals with the intent of stimulating the animal's immune system such that subsequent exposure to the immunizing or natural agent yields a rapid and specific protective response, thereby avoiding or reducing the severity of disease.
[0005] The common means by which commercial vaccines have been administered to animals involves injecting (by use of hypodermic needles) the vaccine material in the skin (intradermal “ID”), in the muscle (intramuscular “IM”), in the subcutaneous tissue (“SC” or “sub-Q”)) or applying the product to readily available mucus membranes (in the eye (intraocular “IO”), in the oral cavity (peros “PO”), or in the nasal cavity (intranasal “IN”)). Although the poultry industry has used aerosols and water as means of vaccine delivery to large numbers of birds, and the swine industry has used water as a delivery method, there are no aerosol, water or feed vaccines approved for commercial use in cattle, dogs, cats or horses.
[0006] In the case of injected products (pharmaceutical or biological), a number of concerns arise. With respect to food safety and consumer concern about meat quality, introduction of material into the animal via injection carries with it the potential of altering the edible product by scaring, staining, infection or adulteration due to components of the product and/or by carrying foreign material into the body as a result of the injection process as well as the potential for needles being left in the animal. The National Cattlemen's Beef Association has identified losses associated with injection site reactions resulting in damage to the animal, meat, hides and undermining consumer confidence in the safety and quality of beef. Additionally, injection requires close physical contact between the animal and the person administering the vaccine. This close physical contact entails risk of injury to both the animal and the person. There is a potential for accidental injection of workers or non-target animals. Proper disposal of used needles is an ongoing concern. With respect to application of the vaccine, it is difficult to assure or identify proper deposition of the dose volume into the approved target tissue, particularly under modern management practices where large numbers of animals are rapidly processed. Injection of companion animals (dog, cat, horse) has animal welfare and owner acceptability concerns as well as the potential for infection, pain and tissue damage at the site of administration,
[0007] Administration via mucus membranes has several advantages over injected vaccines. Entry of foreign material into edible tissues is avoided. Some pharmaceutical products (insulin—West Pharmaceuticals) have been shown to perform better when applied to mucus membranes as compared to IM or SC injection. The natural route of exposure to the common respiratory and enteric pathogens is via the oral and or nasal route. Stimulation of a mucosally active immune response is better able to prevent or minimize colonization (a prerequisite to infection and disease) by invading pathogens.
[0008] Additionally, intranasal administration of vaccines typically stimulates a rapid response and has been shown to be effective in the presence of maternal antibody. There are, however, drawbacks to commercially available cattle vaccines. Products approved for intranasal administration require direct deposition of the vaccine into the nasal cavity (one or both naries). This is stressful to the animal and requires restraint and close physical contact between the animal and person administering the vaccine. In addition, the animal's immediate response is to resist head restraint and attempt to dispel the injected material from the nasal cavity during or immediately following vaccine administration, sometimes into the operator's face, with resulting safety and efficacy concerns.
[0009] Water and feed have been used experimentally as a means of vaccine delivery to cattle, however, there are concerns relating to proper dose intake of individual animals. There are no commercial cattle vaccines currently approved for use via feed or water.
[0010] Mucosal administration of vaccines has been shown to provide a broad based immune response. This involves both a local and systemic response. Traditionally, vaccines used for mucosal administration have been live or attenuated; as killed antigens tended to be minimally effective when given IN or PO. While live or attenuated vaccines provide a rapid response, the duration of immunity has typically been less than with IM administered products. With the advancement in adjuvant technology and vaccine formulation, it is now possible to increase the duration of immunity as well as allow use of inactivated antigens via the mucosal route. Advancement in formulation of pharmaceutical preparations has also led to development efforts for orally and/or nasally administered products (West Pharmaceutical).
[0011] Despite the advances in intranasal and other mucosal administrations of vaccination and therapeutic materials, there remain many needs in the development of safe, effective, and efficient methods of administration of such materials to animals. In particular, the following needs remain unmet by the methods of the prior art:
[0012] 1. The need to avoid use of needles which may (a) cause damage to edible tissues and hides, (b) incite consumer concern over pet and livestock animal welfare, (c) incite consumer and food industry concern over food safety, (d) raise concerns related to worker safety, and (e) give rise to issues concerning disposal of contaminated medical waste.
[0013] 2. The need and desire to administer the vaccine to mucosal membranes which is the natural route of infection.
[0014] 3. The need to avoid (or minimize) close physical contact between the worker and animal in order to reduce the risk of injuries to both.
[0015] 4. The need to have a visual indicator of vaccination in order to increase compliance and proper administration of vaccine, and to reduce inadvertent multiple vaccination.
BRIEF DESCRIPTION OF THE INVENTION
[0016] According to the present invention, a vaccine/pharmaceutical-containing composition is applied to the muzzle of the animal, which will then naturally use its tongue to clean itself. This behavior will cause the animal to deposit a therapeutically effective amount of the applied composition to the mucosa of the nasal and oral cavities, thus meeting the need for a simple, effective, and efficient vaccination/treatment method of administration.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The present invention comprises a method for immunizing and/or treating cattle or other animals via application of an approved dose of biological vaccines (antigens) or pharmaceuticals to the muzzle and/or nares area of cattle or other animals via direct application such as a liquid or emulsion paint, spray, paste, mist, roll-on or bio-film. The muzzle of an animal is defined as the facial portion of the respiratory system and rostral portion of the upper and lower jaws collectively, to include the nasal plane, nostrils, medial, lateral, dorsal and ventral borders of the nostrils, the philtrum, superior and inferior lips (labia oris) and the angle of the mouth (angulus oris). This method of application takes advantage of the normal behavior of cattle and other animals to clean their muzzle with their tongue and thereby deposit the vaccine or pharmaceutical material to the nasal and/or oral mucosa. The method thus minimizes the need for physical contact between the human operator and animal, and eliminates the use of needles. The delivery composition of the present invention may contain any formulation comprised of mucosally active antigens and/or biologically active proteins and/or biologically active chemicals (pharmaceuticals) and/or biologically active carbohydrates with or without adjuvants, with or without adherent/viscous components, with or without aromatic and palatable components and with or without a visual or non-visible indicator of application.
Method of Administration
[0018] The composition described above may be applied to the muzzle of the animal in any of a variety of methods according to the present invention. For example, the composition may have a viscosity and concentration appropriate for application by brush or roller. It may be applied by liquid spray, with or without atomization. It may be manually applied as a paste, salve, or film. It may be carried on a carrier web such as a tape, adhesive strip, or patch. In short, any method of contacting the animal's muzzle and transferring to it an effective dose of the composition may be employed.
Formulation
[0019] The formulation of the compound of the present invention includes, but is not limited to various combinations of the following components for use in all animal species, including cattle, sheep, pigs, cats, dogs, horses, deer, buffalo and other wildlife:
[0020] 1. Adjuvants or other immune stimulating compounds, such as that described in U.S. Pat. No. 6,262,029 “Chemically Modified Saponins and the Use Thereof as Adjuvants”, Aluminum hydroxide salts, Aluminum hydroxide gels, Alum, “Superantigens” which are molecules that stimulate, independent of antigen, those T-cells displaying a particular beta chain variable region (Vbeta) of the T-cell receptor. These molecules are the most powerful T-cell mitogens known, inducing biological effects at femtomolar concentrations. The best characterized superantigens are the microbial toxins from Staphylococcus aureus and Streptococcus pyogenes.
[0021] Other adjuvants useful for the present invention include natural and synthetic immuno-modulating agents, other saponin and saponin derivatives, mycobacterial cell wall extract—Immnoboost® Bioniche Life Sciences Inc., oil emulsions (water in oil or oil in water) such as Amphigen® from Pfizer, Inc., oils (mineral oil, animal derived oils, plant derived oils such as carbopal), or other proprietary and non-proprietary immuno-modulating agents.
[0022] 2. Palatability enhancers, intended to be attractive to the animal's senses of smell and taste, such as plant-derived flavoring agents including but not limited to molasses, sucrose, fructose and anise.
Biological Antigens/Vaccines
[0023] Vaccines are used to prevent and/or treat a multitude of diseases in cattle and other animals. These include diseases of, but are not limited to, the respiratory system, the reproductive system, the urinary system, the gastrointestinal/digestive system, the integument/musculoskeletal system, the hemolymphatic system, the endocrine system, the nervous system, and disease of the eye and ear (Current Veterinary Therapy—Food Animal Practice, Howard, 1981, W. B. Saunders Co.). Organisms included are, but are not limited to, viruses, mycoplasma, chlamydia, protozoa, rickettsia, coccidia, bacteria, fungus (Current Veterinary Therapy—Food Animal Practice, Howard, 1981, W. B. Saunders Co.) and internal and external parasites including, but not limited to, helminths and arthropod parasites as identified in Principle Parasites of Domestic Animals in the United States, Ivens, et. al. 1978, University of Illinois, pp. 30-71. All current licensed products for cattle or other animals are administered via injection, via direct deposit in the nasal cavity, via direct deposit in the oral cavity, in water or in feed, topically applied, or by aerosol. The products are composed of from one to many antigens from a multitude of pathogenic and non-pathogenic biological organisms. The specific formulation may be composed of live, attenuated, killed or altered individual biological organisms acting as the immunizing antigen directly or serving as vectors to deliver the antigen of interest. The biologically relevant protective portion of the organism, be they recombinant or natural, can be present as the whole organism, specific and non-specific subunits of the organisms structural and non-structural components including cell wall, cell wall components, endotoxins, exotoxins (e.g. leukotoxin from M. haemolytica ), culture media supernatant, intracellular proteins and organelles including nuclear (including DNA/cDNA) and non nuclear elements (including RNA/cRNA). All and/or part of the fore going elements and organisms can be combined with or without immuno-modulating substances (adjuvants) to produce a vaccine designed to prevent and/or treat from one to many diseases following single and/or multiple administrations.
[0024] Currently Licensed Veterinary Products may be referenced in the Compendium of Veterinary Products (CVP); Fifth Edition, January 1999; Distributed by North American Compendium, Inc. 942 Military Street, Port Huron, Mich. 48060
[0025] The CVP provides a list of all current Federally (USDA/APHIS, FDA, EPA) approved products for use in cattle or other animals in the United States. This list includes brand names, antigens included, formulations, specific claims, and manufacturer for each product. In addition to those listed, there are non-USDA/APHIS approved or products with USDA/APHIS conditional approvals sold in the United States. These include, but are not limited to, vaccines classified as autogenous vaccines which are compounded for individual customers with organisms originating from the particular customers operation (provided by companies including ImmTech, Grand Laboratories, Texas Vet Labs, American Animal Health, individual practicing veterinarians, Universities and others) conditional licenses are granted for disease such as mycoplasmosis (Texas Vet Labs) where no Federally approved vaccine has been developed. In addition, there are new vaccines, and new claims for existing vaccines under development by many companies that can potentially be administered to cattle and other animals via the mucosal surfaces of the nasal and oral cavities. Outside the United States, similar products, antigens, antigen combinations composed and formulated in a manner similar to those produced and/or sold in the United States are common. All known biological agents can potentially be formulated (as the natural agent, or as a component of the organism via traditional and/or recombinant technology and/or as vectors) into a vaccine such that an immune response will be engendered in an animal when administered to the nasal and/or oral mucosa. The scope of this invention is intended to encompass all such current or future developed products or technologies, when the administration method involves application to the external structure of a bovine (or other animal's) muzzle and/or nares without the specific requirement of deposition onto or into the internal nasal and/or oral cavity.
Viscosity
[0026] The consistency of the product should be such that it remains in place long enough to allow proper dosage. Mediators of viscosity may be included into the compound formulation to ensure this goal is met.
Aroma
[0027] Ingredients may be used to enhance the aroma so as to contribute to palatability, or not detract from animal acceptance and natural behavior.
Identifier
[0028] In order to provide post-dosing identification of dose animals, a Light visible (e.g. orange, yellow) or UV or other nonvisible dye may be included in the compound formulation. In this manner, dosed animals may be easily recognized and one may avoid re-dosing them, ensuring proper dosage and saving on materials and labor.
Stabilizers
[0029] Appropriate product stabilizers such as to allow for antigen integrity and presentation may be included in the compound formulation.
Preservatives
[0030] The compound formulation may contain appropriate preservative ingredients such as antibiotics (e.g. gentamicin, amphotericin B, penicillin, polymyxin B or others), antibacterials or antifungal agents, (e.g. thimerosal, formaldehyde) as deemed appropriate or necessary by APHIS or other relevant regulatory authorities.
Sustained Release Substances
[0031] To promote release of active components over a longer time period, ingredients may be included such as inert or biologically active substances so as to extend the time of presentation of the antigen/chemical to the animal's immune system.
Adhesive Components
[0032] The compound formulation may contain appropriate component(s), which create additional adhesive capability of the product to adhere to the external nasal mucosa and to the internal oral and nasal tracts. These may include a bio-adhesive type of material that extends the time drug/antigen is available on the nasal or oral mucosa.
[0033] While the invention has been described in its preferred embodiments, it is to be understood that the words which have been used are words of description rather than of limitation and that changes may be made within the purview of the appended claims without departing from the true scope and spirit of the invention in its broader aspects. The inventors further require that the scope accorded their claims be in accordance with the broadest possible construction available under the law as it exists on the date of filing hereof, and that no narrowing of the scope of the appended claims be allowed due to subsequent changes in the law, as such a narrowing would constitute an ex post facto law, and a taking without due process or just compensation. | According to the present invention, a vaccine or pharmaceutical-containing composition is applied to the muzzle area of the animal, which will then naturally use its tongue to clean itself. This behavior will cause the animal to deposit applied composition to the mucosa of the nasal and oral cavities, thus meeting the need for a simple, effective, and efficient vaccination or treatment method. | 0 |
This invention relates to a slide gate damper system. More particularly, the invention relates to a slide gate damper system wherein a power source is mounted on the slide gate with the system having reduced overall weight, support structure and drive components.
BACKGROUND OF THE INVENTION
Ducts are found extensively in commercial and industrial buildings. Ducts are used for conveying heated air and toxic gases as a part of many power plants' electricity generating systems. They are also used for directing the flow of gases in many industrial processes. A necessary part of such ducts is the provision of dampers for regulating and isolating the flow of air and other gases through the ducts. There are various types of dampers. One widely used damper is commonly referred to as a slide gate damper. These dampers have gates which are essentially flat surfaces. The gates function by sliding in a track from outside a duct, through the duct wall, and into the duct passageway. Such dampers are used in ducts having cross surface areas ranging from about one square foot to about 500 square feet.
Gates on the dampers can be manually operated, though, because of their size and placement, are normally provided with a power source. A power source such as a electric motor with a drive mechanism is associated with the gate to open or close the gate in response to a command. The power source and drive mechanism for many slide gates require extensive mechanical drive components. Additionally, sufficient space must be allowed for all the necessary components to connect the power source to the gate. The resultant support frames, power source and drive mechanisms are very heavy overall.
There has now been developed an opening and closing system for slide gate dampers which requires a minimum of support structure. The motor and drive mechanism of the system make use of known dampers with a minimum of structural change required.
SUMMARY OF THE INVENTION
A slide gate damper system has reduced overall weight and support structure for use in ducts. The system comprises (a) a duct frame adapted for mounting in a duct, (b) a gate support frame mounted outside the duct in association with the duct frame (c) guide rails positioned on substantially parallel members of the gate support frame (d) a slide gate positioned within the gate support frame and dimensioned to ride along the guide rails, (e) a power source and (f) a drive mechanism. The power source is mounted on the slide gate for movement therewith. The drive mechanism associated with the power source and the gate support frame causes movement of the slide gate along the guide rails to varying positions.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a duct partially cut away to show the slide gate damper system of this invention.
FIG. 2 is a partial top view of the slide gate damper system of FIG. 1 showing the drive mechanism.
FIG. 3 is a side view of a roller lock mechanism found on the slide gate damper system of FIG. 1.
FIG. 4 is a back view of the roller lock mechanism of FIG. 3.
FIG. 5 is a partial view in perspective showing an alternative drive mechanism based on a gear wheel and chain drive.
FIG. 6 is a partial view in perspective showing another drive mechanism based on a rack and pinion drive system.
DETAILED DESCRIPTION OF THE INVENTION
The invention described herein is made with particular reference to the drawings. Referring to FIG. 1, there is shown duct 10 with a slide gate 11. A duct frame shown generally as 12 for receiving slide gate 11 is positioned in the duct. Members 13, 14 and 15 of the duct frame have recesses 16 which are positioned to accommodate the slide gate as it descends into the duct. Frame member 17 and a like member behind the slide gate each extend across the top of the duct with a slot 18 through which passes the slide gate when opened or closed. The duct frame is secured to the walls of the duct in a conventional fashion e.g., bolts typically extend through the frame members into the duct's walls. If required, zero leak means can also be provided to ensure that unwanted leakage does not occur. Ducts with such a frame and slide gate provided with zero leak means are well known.
Substantially parallel gate support members 19 and 20 in the form of I-beams are mounted on opposite sides of the frame member 18 and extend beyond the duct's outer surface. Cross support members 21 are provided for stability reasons. The slide gate 11 is dimensioned to fit within the parallel support members and is capable of moving up or down along guide rails 22 upon command. The guide rails 22 found on gate support frame members 19 and 20 are for the purpose of guiding the slide gate during any movement. The guide rails are secured along the inside surfaces of the gate support members for essentially the whole length. Conventional fastening members such as welds, screws and bolts maintain the guide rails in place.
In accordance with the invention, a power source is mounted on the slide gate. Power sources primarily include electric motors with appropriate gear reduction means. Electric motors are highly preferred because of their ease of operation. The power source is mounted to allow the slide gate to move to a fully open or fully closed position. The power source can be bolted directly to the slide gate or bolted to support brackets and braces mounted on the slide gate. As evident from FIG. 2, support bracket 25 is bolted to a face of the slide gate near the gate's top edge. An electric motor 26 and gear reduction means 27 are securely attached to bracket 25. Drive shaft 28 extends from the gear reduction means of the motor towards each side edge of the slide gate. The drive shaft passes through braces 29 and bearing supports 30. Preferably, the top edge of the slide gate is cut-away to accommodate the power source 26 with an overall reduction in height of the system. The electric motor is fed by an electric line (not shown). Provision is made in a known manner to ensure the electric line is maintained a safe distance from any possible pinch points.
An important feature of this invention is the positioning of the power source on the slide gate to move therewith. Placement of the power source on the slide gate itself simplifies the support structure and drive mechanism of the total system. Necessarily, the slide gate is a substantial structure often built to handle hot gases flowing at high speeds. A tremendous force is exerted against the slide gate. Using the slide gate to hold the power source eliminates a need to position it elsewhere with additional drive components, for the power source. The result is a damper system wherein the slide gate is more fully utilized with a consequent reduction in framing and hardware components to move the slide gate. An added benefit is the compactness of the total damper system.
Any drive mechanism which operably connects the power source to the immovable gate support members to cause movement of the slide gate is used. Preferred are gear wheels 33 mounted on each end of the drive shaft 28 and a cooperatively acting member fixedly mounted on the gate support members 19 and 20. The cooperatively acting member depicted in FIGS. 1 and 2 is a series of cross pins 34 spaced vertically along the gate support members to match with the teeth of the gear wheels as they revolve. The cross pins are fixed to side members 35 and 36 of the I-beam gate support members. Thus, actuation of the electric motor causes the drive shaft 27 to turn the gear wheels 33. The meshing of the teeth of the gear wheels with the cross pins 34 causes the slide gate to move along the guide rails until the desired gate position is achieved.
The power source is reversible, responsive to signals to either move the slide gate into or out of the duct to effect closing or opening of the duct. Stop limits are provided to prevent the slide gate from moving too far. Additionally, a manual means such as hand wheel 37 and worm gear are provided with the system as an emergency measure to move the gate in case of a power failure or other mechanical failure.
A roller lock mechanism shown generally as 40 is best depicted in FIGS. 2-4. The lock mechanism is intended as a means to securely hold the gear wheels 33 and cross pins 34 in mesh. In effect, this ensures that the slide gate will not inadvertantly slip off the cross-pins during operation. The lock mechanism comprises a plate 41 with a hole in one end to receive the end of the drive shaft 28. A bearing 42 is fitted in the plate hole to accommodate the drive shaft. An opposite side of the plate has two axles 43 and 44 secured in bearings 45 thereon and extending completely across the gate frame member 20. Rollers 46 are positioned to ride along the outside surface of side member 35 while rollers 47 are positioned to ride along the outside surface of side member 36 of the gate support member. Recessed portions of the rollers ride along the side members 35 and 36 for ease of operation of the lock mechanism. Brace 48 provides lateral movement stability for the lock mechanism. Still added stability is provided by substitution of the brace 48 with a plate which fixedly receives the axles 43 and 44 and the drive shaft 28.
FIG. 5 shows an alternative drive mechanism to be used in place of that depicted in FIGS. 1-4. A sprocket chain 50 is bolted at least on each end directly to an inside surface of the gate support member 19. One end of the chain is bolted with an adjustable take-up to accommodate any chain stretching over extended use. Individual links 51 receive the gear wheel teeth as it revolves. In this embodiment of the invention, guide rails 22 are positioned on each of the two parallel gate support frame members 19 and 20.
Another drive system shown in FIG. 6 utilizes a rack and pinion system. In this embodiment of the invention, the rack 60 is positioned on the gate support member 19. Individual members 61 of the rack are in mesh with the gear wheel teeth to cause movement of the slide gate in a manner similar to the system described with reference to FIG. 5.
In operation, actuation of the power source will cause the power source's drive shaft to revolve. The power from the drive shaft is transferred to the gear wheels. Cooperatively acting members on the system's gate support frame are in mesh with the revolving gear wheels. As the gear wheels revolve, the gear teeth mesh with the cooperatively acting members and move along them to cause the slide gate to open or close. Reversing the power source causes the slide gate to move in the other direction.
Obvious modifications may be made to the invention described herein. For example, a single vertical support member can be positioned laterally at approximate mid-point on the gate support frame. The cooperatively acting member of the drive system is associated with this vertical support member. All such obvious modifications and variations are within the scope of the invention. | A slide gate damper system comprises (a) a duct frame adapted for mounting in a duct, (b) a gate support frame mounted outside the duct in association with the duct frame; (c) guide rails positioned on the frame members of the gate support frame, (d) a slide gate positioned within the gate support frame, (e) a power source mounted on the slide gate and movable therewith and (f) a drive mechanism operatively connecting the power source to the gate support frame. Mounting of the power source on the slide gate and adapting the drive mechanism accordingly results in a slide gate damper system with reduced overall weight and support structure. | 4 |
FIELD
[0001] The present disclosure relates to a method for production of liquid natural gas (LNG) at midstream natural gas liquids (NGLs) recovery plants. More particularly, the present disclosure provides methods to efficiently and economically produce LNG at NGL recovery plants.
BACKGROUND
[0002] Natural gas from producing wells contain natural gas liquids (NGLs) that are commonly recovered. While some of the needed processing can be accomplished at or near the wellhead (field processing), the complete processing of natural gas takes place at gas processing plants, usually located in a natural gas producing region. In addition to processing done at the wellhead and at centralized processing plants, some final processing is also sometimes accomplished at Midstream NGLs Recovery Plants “straddle plants.” These plants are located on major pipeline systems. Although the natural gas that arrives at these straddle plants is already of pipeline quality, there still exists quantities of NGLs, which are recovered at these straddle plants.
[0003] The straddle plants essentially recover all the propane and a large fraction of the ethane available from the gas before distribution to consumers. To remove NGLs, there are three common processes; refrigeration, lean oil absorption, and cryogenic.
[0004] The cryogenic processes are generally more economical to operate and more environmentally friendly; current technology generally favors the use of cryogenic processes over refrigeration and oil absorption processes. The first-generation cryogenic plants were able to extract up to 70% of the ethane from the gas; modifications and improvements to these cryogenic processes over time have allowed for much higher ethane recoveries (>90%).
SUMMARY
[0005] The present disclosure provides a method for maximizing NGLs recovery at straddle plants and produces LNG. The method involves producing LNG and using the produced LNG as an external cooling source to control the operation of a de-methanizer column. According to at least one embodiment, the method furthers the production of ethane and generates LNG.
[0006] As will hereinafter be further described, the production of LNG is determined by the flow of a slipstream from the de-methanizer overhead stream in an NGL recovery plant. An NGLs recovery plant de-methanizer unit typically operates at pressures between 300 and 450 psi. When the de-methanizer is operated at higher pressures, the objective is to reduce re-compression costs, resulting in lower natural gas liquids recoveries. At lower operating pressures in the de-methanizer, natural gas liquids yields and compression costs are increased. The typical selected mode of operation is based on market value of natural gas liquids. The proposed method allows for an improvement in de-methanizer process operations and production of additional sources of revenue, LNG, and electricity. This method permits selective production of LNG and maximum recovery of natural gas liquids. The LNG is produced by routing a slipstream from the de-methanizer overhead stream through an expander generator. When the pressure is reduced through a gas expander, the expansion of the gas results in a considerable temperature drop of the gas stream, liquefying the slipstream. The nearly isentropic gas expansion also produces torque and therefore shaft power that can be converted into electricity. A portion of the produced LNG is used as a reflux stream in the de-methanizer, to control tower overhead temperature and hence ethane recovery. Moreover, generating an overhead de-methanizer stream substantially free of natural gas liquids is made possible.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] These and other features of the disclosure will become more apparent from the following description in which reference is made to the appended drawings; the drawings are for the purpose of illustration only and are not intended to in any way limit the scope of the invention to the particular embodiment or embodiments shown.
[0008] FIG. 1 is a schematic diagram of a facility equipped with a gas expander installed after the de-methanizer overhead stream to produce LNG; and
[0009] FIG. 2 is a schematic diagram of a facility equipped with a JT valve after the de-methanizer overhead stream to produce LNG.
DETAILED DESCRIPTION
[0010] The method will now be described with reference to FIG. 1 .
[0011] Referring to FIG. 1 , a pressurized natural gas stream 1 is routed to heat exchanger 2 where the temperature of the feed gas stream is reduced by indirect heat exchange with counter-current cool streams 6 , 29 , 30 , 32 , and 36 . The cooled stream 1 enters feed separator 3 where it is separated into vapour and liquid phases. The liquid phase stream 4 is expanded through valve 5 and pre-heated in heat exchanger 2 prior to introduction into de-methanizer column 11 through line 6 . The gaseous stream 7 is routed to gas expander 8 . The expanded and cooler vapor stream 9 is mixed with LNG for temperature control and routed through stream 10 into the upper section of distillation column 11 . The overhead stream 12 from de-methanizer column 11 is split into streams 13 and 32 . Stream 13 is routed to gas pre-treatment unit 14 to remove CO 2 , then through stream 15 enters gas expander 16 . Stream 15 pressure is dropped at gas expander 16 , the expansion of the gas results in a considerable temperature drop of the gas stream causing it to liquefy upon exiting gas expander 16 . The nearly isentropic expansion across the gas expander produces torque and therefore shaft power. The result of this energy conversion process is that the horsepower extracted from the natural gas stream is then transmitted to a shaft that drives an electrical generator 17 to produce electricity. The condensed stream 18 enters vessel 19 , the LNG receiver. The gaseous fraction in vessel 19 is routed through stream 36 into heat exchanger 2 to give up its cold, enters compressor 37 and the compressed gas stream 38 is mixed with compressed gas stream 34 to become stream 35 for distribution. LNG is fed through line 20 into pump 21 . The pressurized LNG stream 22 feeds streams 23 and 24 . Stream 23 is routed to LNG storage. The pressurized LNG stream 24 is routed through reflux temperature control valve 25 providing the reflux stream 26 to de-methanizer column 11 . A slipstream from the pressurized LNG stream 24 provides temperature control to stream 9 through temperature control valve 27 , temperature controlled stream 10 enters the upper section of de-methanizer column 11 . The controlled temperature of stream 10 by addition of LNG enables operation of the de-methanizer column at higher pressures to compensate for the loss of cool energy generated by the expander at higher backpressures. A second slipstream from pressurized LNG stream 24 provides methane for carbon dioxide stripping through flow control valve 28 , this LNG stream 29 is pre-heated in heat exchanger 2 before introduction into the lower section of the distillation column 11 as a stripping gas. The liquid fraction stream 30 is reboiled in heat exchanger 2 and routed back to the bottom section of de-methanizer column 11 , to control NGL product stream 31 . The distilled stream 32 , primarily methane, is pre-heated in heat exchanger 2 and routed to compressor 33 for distribution and or recompression through line 34 .
[0012] Referring to FIG. 2 , the main difference from FIG. 1 is the substitution of a gas expander to a JT valve 39 to control the pressure drop of stream 15 . This process orientation provides an alternative method to produce LNG at NGLs recovery plants albeit less efficient than when using an expander as shown in FIG. 1 . A pressurized natural gas stream 1 is routed to heat exchanger 2 where the temperature of the feed gas stream is reduced by indirect heat exchange with counter-current cool streams 30 , 29 , 6 , 32 and 36 . The cooled stream 1 enters feed separator 3 where it is separated into vapour and liquid phases. The liquid phase stream 4 is expanded through valve 5 and pre-heated in heat exchanger 2 prior to introduction into distillation column 11 through line 6 . The gaseous stream 7 is routed to gas expander 8 , the expanded and cooler vapor stream 9 is temperature controlled by LNG addition valve 27 , the cooler stream 10 is routed into the upper section of de-methanizer column 11 . The overhead stream 12 from de-methanizer column 11 is split into streams 13 and 32 . Stream 13 is routed to gas pre-treatment unit 14 to remove CO 2 , then through stream 15 enters JT valve 39 . Stream 15 pressure is dropped through JT valve 39 , the expansion of the gas results in a temperature drop of the gas stream causing it to partially condense upon exiting JT valve 39 . The partially condensed stream 18 enters vessel 19 , the LNG receiver, where the liquid components are separated from the gaseous phase components. The liquid phase stream, LNG, is fed through line 20 into pump 21 . The pressurized LNG stream 22 feeds streams 23 and 24 . Stream 23 is routed to LNG storage. The pressurized LNG stream 24 is routed through reflux temperature control valve 25 providing the reflux stream 26 to de-methanizer column 11 . A slipstream from the pressurized LNG stream 24 provides temperature control to stream 9 through temperature control valve 27 , temperature controlled stream 10 enters the upper section of de-methanizer column 11 . The controlled temperature of stream 10 by addition of LNG enables operation of the de-methanizer column at higher pressures to compensate for the loss of cool energy generated by the expander at higher backpressures. A slipstream from pressurized LNG stream 24 provides methane for carbon dioxide stripping through flow control valve 28 , the LNG stream 29 is pre-heated in heat exchanger 2 before introduction into the lower section of the de-methanizer column 11 as a stripping gas. The liquid fraction stream 30 is reboiled in heat exchanger 2 and routed back to the bottom section of de-methanizer column 11 , to control NGL product stream 31 . The gaseous stream 36 exits the LNG receiver 19 and is pre-heated in heat exchanger 2 , the now warmed gas stream enters compressor 37 and exits through line 38 and mixes with compressed gas stream 34 into natural gas distribution line 35 . The distilled stream 32 , primarily methane, is pre-heated in heat exchanger 2 and routed to compressor 33 the compressed gas stream 34 is mixed with compressed gas stream 38 for distribution and or recompression through line 35 .
[0013] In the preferred method, LNG is produced through a gas expander. A portion of the produced LNG provides cold energy that improves the operation and efficiency of NGL de-methanizer columns. Moreover, the gas expander generates electricity which reduces the energy required for recompression of gas for distribution.
[0014] In this patent document, the word “comprising” is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. A reference to an element by the indefinite article “a” does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one and only one of the elements.
[0015] The following claims are to be understood to include what is specifically illustrated and described above, what is conceptually equivalent, and what can be obviously substituted. The scope of the claims should not be limited by the embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole. | A method to recover natural gas liquids (NGLs) from natural gas streams at NGL recovery plants. The present disclosure relates to methods using liquid natural gas (LNG) as an external source of stored cold energy to reduce the energy and improve the operation of NGL distillation columns. More particularly, the present disclosure provides methods to efficiently and economically achieve higher recoveries of natural gas liquids at NGL recovery plants. | 5 |
The present application claims the benefit of the filing date U.S. Provisional Application Ser. No. 60/003,379, filed Sep. 7, 1995.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the manufacture of high strength, light weight parts made of composite materials. In particular, the present invention is a method for fabricating complex hollow composite structures from laminates of fiber reinforced synthetic resins.
2. Background
Bicycle frames and other hollow core structures have been traditionally been made from tubes of iron or steel brazed or welded together. More recently materials such as aluminum or titanium have been used to reduce weight. The use of composite structures of fiber reinforced resins have further reduced weight while maintaining high strength. Rather than utilizing welding or brazing for connecting tubing, composite structures can be made from layers of fiber material impregnated with thermosetting or thermoplastic resins. These sheets of impregnated fibers are called "prepregs" and are usually cured under heat and pressure in a mold to define the shape.
One of the problems with tubular structures, such as bicycle frames, is that stresses are highest at the tubing junctions. Thus the bicycle tubing should be thicker near the junctions for strength, and thinner in the long straight sections.
Some methods have utilized previously-cured tubing and used various methods for joining the tubes together by cementing, foam filling, or wrapping with prepreg and a second cure. For example, Derujinsky in U.S. Pat. No. 4,900,048 produces tubes by wrapping fabric on a tube mandrel, painting it with a resin, and applying pressure to it by wrapping with a peel ply tape. This results in low and uneven pressure which tends to leave voids and resin rich areas. It also gives a low content of reinforcing fiber.
The tubes are then cut and joined by wrapping the joints with fabric, painting them with resin, and using a peel ply tape wrapping to force the painted-on resin through the fabric. This is followed by a second cure. A second or separate cure cycle creates residual cure stresses at the interface of the different materials due to cure shrinkage. Also the load path is not direct from one tube member to the other because they have a joint. Thus it is not a true one piece seamless monocoque tubular structure.
Pai in U.S. Pat. No. 5,318,819 also uses pre-cured tubes with lugs at the joints. Tube and lug structures are intrinsically weaker than a seamless monocoque structure. Bags of expanding foaming adhesive are used for compacting the material wrapped over the pre-cured tubes. This second cure creates residual stresses at the interface due to cure shrinkage. Additionally the foam cannot be nearly as strong as the fiber reinforced material.
Duplessis in U.S. Pat. No. 5,080,385 uses inflatable bladders for compaction of prepreg material. Separate metal parts are also incorporated in the structure. However, the use of separate structural components that are joined together compromises the strength of the structure. Overlapping tabs are cut in the preformed tubes to form connections which can lead to undesirable wrinkles. Also, since the bladders do not provide proper compaction in the metal inserts, an expandable epoxy foam is used to fill sharp acute angles and voids in the metal pieces.
Trimble in U.S. Pat. No. 5,158,733 uses prepreg material of fiber reinforced heat curable resin laid up in female mold cavities. A bladder is used inside the mold to compact the prepreg from the inside, while the prepreg is held from the outside by the two halves of the mold. This technique allows only a single shear area to join and transfer all of the loads and stresses from one side of the frame to the other. The seam between the frame halves is created by extending the laminate on one side out past the mold surface and folding it over the expanding bladder. Upon pressurization, the bladder forces the folded laminate over against the opposite side creating a seam, which joins the two laminates at a single layer shear interface. This seam can fail under stress. A further problem is that the overlapped material may not be compressed properly by the bladder.
The use of inflatable bladders to supply compaction pressure often results in wrinkles caused by uneven pressure distribution. This further results in resin rich areas and high void regions. The laminate design must allow for these weak regions by adding more material and therefore weight. Also bridging may occur if the prepreg ply does not lay down properly in interior corners, and leaves voids in the laminate. In addition, the bladders must often be left inside the finished part, whenever a complex tubular path prevents mechanical extraction of the bladders.
Accordingly, forming thicker sections near junctions has not been practical in prior art. In some case, foam or resin filling has to be inserted in finished parts to increase the strength at junctions. This can result in bicycle frame failure under high stress conditions. Also, in female mold layups, it is difficult to work the layers of ply into position, because they must be pressed in with a rod or tool. This results in a high bulk factor. (The bulk factor is the ratio of the uncured thickness to the cured thickness. A lower bulk factor results in a stronger finished piece.) With a large bulk factor, the fibers at the outer surface may become wrinkled during compaction. The result is a reduction in the outer fibers' ability to carry the high loads and stress that are present under normal use.
SUMMARY OF THE INVENTION
The present invention is a method for fabricating hollow composite structures using a dimensional inner mandrel that expands during cure to provide laminate consolidation. After the curing process is complete, the inner mandrel is removed from inside of the laminate by solvent extraction.
The process starts with a hollow semi-rigid inner mandrel made of thermoplastic material such as polystyrene or ABS (acrylonitrile-butadiene-styrene co-polymer). Inside the thermoplastic mandrel is an elastomeric tube that is pressurized during cure. The thermoplastic mandrel is wrapped with plies of composite prepreg material. A prepreg of thermosetting or thermoplastic resin with high strength fiber reinforcement is used. Wrapping the mandrel is a quick and easy process. The mandrel is a semi-rigid structure and the tack of the prepreg conveniently holds the plies in place during lamination. Wrapping the prepreg on a male mandrel allows for accurate ply placement and control of laminate thickness. Fiber orientations are made at 0°, ±30°, ±45°, ±60°, and 90° overlaps to maximize strength at high stress points.
The mandrel, laminated with prepreg, is then placed in a mold and heated. The mandrel is inflated to the desired pressure. The consolidation pressure can range from 20-200 psi and even higher, while the curing temperature can range from 200°-600° F. (All pressures listed herein are relative to atmospheric pressure.) The pressure generated by the expanding core produces a highly consolidated composite structure that has fewer voids, a more uniform thickness, and an increased fiber content compared to hollow composites made by other fabrication methods. When an autoclave is used for curing, in which the pressure is exerted both on the external mold surface and the interior of the mandrel at the same time, soft tooling and high pressure may be used because of the absence of a differential pressure across the mold. These factors make a much stronger structure. The process is particularly useful for, but not limited to, fabricating high strength, lightweight structures such as bicycle frames.
The bulk factor of the material is minimized because the prepreg is pressed against the exterior surface of the semi-rigid mandrel, eliminating entrapped air and ply wrinkles.
The present invention allows for additional shapes to be molded into the interior of the hollow structure, with excellent dimensional control. This is accomplished by forming a mandrel to the desired section, prior to wrapping the mandrel with plies of the composite material.
The present invention is described herein in terms of fabricating bicycle frames. However, the present invention can be used in a wide variety of applications, and is not limited to bicycle frames. For example, as described in greater detail below, the present invention can be used for aerospace/aircraft applications such as for ducts, small wing structures, flaps, fins, and fuel cells; for model aircraft applications such as for frames or fuselages, fuel tanks, and wings; for motorcycle applications such as for handlebars, forks, swing arms, frames, fuel tanks, and seat structures; for automobile applications such as gas tanks or fuel cells, structural fluid containers, and electric car bodies and frames; for snowmobile applications such as for frames, bars, struts, and gas tanks; for watercraft, such as surfboards, bodyboards, kayaks, wind surfboards, and masts; for wheelchairs; for tractors and other utility vehicles; and for sporting goods such as tennis racquet or golf clubs.
Accordingly, it is an object of this invention to produce hollow composite structures that are true one piece seamless monocoque structures.
Another object of this invention is to produce hollow composite structures with less voids and higher fiber content for increased strength and more uniform thickness.
Another object of this invention is to use a semi-rigid mandrel to eliminate wrinkles, which often occur when pressurized air bags are used, and which cause resin-rich areas and voids in the composite structure.
Another object of this invention is to use a semi-rigid male mandrel to facilitate the lamination and layup of the prepreg thus minimizing the material bulk factor.
Another object of the present invention is to use a semi-rigid male mandrel that can incorporate dimensionally accurate, repeatable internal reinforcements on the inside surface of complex hollow structures. The reinforcements include, but are not limited to, hat stiffeners, bead stiffeners, blade stiffeners, ribs, and networks of ribs.
Another object of the invention is to consolidate prepreg laminates under high pressure which reduces void content, and improves the strength of the composite.
Another object of this invention is to make complex hollow composite structures with closely controlled external and internal dimensions.
Another object of this invention is to provide a means for removing the mandrel after cure in order to reduce weight.
Another object of the invention is to provide a method that uses soft tooling, yet allows for the use of high compaction pressures and autoclave curing.
Another object of the invention is the use of an internal mandrel which lends itself to several methods of pressurization during cure.
Another object of the invention is the use of a single cure cycle to produce complete homogeneity of material throughout the structure.
DESCRIPTION OF THE DRAWINGS
FIG. 1A is a schematic diagram of the mandrel thermal forming tool with thermoplastic sheet.
FIG. 1B is a schematic diagram of the thermal forming tool with thermoplastic sheet taped in place, assembled in the vacuum envelope bag.
FIG. 2A is a schematic diagram of two semi-rigid mandrel halves with elastomeric bladder.
FIG. 2B is a schematic diagram of the placement of the elastomeric bladder within the semi-rigid mandrel.
FIG. 2C is a schematic diagram of the assembled semi-rigid mandrel prepared for prepreg ply layup.
FIG. 3 is a schematic diagram illustrating a method of orienting fiber directions during layup for increased strength in high stress areas.
FIG. 4 is a schematic diagram of examples of tube cross sections and internal reinforcing structures.
FIG. 5A is a schematic diagram of a mandrel with applied laminations and curing mold halves.
FIG. 5B is a schematic diagram of the curing mold assembly in its vacuum bag.
FIG. 5C is a schematic diagram of the present invention.
FIG. 6 is a schematic diagram showing how the wall thickness of the composite can be varied, to reduce the overall weight of the structure while maintaining its structural strength near junctions.
FIG. 7 is a schematic diagram of a typical curing cycle.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described with reference to FIGS. 1-7.
A preferred method for fabricating the expandable, semi-rigid mandrel is by vacuum forming the mandrel in a mold. Molds can be fabricated, e.g., by machining wood such as mahogany to form the desired pattern. As shown in FIG. 1, mold 1 is used to form an expandable core. A sheet of 1/16 inch thick polystyrene 3, larger than the mold cavities 2, is placed on top of the mold, fully covering the cavity. The sheet is taped at the edges with high temperature tape to prevent movement during processing. The tape is shown as 4 in FIG. 1A. The mold is placed in an envelope vacuum bag 5 made of high elongation elastomer, preferably silicone with a minimum elongation of 400 percent.
The silicone vacuum bag, with vacuum connection 6, containing the mold is placed in an oven. The oven is heated to 275°-300° F. When the polystyrene sheet reaches 265°-285° F., as measured by thermocouples in direct contact with the polystyrene sheet, vacuum is applied to the silicone vacuum bag, and the polystyrene sheet is forced into the mold cavities, forming one half of a mandrel. The formed half of the mandrel is held at temperature, under vacuum, for a maximum of 5 minutes. The mold is removed from the oven and the formed mandrel half is allowed to cool below 200° F. prior to removal from the mold.
An elastomeric bladder is then placed inside a trimmed mandrel half, and a second mandrel half is taped to the first mandrel half, as shown in FIGS. 2A and 2B. The elastomeric bladder may be made of silicone or nylon films, or EPDM (ethylene-propylene terpolymer) rubber (which is the preferred material). The bladder is made by thermally sealing two flat layers of the bladder material to each other at their edges, using heat and pressure. The bladder is knotted at one end and inverted on itself to position the knot inside the tubing. This placement of the bladder in the mandrel prevents overexpansion and possible failure during pressurization.
FIG. 2B shows the proper placement of the bladder with a breather strip 10 placed inside the bladder to ensure a path for pressurization over the full length of the bladder. The semi-rigid mandrel, containing the elastomeric tubing, is taped together using Nylon tape 4 around the full perimeter as shown in FIG. 2C.
The assembled semi-rigid laminating mandrel is used for laying up sheets or tapes of the preferred prepreg material, which is standard 33 Msi modulus graphite fiber with epoxy resin. The preferred epoxy resin is a modified 250° F. curing system. The modifiers provide increased toughness and abrasion resistance. Other reinforcing fibers such as fiberglass, aramid, and boron may also be used. Thermoplastic as well as thermosetting resins may also be used. The semi-rigid mandrel facilitates the laying up process. The tack of the prepreg material allows for very accurate ply placement with no chance of movement as the male mandrel is loaded into the curing mold.
Multiple layers of prepreg overlaid at 0, ±45°, ±60° or 90° fiber orientation can be readily applied at junctions, for example, for local increases in strength and stiffness. Any orientation can be used depending upon the end use of the composite structure.
Different reinforcement fibers may be used in different layers on the same composite. In the preferred method, a combination of graphite, fiberglass, and aramid fibers are used depending upon the end use of the laminate. The preferred wall thickness for using the tubular composite in a bicycle frame is 0.100-0.125 inch in highly stressed areas, and 0.040-0.060 inch in low stress areas. Other thicknesses may be used in other structures.
FIG. 3 shows a ±45° orientation of laminate prepreg 12 with plain weave fabric, prepreg 13 with a 90° orientation, and prepreg 14 with a 0° orientation. FIG. 4 shows possible reinforcing structures that can be molded with proper mandrel geometries where 15 is a rib reinforced tube cross-section; 16 a hat stiffener reinforced tube cross-section; and 17 is a bead stiffener reinforced tube cross-section.
FIG. 5A shows a mandrel 18 with uncured laminate, curing mold 19, and vacuum-pressure port 21. The uncured laminate and mandrel are placed in a curing mold half. The other half of the split mold is aligned and bolted in place. The mold is placed into an envelope vacuum bag that is sealed around the base of the pressure nipple (as shown in detail in FIG. 5B),and the full perimeter of the vacuum bag. A vacuum source and monitor fitting are attached and connected to the corresponding autoclave fittings. Thermocouples are attached to the vacuum bag over the tool and to the readout instruments on the autoclave. Vacuum is applied, which is nominally 25-29 inches of mercury. Thermocouples are then checked for proper operation.
After the autoclave is closed, it is pressurized to at least 20 psi (typically 100 psi), at a rate of 5-10 psi per minute. The thermal cycle starts with a ramp rate of 3°-5° F. per minute and the pressure is maintained at 100 psi. At a predetermined temperature of at least 125° F. (typically, 150°±10° F.), the temperature is held for at least 5-10 minutes (typically, about 60 minutes). The temperature is then ramped at, e.g., 20 per minute to at least 200° F. (typically, 250° F.) and the part is held at that temperature for 90 minutes. The part is cooled to below 150° F. at a maximum rate of 5°-7° F. per minute.
FIG. 7 illustrates two exemplar curing cycles. The lower plots in FIG. 7 illustrate the pressure cycles (right-hand axis), and the upper plot illustrates the temperature cycle (left-hand axis). In the first example, the pressure is raised from atmospheric pressure to 100 psi at about 6-7 psi per minute over about 15 minutes, the pressure is maintained at 100 psi for an additional 4 hours and 15 minutes, and the pressure is allowed to ramp back down to atmospheric pressure at about 3-4 psi per minute over 30 minutes. The temperature is raised from ambient temperature to the curing temperature, 250° F. in this case, at a rate of 1.5° to 5° F. per minute It is maintained at 250° F. for an additional 90 minutes, and is then reduced to 100° F. over an additional 60 minutes, at a rate of 1.5°-2° F. per minute.
In the second example, the sample is subjected to an additional pressure step prior to the main curing step. As shown by the lower pressure plot in FIG. 7, the pressure is ramped at 3-5 psi/minute from atmospheric pressure to 25 psi. The pressure is held at 25 psi for 10 to 15 minutes, and then ramped up to 100 psi at 3-5 psi/minute. It is then held at 100 psi for 2.5 to 4.5 hours (in the case shown in FIG. 7 for about 3 hours and 15 minutes). The temperature cycle consists of heating the sample to about 150° F. over about 30 minutes, holding the sample at about 150° F. for about one hour, then heating the sample to about 250° F. over about one hour, then holding the sample at about 250° F. for about 90 minutes, and then allowing the sample to cool below 150° F. over about one hour, at a maximum cooling rate of 5° to 7° F. per minute. Once the temperature is below 150° F., the pressure is reduced to atmospheric pressure over about 30 minutes.
After the assembly is cured, it is removed from the autoclave and the composite structure is removed from the curing mold. The mandrel is then removed by solvent extraction, leaving no bag or bladder to snag control cables inside the bicycle frame. The solvent used is methyl-ethyl-ketone (MEK). The composite part can then be machined for metal fittings, finish sanded, and painted. FIG. 6 shows a cross-section of a cured part 25 illustrating the thickness variation for weight reduction.
An autoclave method for curing is preferred because soft tooling may be used with autoclave curing. Because there is minimal differential pressure across the mold, expensive hard metal molds are not required. Additionally, complex pressure connections do not need to be made to the mold, or to an enclosed pressurization bag. It also allows higher pressures to be used, e.g., 100-200 psi and even higher, which consolidates the laminate better than previous methods. Thus the present invention produces a fully monocoque, seamless structure which is strong and lightweight.
Although the preferred method of pressurization is to cure the assembly in an autoclave, methods using pressurized gas, pressurized liquids, or heat-expandable foams, paste, or beads may be used.
Additional Examples of Applications for the High Pressure Hollow Process
In addition to bicycles, many other structures have the bicycle's structural requirements of high strength, high rigidity, and light weight. For example, motorcycle frames, on a larger scale, share the bicycle's requirement for strong lightweight components, and thus would constitute a good application of the present invention. Placing strengthening material at the frame intersections without the usual limitations of seams and bonded joints allows large composite frames to be efficiently produced using the present invention. Channels could be incorporated into the resultant hollow frame to separate wiring from hot engine components and to ease installation. Strong lightweight composite frames would be especially desirable to drag racers, endurance racers and high performance sport bike enthusiasts. Similarly, frames for snowmobiles, tractors, buggies, aircraft and other vehicles could also be produced by the present invention, as well as bars and structural members such as handlebars, forks, swing arms and roll cages.
The present invention could also be used to manufacture a lightweight wheelchair chassis. The weight of a wheelchair is an important factor in its design and function since lightweight wheelchairs reduce fatigue when human-powered and consume less energy when electric-powered. Wheelchairs composed of lightweight composite materials are also more maneuverable and allow greater portability. The process used to make a wheelchair chassis would be similar to the bicycle frame except that the wheelchair frame would be created as two components connected by folding bars.
Other sporting goods besides bicycles can be produced using the present invention, including tennis, badminton and racquetball racquets. A flexible, semi-rigid mandrel would be formed in a general racquet shape, with the final form of the product being determined by the particular mold used. While other composite molding processes require the mandrel to remain in the finished product, the present invention allows the mandrel to be removed after the heating and curing process, producing a higher quality composite racquet.
The present invention could also be used to strengthen lightweight golf clubs. The two main parts of the golf club, the head and the shaft, are currently produced separately and then fastened or bonded together. While many golf club shafts are carbon fiber composite, golf club heads are still generally metallic. The present invention would allow a composite club with an integral shaft and head to be manufactured from one mold, eliminating the joint between the head and shaft. The integral head and shaft would allow the club to absorb more force without a corresponding weight penalty. Composite materials also dampen inherent vibration, reducing stress on the club itself and the hands, arms and shoulders of the golfer.
The rollerblade boot is another sporting good item which could be improved using the present invention. Currently many rollerblade boots are made from relatively heavy plastic. Composite boots would result in lighter, stiffer, faster and stronger rollerblades, reducing overall user fatigue. Few rollerblade boots are presently created from composite materials since many composite molding methods require the mandrel to become part of the finished product. The present invention would facilitate production of variously shaped composite rollerblade boots since the mandrel is dissolved after curing.
Larger structures, such as vehicle shells ranging from boat hulls and aircraft fuselages to automobile bodies, could also be manufactured using the present invention. A large mandrel would be wrapped with prepreg composite material, then heated and cured in a female mold. After removal from the mold, the mandrel is dissolved, resulting a strong, lightweight, hollow composite shell. Stringers and bulkheads could be incorporated into present invention hull molds instead of being produced separately and then bonded to the hull. The present invention would produce stronger joints between the hull and stringers without adding the bulk of extra bonding.
To fabricate an aircraft fuselage, a mandrel would be completely wrapped around prepreg to form a hollow shell of varying diameters from firewall to tail. The present invention could be used for sport aircraft where the entire fuselage would be fabricated in one mold, or for commercial aircraft where fuselage sections would be created from various molds and then bonded together. The present invention would also be appropriate for manufacturing other aircraft parts including wings, control surfaces, rotor blades, propeller blades, and antennae. On a smaller scale, the same process can be used for model aircraft component including fuselages, wings, frames and fuel cells.
Composite fuel cells are currently manufactured for several applications, including automobiles, aircraft, helicopters, ships, and other vehicles. The present invention would facilitate the production of complex fuel cells incorporating valve and fitting recesses or protrusions by increasing strength in corresponding joints without increasing the weight and need for various secondary operations required by prior art processes.
The foregoing disclosure of the preferred invention has been presented for the purpose of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many variations and modifications of the embodiments described herein will be obvious to one of ordinary skill in the art in light of the above information. The scope of the invention is to be defined only by the claims appended hereto. | A method of fabricating complex hollow composite structures from laminates of fiber reinforced synthetic resins. The structures are fully monocoque tubes with no seams. The tubes are manufactured by wrapping a hollow semi-rigid inner mandrel made of thermoplastic material such as polystyrene or ABS (acrylonitrile-butadiene-styrene co-polymer) with layers of composite sheets. The sheets are made from high-strength fibers impregnated with thermosetting or thermoplastic resins.
The laminated mandrel is placed in a mold, heated and inflated to a predetermined pressure. The pressure can range from 20-200 psig and even higher, while the curing temperature can range from 200°-600° F. The pressure generated by the expanding core produces a highly consolidated composite structure that has fewer voids, a more uniform thickness, and an increased fiber content compared to hollow composites made by other fabrication methods. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a United States National Stage Application under 35 USC §371 of PCT/IB2007/055245, filed Dec. 20, 2007, which claims the benefit of PCT/IB2006/055019, filed Dec. 22, 2006, the contents of each of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to novel 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives of formula (I) and their use as pharmaceuticals. The invention also concerns related aspects including processes for the preparation of the compounds, pharmaceutical compositions containing one or more compounds of formula (I), and especially their use as orexin receptor antagonists.
Orexins (orexin A or OX-A and orexin B or OX-B) are novel neuropeptides found in 1998 by two research groups, orexin A is a 33 amino acid peptide and orexin B is a 28 amino acid peptide (Sakurai T. et al., Cell, 1998, 92, 573-585). Orexins are produced in discrete neurons of the lateral hypothalamus and bind to the G-protein-coupled receptors (OX 1 and OX 2 receptors). The orexin-1 receptor (OX 1 ) is selective for OX-A, and the orexin-2 receptor (OX 2 ) is capable to bind OX-A as well as OX-B. Orexins are found to stimulate food consumption in rats suggesting a physiological role for these peptides as mediators in the central feedback mechanism that regulates feeding behaviour (Sakurai T. et al., Cell, 1998, 92, 573-585). On the other hand, it was also observed that orexins regulate states of sleep and wakefulness opening potentially novel therapeutic approaches to narcolepsy as well as insomnia and other sleep disorders (Chemelli R. M. et al., Cell, 1999, 98, 437-451).
Orexin receptors are found in the mammalian brain and may have numerous implications in pathologies as known from the literature.
Up to now, some low molecular weight compounds are known having a potential to antagonise either specifically OX 1 or OX 2 , or both receptors at the same time. In WO01/85693, Banyu Pharmaceuticals claimed N-acyltetrahydroisoquinoline derivatives.
Other orexin receptor antagonists such as novel benzazepine derivatives are disclosed in WO02/051838. Pyrazolo-tetrahydropyridine derivatives as orexin receptor antagonists are known from WO07/122,591.
Furthermore, the use of solution-phase chemistry for the lead optimization of 1,2,3,4-tetrahydroisoquinoline derivatives as potential orexin receptor antagonists has been reported (Chimia, 2003, 57, 270-275).
BRIEF SUMMARY OF THE INVENTION
The present invention provides novel substituted 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives, which are non-peptide antagonists of human orexin OX 1 and/or OX 2 receptors. These compounds are in particular of potential use in the treatment of e.g. eating disorders, drinking disorders, sleep disorders, or cognitive dysfunctions in psychiatric and neurologic disorders.
Various embodiments of the invention are presented hereafter:
i) A first aspect of the invention relates to 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives of formula (I),
wherein
X represents CH 2 or O;
R 1 represents a phenyl group, which group is independently mono-, di-, or tri-substituted wherein the substituents are independently selected from the group consisting of (C 1-4 )alkyl, (C 1-4 )alkoxy, halogen, cyano, trifluoromethoxy and trifluoromethyl;
R 2 represents (C 1-4 )alkyl, (C 1-4 )alkoxy, (C 2-4 )alkenyl, halogen, cyano, hydroxymethyl, trifluoromethyl, C(O)NR 5 R 6 or cyclopropyl;
R 3 represents (C 1-4 )alkyl, (C 1-4 )alkoxy-methyl or halogen;
R 4 represents (C 1-4 )alkyl;
R 5 represents hydrogen or (C 1-4 )alkyl;
R 6 represents hydrogen or (C 1-4 )alkyl.
In another embodiment of the invention, compounds of formula (I) and (II; see below) also encompass pure enantiomers, mixtures of enantiomers, pure diastereoisomers, mixtures of diastereoisomers, diastereoisomeric racemates, mixtures of diastereoisomeric racemates, pharmaceutically acceptable salts and solvation complexes thereof. In preferred embodiment of the invention, compounds of formula (I) and (II) also encompass pharmaceutically acceptable salts thereof.
As above-mentioned, the present invention encompasses also solvation complexes of compounds of formula (I) and (II). The solvation can be effected in the course of the manufacturing process or can take place separately, e.g. as a consequence of hygroscopic properties of an initially anhydrous compound of formula (I) and (II).
In the present description the term “halogen” means fluorine, chlorine, bromine or iodine.
For the substituent R 1 , the term “halogen” means fluorine, chlorine, or bromine, and preferably fluorine or chlorine. More preferred the term “halogen” means fluorine.
For the substituent R 2 , the term “halogen” means fluorine, chlorine, bromine or iodine, and preferably chlorine.
For the substituent R 3 , the term “halogen” means fluorine, chlorine, bromine or iodine, and preferably chlorine.
The term “(C 1-4 )alkyl”, alone or in combination, means a straight-chain or branched-chain alkyl group with 1 to 4 carbon atoms. Examples of (C 1-4 )alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl or tert.-butyl; the term “(C 1-2 )alkyl” means a methyl or ethyl group. Preferred are methyl and ethyl.
For the substituent R 1 , the term “(C 1-4 )alkyl” means preferably methyl or ethyl. More preferred the term “(C 1-4 )alkyl” means methyl.
For the substituent R 2 , the term “(C 1-4 )alkyl” means preferably methyl or ethyl.
For the substituent R 3 , the term “(C 1-4 )alkyl” means preferably methyl, ethyl, n-propyl or isopropyl. More preferred the term “(C 1-4 )alkyl” means methyl or ethyl. Most preferred the term “(C 1-4 )alkyl” means ethyl.
For the substituent R 4 , the term “(C 1-4 )alkyl” means preferably methyl.
For the substituent R 5 , the term “(C 1-4 )alkyl” means preferably methyl.
For the substituent R 6 , the term “(C 1-4 )alkyl” means preferably methyl.
The term “(C 2-4 )alkenyl”, alone or in combination, means a straight-chain or branched-chain alkenyl group with 2 to 4 carbon atoms, preferably vinyl and allyl.
The term “(C 1-4 )alkoxy”, alone or in combination, means a group of the formula (C 1-4 )alkyl-O— in which the term “(C 1-4 )alkyl” has the previously given significance, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxy or tert.-butoxy. Preferred are methoxy and ethoxy.
For the substituent R 1 , the term “(C 1-4 )alkoxy” means preferably methoxy.
For the substituent R 2 , the term “(C 1-4 )alkoxy” means preferably methoxy.
The term “(C 1-4 )alkoxy-methyl”, alone or in combination, means a group of the formula (C 1-4 )alkoxy-CH 2 — in which the term “(C 1-4 )alkoxy” has the previously given significance. An example is methoxymethyl.
For the substituent R 1 , the term phenyl group is preferably independently mono-, di-, or tri-substituted wherein the substituents are independently selected from the group consisting of (C 1-4 )alkyl, (C 1-4 )alkoxy, halogen, cyano, trifluoromethoxy and trifluoromethyl. Examples are trifluoromethyl-phenyl (e.g. 4-trifluoromethyl-phenyl, 3-trifluoromethyl-phenyl), trifluoromethoxy-phenyl (e.g. 4-trifluoromethoxy-phenyl), chloro-phenyl (e.g. 2-chloro-phenyl, 3-chloro-phenyl and 4-chloro-phenyl), methyl-phenyl (e.g. 2-methyl-phenyl, 3-methyl-phenyl, 4-methyl-phenyl), cyano-phenyl (e.g. 4-cyano-phenyl), dimethyl-phenyl (e.g. 2,3-dimethyl-phenyl, 2,4-dimethyl-phenyl, 3,4-dimethyl-phenyl), dimethoxy-phenyl (e.g. 2,5-dimethoxy-phenyl, 2,4-dimethoxy-phenyl), fluoro-methoxy-phenyl (e.g. 3-fluoro-4-methoxy-phenyl), fluoro-trifluoromethyl-phenyl (e.g. 3-fluoro-4-trifluoromethyl-phenyl, 2-fluoro-4-trifluoromethyl-phenyl, 4-fluoro-3-trifluoromethyl-phenyl), dichloro-phenyl (e.g. 2,4-dichloro-phenyl), difluoro-phenyl (e.g. 3,4-difluoro-phenyl), fluoro-methyl-phenyl (e.g. 3-fluoro-4-methyl-phenyl), chloro-trifluoromethyl-phenyl (e.g. 3-chloro-4-trifluoromethyl-phenyl), difluoro-methyl-phenyl (e.g. 3,5-difluoro-4-methyl-phenyl, 2,4-difluoro-3-methyl-phenyl), difluoro-methoxy-phenyl (e.g. 3,5-difluoro-4-methoxy-phenyl, 2,5-difluoro-4-methoxy-phenyl), difluoro-trifluoromethyl-phenyl (e.g. 3,5-difluoro-4-trifluoromethyl-phenyl, 2,5-difluoro-4-trifluoromethyl-phenyl), trifluoro-phenyl (e.g. 2,3,5-trifluoro-phenyl, 3,4,5-trifluoro-phenyl), and chloro-difluoro-phenyl (e.g. 4-chloro-3,5-difluoro-phenyl). Especially examples are trifluoromethyl-phenyl (e.g. 4-trifluoromethyl-phenyl), chloro-phenyl (e.g. 2-chloro-phenyl, 3-chloro-phenyl and 4-chloro-phenyl), methyl-phenyl (e.g. 2-methyl-phenyl, 3-methyl-phenyl, 4-methyl-phenyl), dimethyl-phenyl (e.g. 2,3-dimethyl-phenyl, 2,4-dimethyl-phenyl, 3,4-dimethyl-phenyl), dimethoxy-phenyl (e.g. 2,5-dimethoxy-phenyl, 2,4-dimethoxy-phenyl), fluoro-methoxy-phenyl (e.g. 3-fluoro-4-methoxy-phenyl), dichloro-phenyl (e.g. 2,4-dichloro-phenyl), difluoro-phenyl (e.g. 3,4-difluoro-phenyl), fluoro-methyl-phenyl (e.g. 3-fluoro-4-methyl-phenyl), difluoro-methyl-phenyl (e.g. 3,5-difluoro-4-methyl-phenyl), fluoro-trifluoromethyl-phenyl (e.g. 3-fluoro-4-trifluoromethyl-phenyl) and difluoro-trifluoromethyl-phenyl (e.g. 3,5-difluoro-4-trifluoromethyl-phenyl). In another embodiment examples are trifluoromethyl-phenyl (e.g. 4-trifluoromethyl-phenyl, 3-trifluoromethyl-phenyl), trifluoromethoxy-phenyl (e.g. 4-trifluoromethoxy-phenyl), chloro-phenyl (e.g. 3-chloro-phenyl), methyl-phenyl (e.g. 4-methyl-phenyl), cyano-phenyl (e.g. 4-cyano-phenyl), dimethyl-phenyl (e.g. 2,3-dimethyl-phenyl, 2,4-dimethyl-phenyl, 3,4-dimethyl-phenyl), dimethoxy-phenyl (e.g. 2,4-dimethoxy-phenyl), fluoro-methoxy-phenyl (e.g. 3-fluoro-4-methoxy-phenyl), fluoro-trifluoromethyl-phenyl (e.g. 3-fluoro-4-trifluoromethyl-phenyl, 2-fluoro-4-trifluoromethyl-phenyl, 4-fluoro-3-trifluoromethyl-phenyl), dichloro-phenyl (e.g. 2,4-dichloro-phenyl), difluoro-phenyl (e.g. 3,4-difluoro-phenyl), fluoro-methyl-phenyl (e.g. 3-fluoro-4-methyl-phenyl), chloro-trifluoromethyl-phenyl (e.g. 3-chloro-4-trifluoromethyl-phenyl), difluoro-methyl-phenyl (e.g. 3,5-difluoro-4-methyl-phenyl, 2,4-difluoro-3-methyl-phenyl), difluoro-methoxy-phenyl (e.g. 3,5-difluoro-4-methoxy-phenyl, 2,5-difluoro-4-methoxy-phenyl), difluoro-trifluoromethyl-phenyl (e.g. 3,5-difluoro-4-trifluoromethyl-phenyl, 2,5-difluoro-4-trifluoromethyl-phenyl), trifluoro-phenyl (e.g. 2,3,5-trifluoro-phenyl, 3,4,5-trifluoro-phenyl), and chloro-difluoro-phenyl (e.g. 4-chloro-3,5-difluoro-phenyl).
The term “C(O)NR 5 R 6 ” means for example C(O)N(CH 3 ) 2 .
Also part of the invention are compounds of the formula (I) and/or (Ia) and pharmaceutically acceptable salts thereof.
The term “pharmaceutically acceptable salts” refers to non-toxic, inorganic or organic acid and/or base addition salts. Reference can be made to “Salt selection for basic drugs”, Int J. Pharm . (1986), 33, 201-217.
The compounds of general formula (I) and (II) may contain two or more stereogenic or asymmetric centers, such as two or more asymmetric carbon atoms. Substituents at a double bond or a ring may be present in cis- or trans-form unless indicated otherwise. The compounds of formula (I) and (II) may thus be present as mixtures of stereoisomers or preferably as pure stereoisomers. Mixtures of stereoisomers may be separated in a manner known to a person skilled in the art.
ii) A further embodiment of the invention relates to compounds of formula (I) according to embodiment i), wherein, in case X represents CH 2 , the absolute configuration is [(R)-2′; (S)-8] or [(R)-2′; (R)-8]; or, in case X represents O, the absolute configuration is [(R)-2′; (S)-8] or [(R)-2′; (R)-8].
iii) A further embodiment of the invention relates to compounds of formula (I) according to embodiment i) or ii) which are also compounds of formula (II), wherein, in case X represents CH 2 , the absolute configuration is [(R)-2′; (S)-8]; or, in case X represents O, the absolute configuration is [(R)-2′; (R)-8]:
iv) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to iii), wherein
R 1 represents a phenyl group, which is independently mono-, di-, or tri-substituted wherein the substituents are independently selected from the group consisting of (C 1-4 )alkyl, (C 1-4 )alkoxy, halogen, trifluoromethoxy and trifluoromethyl;
R 2 represents (C 1-4 )alkoxy, halogen, cyano or trifluoromethyl; and
R 3 represents (C 1-4 )alkyl or halogen.
v) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to iv), wherein
R 1 represents a phenyl group, which is independently mono-, di-, or tri-substituted wherein the substituents are independently selected from the group consisting of (C 1-4 )alkyl, halogen and trifluoromethyl.
vi) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to iv), wherein
R 1 represents a phenyl group, which is independently di-, or tri-substituted wherein the substituents are independently selected from the group consisting of methyl, methoxy, fluorine, chlorine and trifluoromethyl.
vii) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to vi), wherein
R 1 represents a phenyl group, which is independently di-, or tri-substituted wherein the substituents are independently selected from the group consisting of methyl, fluorine and trifluoromethyl.
viii) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to vi), wherein
R 2 represents (C 1-4 )alkoxy, halogen, cyano or trifluoromethyl.
ix) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to viii), wherein
R 2 represents methoxy, chlorine, cyano or trifluoromethyl.
x) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to ix), wherein
R 2 represents methoxy, chlorine or cyano.
xi) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to x), wherein R 2 represents chlorine.
xii) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to xi), wherein
R 3 represents (C 1-4 )alkyl or halogen.
xiii) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to xii), wherein
R 3 represents methyl, ethyl, n-propyl, isopropyl or chlorine.
xiv) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to xiii), wherein
R 3 represents methyl or ethyl.
xv) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to xiv), wherein
R 3 represents ethyl.
xvi) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to xv), wherein R 4 represents methyl.
xvii) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to xvi), wherein
R 5 represents hydrogen or methyl; and
R 6 represents hydrogen or methyl.
xviii) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to xvii), wherein X represents CH 2 .
xix) A further embodiment of the invention relates to compounds of formula (I) according to any one of embodiments i) to xvii), wherein X represents O.
xx) In another embodiment of the invention compounds of formula (I) according to embodiment i) are selected from the group consisting of:
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(R)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(R)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-isopropyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-isopropyl-(R)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-isopropyl-1-methoxy-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{(S)-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{(R)-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1,3-dimethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-ethyl-1-methyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{8-[2-(3-chloro-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-[1,3-dimethyl-8-(2-p-tolyl-ethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide; (R)-2′-{8-[2-(2,3-dimethyl-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{8-[2-(2,4-dimethyl-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{8-[2-(2,4-dimethoxy-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{8-[2-(2,4-dichloro-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{(S)-8-[2-(3,4-difluoro-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-ethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-cyano-3-ethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-cyano-3-ethyl-(R)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-ethyl-1-hydroxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-ethyl-1-trifluoromethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-ethyl-1-trifluoromethyl-(R)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; 3-ethyl-7-(methylcarbamoyl-phenyl-methyl)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carboxylic acid methylamide; (R)-2′-{1,3-dichloro-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(4-cyano-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-cyano-3-ethyl-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-cyano-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-propyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-cyclopropyl-3-methyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-[1-chloro-3-ethyl-(R)-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide; (R)-2′-[1-chloro-3-ethyl-(R)-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide; (R)-2′-[1-chloro-(R)-8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide; and (R)-2′-[1-chloro-3-ethyl-(R)-8-(3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide;
wherein the first 42 compounds of the above list are especially preferred.
xxi) In another embodiment of the invention compounds of formula (I) according to embodiment i) are selected from the group consisting of:
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(R)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(R)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-isopropyl-1-methoxy-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{(S)-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-ethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-cyano-3-ethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-ethyl-1-trifluoromethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-isopropyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-isopropyl-(R)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{3-ethyl-1-methyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{8-[2-(3-chloro-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-[1,3-dimethyl-8-(2-p-tolyl-ethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide; (R)-2′-{8-[2-(2,4-dimethyl-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{(R)-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; 3-ethyl-7-(methylcarbamoyl-phenyl-methyl)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carboxylic acid methylamide; (R)-2′-{(S)-8-[2-(3,4-difluoro-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1,3-dichloro-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(4-cyano-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-cyano-3-ethyl-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-cyano-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-propyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-cyclopropyl-3-methyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-{1-chloro-(S)-8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide; (R)-2′-[1-chloro-3-ethyl-(R)-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide; (R)-2′-[1-chloro-3-ethyl-(R)-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide; (R)-2′-[1-chloro-(R)-8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide; and (R)-2′-[1-chloro-3-ethyl-(R)-8-(3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide;
wherein the first 34 compounds of the above list are especially preferred.
The compounds of general formula (I) and (II) and their pharmaceutically acceptable salts can be used as medicaments, e.g. in the form of pharmaceutical compositions for enteral or parenteral administration.
A further aspect of the invention is a pharmaceutical composition containing at least one compound according to formula (I) and/or (Ia), or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier material.
The production of the pharmaceutical compositions can be effected in a manner which will be familiar to any person skilled in the art (see for example Remington, The Science and Practice of Pharmacy, 21st Edition (2005), Part 5, “Pharmaceutical Manufacturing” [published by Lippincott Williams & Wilkins]) by bringing the described compounds of Formula (I) and (II) or their pharmaceutically acceptable salts, optionally in combination with other therapeutically valuable substances, into a galenical administration form together with suitable, non-toxic, inert, therapeutically compatible solid or liquid carrier materials and, if desired, usual pharmaceutical adjuvants.
The compounds of general formula (I) and (II) are useful for the treatment and/or prevention of the diseases mentioned herein.
Where the plural form is used for compounds, salts, pharmaceutical compositions, diseases or the like, this is intended to mean also a single compound, salt, disease or the like.
In one embodiment, the invention relates to a method for the treatment and/or prevention of the diseases mentioned herein, said method comprising administering to a subject a pharmaceutically active amount of a compound of general formula (I) and (II).
The compounds according to general formula (I) and (II) may be used for the preparation of a medicament and are suitable for the prevention or treatment of diseases selected from the group consisting of dysthymic disorders including major depression and cyclothymia, affective neurosis, all types of manic depressive disorders, delirium, psychotic disorders, schizophrenia, catatonic schizophrenia, delusional paranoia, adjustment disorders and all clusters of personality disorders; schizoaffective disorders; anxiety disorders including generalized anxiety, obsessive compulsive disorder, posttraumatic stress disorder, panic attacks, all types of phobic anxiety and avoidance; separation anxiety; all psychoactive substance use, abuse, seeking and reinstatement; all types of psychological or physical addictions, dissociative disorders including multiple personality syndromes and psychogenic amnesias; sexual and reproductive dysfunction; psychosexual dysfunction and addiction; tolerance to narcotics or withdrawal from narcotics; increased anaesthetic risk, anaesthetic responsiveness; hypothalamic-adrenal dysfunctions; disturbed biological and circadian rhythms; sleep disturbances associated with diseases such as neurological disorders including neuropathic pain and restless leg syndrome; sleep apnea; narcolepsy; chronic fatigue syndrome; insomnias related to psychiatric disorders; all types of idiopathic insomnias and parasomnias; sleep-wake schedule disorders including jet-lag; all dementias and cognitive dysfunctions in the healthy population and in psychiatric and neurological disorders; mental dysfunctions of aging; all types of amnesia; severe mental retardation; dyskinesias and muscular diseases; muscle spasticity, tremors, movement disorders; spontaneous and medication-induced dyskinesias; neurodegenerative disorders including Huntington's, Creutzfeld-Jacob's, Alzheimer's diseases and Tourette syndrome; Amyotrophic lateral sclerosis; Parkinson's disease; Cushing's syndrome; traumatic lesions; spinal cord trauma; head trauma; perinatal hypoxia; hearing loss; tinnitus; demyelinating diseases; spinal and cranial nerve diseases; ocular damage; retinopathy; epilepsy; seizure disorders; absence seizures, complex partial and generalized seizures; Lennox-Gastaut syndrome; migraine and headache; pain disorders; anaesthesia and analgesia; enhanced or exaggerated sensitivity to pain such as hyperalgesia, causalgia, and allodynia; acute pain; burn pain; atypical facial pain; neuropathic pain; back pain; complex regional pain syndrome I and II; arthritic pain; sports injury pain; dental pain; pain related to infection e.g. by HIV; post-chemotherapy pain; post-stroke pain; post-operative pain; neuralgia; osteoarthritis; conditions associated with visceral pain such as irritable bowel syndrome; eating disorders; diabetes; toxic and dysmetabolic disorders including cerebral anoxia, diabetic neuropathies and alcoholism; appetite, taste, eating, or drinking disorders; somatoform disorders including hypochondriasis; vomiting/nausea; emesis; gastric dyskinesia; gastric ulcers; Kallman's syndrome (anosmia); impaired glucose tolerance; intestinal motility dyskinesias; hypothalamic diseases; hypophysis diseases; hyperthermia syndromes, pyrexia, febrile seizures, idiopathic growth deficiency; dwarfism; gigantism; acromegaly; basophil adenoma; prolactinoma; hyperprolactinemia; brain tumors, adenomas; benign prostatic hypertrophy, prostate cancer; endometrial, breast, colon cancer; all types of testicular dysfunctions, fertility control; reproductive hormone abnormalities; hot flashes; hypothalamic hypogonadism, functional or psychogenic amenorrhea; urinary bladder incontinence asthma; allergies; all types of dermatitis, acne and cysts, sebaceous gland dysfunctions; cardiovascular disorders; heart and lung diseases, acute and congestive heart failure; hypotension; hypertension; dyslipidemias, hyperlipidemias, insulin resistance; urinary retention; osteoporosis; angina pectoris; myocardial infarction; arrhythmias, coronary diseases, left ventricular hypertrophy; ischemic or haemorrhagic stroke; all types of cerebrovascular disorders including subarachnoid haemorrhage, ischemic and hemorrhagic stroke and vascular dementia; chronic renal failure and other renal diseases; gout; kidney cancer; urinary incontinence; and other diseases related to general orexin system dysfunctions.
Compounds of general formula (I) and (II) are particularly suitable for the treatment of diseases or disorders selected from the group consisting of all types of sleep disorders, of stress-related syndromes, of psychoactive substance use and abuse, of cognitive dysfunctions in the healthy population and in psychiatric and neurologic disorders, of eating or drinking disorders. Eating disorders may be defined as comprising metabolic dysfunction; dysregulated appetite control; compulsive obesities; emeto-bulimia or anorexia nervosa. Pathologically modified food intake may result from disturbed appetite (attraction or aversion for food); altered energy balance (intake vs. expenditure); disturbed perception of food quality (high fat or carbohydrates, high palatability); disturbed food availability (unrestricted diet or deprivation) or disrupted water balance. Drinking disorders include polydipsias in psychiatric disorders and all other types of excessive fluid intake. Sleep disorders include all types of parasomnias, insomnias, narcolepsy and other disorders of excessive sleepiness, sleep-related dystonias; restless leg syndrome; sleep apneas; jet-lag syndrome; shift-work syndrome, delayed or advanced sleep phase syndrome or insomnias related to psychiatric disorders. Insomnias are defined as comprising sleep disorders associated with aging; intermittent treatment of chronic insomnia; situational transient insomnia (new environment, noise) or short-term insomnia due to stress; grief; pain or illness. Insomnia also include stress-related syndromes including post-traumatic stress disorders as well as other types and subtypes of anxiety disorders such as generalized anxiety, obsessive compulsive disorder, panic attacks and all types of phobic anxiety and avoidance; psychoactive substance use, abuse, seeking and reinstatement are defined as all types of psychological or physical addictions and their related tolerance and dependence components. Cognitive dysfunctions include deficits in all types of attention, learning and memory functions occurring transiently or chronically in the normal, healthy, young, adult or aging population, and also occurring transiently or chronically in psychiatric, neurologic, cardiovascular and immune disorders.
In a further preferred embodiment of the invention compounds of general formula (I) and (II) are particularly suitable for the treatment of diseases or disorders selected from the group consisting of sleep disorders that comprises all types of insomnias, narcolepsy and other disorders of excessive sleepiness, sleep-related dystonias, restless leg syndrome, sleep apneas, jet-lag syndrome, shift-work syndrome, delayed or advanced sleep phase syndrome or insomnias related to psychiatric disorders.
In another preferred embodiment of the invention compounds of general formula (I) and (II) are particularly suitable for the treatment of diseases or disorders selected from the group consisting of cognitive dysfunctions that comprise deficits in all types of attention, learning and memory functions occurring transiently or chronically in the normal, healthy, young, adult or aging population, and also occurring transiently or chronically in psychiatric, neurologic, cardiovascular and immune disorders.
In another preferred embodiment of the invention compounds of general formula (I) and (II) are particularly suitable for the treatment of diseases or disorders selected from the group consisting of eating disorders that comprise metabolic dysfunction; dysregulated appetite control; compulsive obesities; emeto-bulimia or anorexia nervosa.
In another preferred embodiment of the invention compounds of general formula (I) and (II) are particularly suitable for the treatment of diseases or disorders selected from the group consisting of psychoactive substance use and abuse that comprise all types of psychological or physical addictions and their related tolerance and dependence components.
DETAILED DESCRIPTION OF THE INVENTION
Compounds of general formula (I) and (II) belonging to this invention could be prepared according to several synthetic routes described below (schemes 1 to 13). All chemical transformations can be performed according to well-known standard methodologies as described in the literature or as described in the procedures below. Starting materials are commercially available or prepared according to procedures known in the literature or as illustrated herein. Some of the examples may be further modified by manipulation of substituents to result in additional examples. These manipulations may include, but are not limited to, reduction, oxidation, alkylation, acylation, and hydrolysis reactions which are commonly known to those skilled in the art. The order of carrying out the foregoing reaction schemes may be varied to facilitate the reaction or to avoid side-products.
An overview of the general synthetic route is presented in scheme 1. Tri-substituted-imidazole derivatives represented key intermediates in this synthesis and therefore their regioselective preparation was envisaged. Thus, the issue of tautomerism associated with imidazoles (and leading to isomeric mixtures) was circumvented in this approach through the use of pseudosymmetric 4,5-diiodoimidazole derivatives. Diiodination (I 2 /Na 2 CO 3 ) of 2-substituted imidazoles A (from commercial sources or from regioselective syntheses as described in scheme 5) gave the corresponding 4,5-diiodoimidazoles B. Deprotonation of pseudosymmetric B (NaH/DMF) and subsequent N-alkylation with (2-bromo-ethyl)-carbamic acid tert-butyl ester furnished exclusively the product C. The pivotal step of this synthetic route was the efficient preparation of the corresponding 4-iodoimidazoles D by using a regioselective exchange of the 5-iodo moiety for MgBr (EtMgBr/THF/−40° C.) followed by trapping of the carbanion with water. This process proved to be highly regioselective and only the expected 4-iodoimidazole derivatives D could be detected (as evidenced by 1 H-NMR). Moreover this approach afforded an operational, convenient and rapid synthesis of these key substrates and could be accomplished on a multigram-scale (see experimental part). Boc-deprotection of D led smoothly to the corresponding primary amines E which were allowed to react with aldehydes R 1 —X—CH 2 —CHO in a microwave-assisted Pictet-Spengler like reaction. Subsequent Boc-protection and purification gave the expected 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives F with good to high overall yields. The versatility of the iodo-substituent allowed the access to a variety of derivatives G (see scheme 6 for the introduction of diverse functional groups and substituents). Boc-deprotection of G followed by N-alkylation with electrophiles H (see schemes 4 and 13) furnished the compounds of formula (I) and (II).
The additional building block O was synthesized (scheme 2) in order to prepare some specific compounds of formula (I) and (II) containing either R 3 substituents which would be too sensitive and therefore incompatible with the quite harsh reaction conditions of the microwave-assisted Pictet-Spengler like reaction or containing specific R 2 /R 3 combinations which would not be conveniently incorporated by application of the general synthesis depicted in scheme 1. Iodination of imidazole J (I 2 /Na 2 CO 3 ) led smoothly to 2,4,5-triiodo-1H-imidazole K which was N-alkylated (NaH/BrCH 2 CH 2 NHBoc) giving compound L. Regioselective one-pot removal of two iodo-substituents with ethylmagnesium bromide (first on position-2, and secondly on position-5) furnished exclusively the expected 4-iodoimidazole derivative M which was Boc-deprotected (HCl in dioxane). The obtained primary amine N was then allowed to react with aldehydes R 1 —X—CH 2 —CHO in a microwave-assisted Pictet-Spengler like reaction. Subsequent Boc-protection and purification afforded the 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives O. With this building block O in hand, the planned specific combinations of R 2 /R 3 substituents could be introduced by iodine/metal exchange and trapping of the resulting carbanion with appropriate electrophiles, by transition metal-catalyzed cross-coupling reactions (mainly Stille cross-coupling reactions), and by aromatic electrophilic substitution reactions performed on the imidazole moiety (scheme 2). This synthetic route was particularly appropriate for the preparation of compounds of formula (I) and (II) with R 3 representing halogen.
As shown in scheme 3, specific R 2 -substituents could be also advantageously introduced at the earlier stage of imidazole derivative D in order to avoid side-reactions susceptible to occur in the remaining steps (e.g. aromatic nucleophilic substitution reactions with some specifically substituted R 1 residues). Remaining steps affording compounds of general formula (I) and (II) were as previously described in scheme 1.
In a slightly different synthetic route, secondary amine Q could be N-alkylated with ester derivative R (instead of amide derivative H) affording intermediate S which can either be directly transformed into target compounds I (by reaction with amine R 4 —NH 2 ) or which can be first hydrolyzed to the corresponding carboxylic acid T followed by coupling with amine R 4 —NH 2 (scheme 4).
A variety of useful 2-substituted imidazoles A were conveniently obtained either from commercial sources or from regioselective synthesis (scheme 5). Treatment of 1-trityl-1H-imidazole with n-butyllithium allowed the abstraction of the most acidic H-2 hydrogen and the generation of the corresponding carbanion. In a next step, this carbanion can react with electrophiles to form 1-trityl-2-E-imidazoles. The triphenylmethyl group could be smoothly removed by acid hydrolysis (AcOH/MeOH) to give the expected 2-substituted imidazoles A. Selected preparations are exemplified in scheme 5 but are not limited to these examples. All the introduced functional groups and substituents could be used for further derivatization (elaboration of R 3 substituents). Thus, iodine constituted a useful electrophile for the efficient synthesis of 2-iodoimidazole derivatives. Moreover 2-iodo-1-trityl-1H-imidazole represented a versatile starting material for the preparation of additional 2-substituted imidazoles via palladium-catalyzed cross-coupling reactions (mainly Stille cross-coupling reactions). 1-Trityl-1H-imidazole-2-carbaldehyde could be also obtained regioselectively and efficiently (after trapping with DMF) allowing further functional group interconversions and therefore access to 2-alkoxymethyl-1H-imidazole (after reduction of the aldehyde moiety and subsequent O-alkylation).
The versatility of the iodo-substituent in 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazines F allowed the access to a variety of derivatives, as exemplified in scheme 6. Thus, treatment of F with n-butyllithium followed by trapping of the resulting carbanion with hexachloroethane afforded the chloro-derivative. Alkoxy-residues could be introduced by copper(I)-catalyzed and microwave-assisted alkoxylation of F (ROH/CuI/1,10-phenanthroline/Cs 2 CO 3 ). The carbanion generated after iodine/metal exchange could be smoothly trapped with N,N-dimethylformamide and the introduced formyl-moiety could be additionally manipulated for the preparation of several derivatives (scheme 6a and 6b). Moreover, trapping of the previous carbanion with CO 2 allowed the direct preparation of carboxylic acid derivatives which in turn could be converted to amides. The iodo-substituent also allowed the introduction of a trifluoromethyl group via copper(I)-catalyzed trifluoromethylation (FSO 2 CF 2 CO 2 Me/CuI). Stille cross-coupling reactions performed with iodo-imidazoles are well documented in the literature, and in our case 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazines F reacted smoothly in such reactions with a variety of organotin derivatives (e.g. with n-tributyl(vinyl)tin).
The preparation of some compounds of formula (I) and (II) could be directly undertaken starting with appropriately disubstituted imidazoles (commercially available or synthesized; scheme 7). Thus, N-alkylation of 2,4-substituted imidazoles with 2-chloroethylamine hydrochloride (in the presence of powdered NaOH and catalytic amounts of tetrabutylammonium hydrogensulfate) afforded a mixture of isomeric products including the expected compound U. Subsequent microwave-assisted Pictet-Spengler like reaction with aldehydes R 1 —X—CH 2 —CHO furnished the expected 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives Q which could be transformed to compounds of formula (I) and (II) according to previously described procedures.
Aldehydes R 1 —X—CH 2 —CHO were pivotal reagents for the preparation of compounds of formula (I) and (II) and several synthetic methods allowed their efficient preparation.
Thus, aldehydes R 1 —CH 2 —CH 2 —CHO (X═CH 2 ) were readily prepared by reduction of the corresponding hydrocinnamic acids (BH 3 .THF) and subsequent oxidation of the obtained alcohols with PCC (scheme 8). Preliminary hydrogenation of commercially available cinnamic acids allowed a convenient access to unavailable hydrocinnamic acid precursors (scheme 8).
Closely related to this method of preparation, another short and convenient synthesis of diversely substituted propanol derivatives was the reduction of corresponding propionic acid methyl esters (scheme 9).
In case neither cinnamic acids nor hydrocinnamic acids were commercially available, additional synthetic routes allowed their successful preparation. Thus, a convenient synthesis was based on a Knoevenagel condensation as depicted in scheme 10. Knoevenagel condensation between aryl aldehydes R 1 CHO and malonic acid (in pyridine and in the presence of piperidine) gave the expected cinnamic acid derivatives. Catalytic hydrogenation under standard conditions (1 atm H 2 ; 10% Pd(C); MeOH; rt) afforded the corresponding hydrocinnamic acids which were converted to the corresponding aldehydes R 1 —CH 2 —CH 2 —CHO by the previously described reduction/oxidation sequence (scheme 10).
An alternative preparation of hydrocinnamic acids was based on a Heck reaction between aryl halides and n-butyl acrylate (with Pd(OAc) 2 /DABCO as catalytic system; scheme 11). Palladium-catalyzed hydrogenation and subsequent saponification afforded the hydrocinnamic acids which were again converted to the expected aldehydes R 1 —CH 2 —CH 2 —CHO by the previously described reduction/oxidation sequence (scheme 11).
Aldehydes R 1 —O—CH 2 —CHO (X═O) were readily prepared according to the synthetic route depicted in scheme 12. Thus, alkylation of phenol derivatives R 1 OH with methyl bromoacetate, and subsequent reduction afforded the alcohol precursors which could be oxidized under Swern conditions in order to obtain the expected aldehyde derivatives (scheme 12).
The synthesis of enantiomerically pure toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester is exemplified in scheme 13. Treatment of methyl (S)-(+)-mandelate with an alcoholic amine solution gave the corresponding amide which could be converted to toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester after reaction with p-toluenesulfonyl chloride.
Whenever the compounds of formula (I) are obtained in the form of mixtures of enantiomers, the enantiomers can be separated using methods known to one skilled in the art: e.g. by formation and separation of diastereomeric salts or by HPLC over a chiral stationary phase such as a Regis Whelk-O1(R,R) (10 μm) column, a Daicel ChiralCel OD-H (5-10 μm) column, or a Daicel ChiralPak IA (10 μm) or AD-H (5 μm) column. Typical conditions of chiral HPLC are an isocratic mixture of eluent A (EtOH, in presence or absence of an amine such as TEA, diethylamine) and eluent B (hexane), at a flow rate of 0.8 to 150 mL/min.
EXPERIMENTAL PART
Abbreviations
As Used Herein and in the Description Above
AcOH acetic acid
anh. anhydrous
aq. aqueous
BH 3 .THF borane-tetrahydrofuran complex
Boc tert-butoxycarbonyl
Boc 2 O di-tert-butyl dicarbonate
Br(CH 2 ) 2 NHBoc (2-Bromo-ethyl)-carbamic acid tert-butyl ester
n-BuLi n-butyllithium
DABCO 1,4-diazabicyclo[2.2.2]octane
DCM dichloromethane
DIBAL diisobutylaluminum hydride
DIPEA N-ethyldiisopropylamine
DMF N,N-dimethylformamide
DMSO dimethyl sulfoxide
EA ethyl acetate
ELSD Evaporative Light-Scattering Detection
eq. equivalent
Et ethyl
EtMgBr ethylmagnesium bromide
ether diethylether
EtOH ethanol
FC flash chromatography on silica gel
FLIPR Fluorescent imaging plate reader
FSO 2 CF 2 CO 2 Me methyl 2,2-difluoro-2-(fluorosulfonyl)acetate
h hour(s)
HCl hydrogen chloride
1 H-NMR nuclear magnetic resonance of the proton
HPLC High Performance Liquid Chromatography
HV High Vacuum
LC-MS Liquid Chromatography-Mass Spectroscopy
MeCN acetonitrile
MeOH methanol
MsCl methanesulfonyl chloride
min. minute(s)
Ms methanesulfonyl
MS Mass Spectroscopy
PBS phosphate buffered saline
PCC pyridinium chlorochromate
Pd(C) palladium over charcoal
Pd(OAc) 2 palladium (II) acetate
Ph phenyl
p-TsOH para-toluenesulfonic acid
rt room temperature
sat. saturated
TBTU O-benzotriazol-1-yl-N,N,N′,N′-tetramethyluronium tetrafluoroborate TEA triethylamine
TFA trifluoroacetic acid
THF tetrahydrofuran
TLC Thin Layer Chromatography
t R retention time
Ts toluenesulfonyl
TsCl p-toluenesulfonyl chloride
UV ultra violet
V is visible
W Watt
I. CHEMISTRY
General Procedures and Examples
The following examples illustrate the preparation of pharmacologically active compounds of the invention but do not at all limit the scope thereof.
All temperatures are stated in ° C.
NMR measurements are done with a Varian Mercury 300 instrument or a Bruker Avance 400 Instrument; chemical shifts are given in ppm relative to the solvent used; multiplicities: s=singlet, d=doublet, t=triplet, m=multiplet, b=broad, coupling constants are given in Hz.
HPLC Conditions:
Analytic: Zorbax 59 SB Aqua column, 4.6×50 mm from Agilent Technologies. Eluents: A: MeCN; B: H 2 O+0.04% TFA. Gradient: 90% B 5% B→over 2 min. Flow: 4.5 ml/min.
Detection: UV/Vis+MS.
Preparative: Waters Xterra RP18 (large), 75×30 mm. Eluent: A: MeCN; B: H 2 O+0.05% NH 4 OH (25% aq.). Gradient: 90% B→10% B over 6.5 min. Flow: 75 ml/min. Detection: UV+ELSD.
A. Synthesis of carboxylic acids R 1 —X—CH 2 —CO 2 H, alcohols R 1 —X—CH 2 —CH 2 OH and aldehydes R 1 —X—CH 2 —CHO
A.1 Synthesis of carboxylic acids R 1 —CH 2 —CH 2 —CO 2 H
A.1.1 Synthesis of carboxylic acids R 1 —CH 2 —CH 2 —CO 2 H via Knoevenagel condensation
3-(3,4-dimethyl-phenyl)-acrylic acid [general procedure for Knoevenagel condensation (GP1)]
A suspension of 3,4-dimethylbenzaldehyde (15.000 g; 111.793 mmol) and malonic acid (22.103 g; 212.410 mmol) in pyridine (85 ml) was heated to 50° C., under nitrogen. Then piperidine (8.5 ml; 86.079 mmol) was added dropwise (over 5 minutes) and the resulting suspension was heated to 75° C. for 2 h. The reaction mixture was cooled to 0° C., and poured into an ice-cooled solution of concentrated hydrochloric acid (12 N; 96 ml) in water (1200 ml). The precipitated colorless product was filtered off, and washed with water (3×100 ml). Remaining water was evaporated under reduced pressure, then under HV to give the dried product 3-(3,4-dimethyl-phenyl)-acrylic acid as a colorless solid (19.230 g; 98%). LC-MS: t R =0.88 min; [M+H] + : no ionisation.
2,4-difluoro-3-methyl-benzaldehyde
A cooled (−78° C.) solution of 2,4-difluoro-3-methylbromobenzene (2.000 g; 9.661 mmol) in anhydrous THF (36 ml) was treated dropwise (over 10 min.) with a solution of 1.6M n-BuLi in hexanes (6.04 ml; 9.661 mmol) while maintaining the temperature below −70° C. This mixture was further stirred at −78° C. for 2 min. before anhydrous DMF (1.49 ml; 19.326 mmol) was added dropwise (over 10 min.) while maintaining the temperature below −70° C. After completion of the addition, the resulting light brown solution was further stirred at −78° C. for 1 h30. The resulting mixture was then quenched at −78° C. with aq. sat. NH 4 Cl (10 ml), and was then allowed to warm-up to rt. Ether (50 ml) and water (20 ml) were added, and the organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure (caution: rotary evaporation bath at 30° C. because the aldehyde is volatile). The crude was purified by FC (DCM) to give the pure product 2,4-difluoro-3-methyl-benzaldehyde as a pale yellow oil (1.250 g; 83%).
3-(2,4-difluoro-3-methyl-phenyl)-acrylic acid
According to the previously described general procedure (GP1), Knoevenagel condensation (75° C.; 3h30) between 2,4-difluoro-3-methyl-benzaldehyde (1.560 g; 9.744 mmol) and malonic acid (1.926 g; 18.515 mmol) gave the product 3-(2,4-difluoro-3-methyl-phenyl)-acrylic acid as a pale yellow solid (1.600 g; 83%). LC-MS: t R =0.86 min; [M+H] + : no ionisation.
3-(2-fluoro-4-trifluoromethyl-phenyl)-acrylic acid
According to the previously described general procedure (GP1), Knoevenagel condensation (75° C.; 3h20) between 2-fluoro-4-(trifluoromethyl)benzaldehyde (5.000 g; 26.027 mmol) and malonic acid (5.145 g; 49.451 mmol) gave the product 3-(2-fluoro-4-trifluoromethyl-phenyl)-acrylic acid as a colorless solid (5.030 g; 82.5%). LC-MS: t R =0.89 min; [M+H] + : no ionisation.
3-(3-fluoro-4-trifluoromethyl-phenyl)-acrylic acid
According to the previously described general procedure (GP1), Knoevenagel condensation (75° C.; 3h20) between 3-fluoro-4-trifluoromethyl-benzaldehyde (9.000 g; 46.848 mmol) and malonic acid (9.262 g; 89.012 mmol) gave the product 3-(3-fluoro-4-trifluoromethyl-phenyl)-acrylic acid as a colorless solid (9.520 g; 87%). LC-MS: t R =0.90 min; [M+H] + : no ionisation.
3-(2,4-dimethyl-phenyl)-acrylic acid
According to the previously described general procedure (GP1), Knoevenagel condensation (75° C.; 3h30) between 2,4-dimethyl-benzaldehyde (10.000 g; 74.528 mmol) and malonic acid (14.735 g; 141.607 mmol) gave the product 3-(2,4-dimethyl-phenyl)-acrylic acid as a colorless solid (9.720 g; 74%). LC-MS: t R =0.86 min; [M+H] + : no ionisation.
3-(3-fluoro-4-methyl-phenyl)-acrylic acid
According to the previously described general procedure (GP1), Knoevenagel condensation (75° C.; 2h30) between 3-fluoro-4-methyl-benzaldehyde (10.519 g; 76.154 mmol) and malonic acid (15.056 g; 144.694 mmol) gave the product 3-(3-fluoro-4-methyl-phenyl)-acrylic acid as a colorless solid (11.860 g; 86%). LC-MS: t R =0.84 min; [M+H] + : no ionisation.
3-(3,4,5-trifluoro-phenyl)-acrylic acid
According to the previously described general procedure (GP1), Knoevenagel condensation (75° C.; 3 h) between 3,4,5-trifluorobenzaldehyde (7.000 g; 43.724 mmol) and malonic acid (8.644 g; 83.076 mmol) gave the product 3-(3,4,5-trifluoro-phenyl)-acrylic acid as a yellow solid (8.600 g; 97%). LC-MS: t R =0.91 min.; [M+H] + : no ionisation.
3-(4-trifluoromethoxy-phenyl)-acrylic acid
According to the previously described general procedure (GP1), Knoevenagel condensation (75° C.; 6 h) between 4-(trifluoromethoxy)benzaldehyde (10.000 g; 52.598 mmol) and malonic acid (10.399 g; 99.937 mmol) gave the product 3-(4-trifluoromethoxy-phenyl)-acrylic acid as a colorless solid (12.080 g; 99%). LC-MS: t R =0.96 min.; [M+H] + : no ionisation.
3-(2,3,5-trifluoro-phenyl)-acrylic acid
According to the previously described general procedure (GP1), Knoevenagel condensation (75° C.; 3h20) between 2,3,5-trifluorobenzaldehyde (9.730 g; 60.777 mmol) and malonic acid (12.016 g; 115.477 mmol) gave the product 3-(2,3,5-trifluoro-phenyl)-acrylic acid as a colorless solid (8.310 g; 68%). LC-MS: t R =0.84 min.; [M+H] + : no ionisation.
3-(3-fluoro-4-methoxy-phenyl)-acrylic acid
According to the previously described general procedure (GP1), Knoevenagel condensation (75° C.; 3 h) between 3-fluoro-4-methoxybenzaldehyde (6.080 g; 39.445 mmol) and malonic acid (7.798 g; 74.946 mmol) gave the product 3-(3-fluoro-4-methoxy-phenyl)-acrylic acid as a colorless solid (7.530 g; 97%). LC-MS: t R =0.86 min.; [M+H] + : no ionisation.
3-(3,4-dimethyl-phenyl)-propionic acid [general procedure for hydrogenation of cinnamic acid derivatives (GP2)]
A mixture of 3-(3,4-dimethyl-phenyl)-acrylic acid (19.269 g; 109.355 mmol) and 10% palladium over activated charcoal (1.920 g) was placed under nitrogen before MeOH (300 ml) was carefully added. The resulting suspension was placed under vacuum, then under hydrogen (1 atm), and the reaction mixture was vigorously stirred at rt for 4 h. The reaction mixture was filtered over a pad of celite, and concentrated under reduced pressure to give the expected product 3-(3,4-dimethyl-phenyl)-propionic acid as a grey solid which was further dried under HV (19.070 g; 98%). LC-MS: t R =0.85 min; [M+H] + : no ionisation.
3-(2,4-difluoro-3-methyl-phenyl)-propionic acid
According to the previously described general procedure (GP2), hydrogenation (1 atm; rt; 3 h) of 3-(2,4-difluoro-3-methyl-phenyl)-acrylic acid (1.568 g; 7.916 mmol) gave the expected product 3-(2,4-difluoro-3-methyl-phenyl)-propionic acid as a grey solid (1.600 g; 100%). LC-MS: t R =0.97 min; [M+H] + : no ionisation.
3-(2-fluoro-4-trifluoromethyl-phenyl)-propionic acid
According to the previously described general procedure (GP2), hydrogenation (1 atm; rt; 4 h) of 3-(2-fluoro-4-trifluoromethyl-phenyl)-acrylic acid (5.937 g; 25.356 mmol) gave the expected product 3-(2-fluoro-4-trifluoromethyl-phenyl)-propionic acid as a grey solid (4.590 g; 77%). LC-MS: t R =0.88 min; [M+H] + : no ionisation.
3-(3-fluoro-4-trifluoromethyl-phenyl)-propionic acid
According to the previously described general procedure (GP2), hydrogenation (1 atm; rt; 3h30) of 3-(3-fluoro-4-trifluoromethyl-phenyl)-acrylic acid (9.510 g; 40.615 mmol) gave the expected product 3-(3-fluoro-4-trifluoromethyl-phenyl)-propionic acid as a grey solid (9.420 g; 98%). LC-MS: t R =0.89 min; [M+H] + : no ionisation.
3-(2,4-dimethyl-phenyl)-propionic acid
According to the previously described general procedure (GP2), hydrogenation (1 atm; rt; 3 h) of 3-(2,4-dimethyl-phenyl)-acrylic acid (9.720 g; 55.160 mmol) gave the expected product 3-(2,4-dimethyl-phenyl)-propionic acid as a grey solid (9.830 g; 100%). LC-MS: t R =0.85 min; [M+H] + : no ionisation.
3-(3-fluoro-4-methyl-phenyl)-propionic acid
According to the previously described general procedure (GP2), hydrogenation (1 atm; rt; 4 h) of 3-(3-fluoro-4-methyl-phenyl)-acrylic acid (11.859 g; 65.824 mmol) gave the expected product 3-(3-fluoro-4-methyl-phenyl)-propionic acid as a grey solid (11.740 g; 98%). LC-MS: t R =0.83 min; [M+H] + : no ionisation.
3-(3,4,5-trifluoro-phenyl)-propionic acid
According to the previously described general procedure (GP2), hydrogenation (1 atm; rt; 5 h) of 3-(3,4,5-trifluoro-phenyl)-acrylic acid (8.600 g; 42.547 mmol) gave the expected product 3-(3,4,5-trifluoro-phenyl)-propionic acid as a colorless solid (8.620 g; 99%). LC-MS: t R =0.90 min.; [M+H] + : no ionisation.
3-(4-trifluoromethoxy-phenyl)-propionic acid
According to the previously described general procedure (GP2), hydrogenation (1 atm; rt; 5h30) of 3-(4-trifluoromethoxy-phenyl)-acrylic acid (14.000 g; 60.304 mmol) gave the expected product 3-(4-trifluoromethoxy-phenyl)-propionic acid as a beige solid (14.120 g; 100%). LC-MS: t R =0.95 min.; [M+H] + : no ionisation.
3-(2,3,5-trifluoro-phenyl)-propionic acid
According to the previously described general procedure (GP2), hydrogenation (1 atm; rt; 3h30) of 3-(2,3,5-trifluoro-phenyl)-acrylic acid (8.310 g; 41.112 mmol) gave the expected product 3-(2,3,5-trifluoro-phenyl)-propionic acid as a grey solid (8.020 g; 96%). LC-MS: t R =0.83 min.; [M+H] + : no ionisation.
3-(3-fluoro-4-methoxy-phenyl)-propionic acid
According to the previously described general procedure (GP2), hydrogenation (1 atm; rt; 2h30) of 3-(3-fluoro-4-methoxy-phenyl)-acrylic acid (3.090 g; 15.751 mmol) gave the expected product 3-(3-fluoro-4-methoxy-phenyl)-propionic acid as a colorless solid (3.080 g; 99%). LC-MS: t R =0.85 min.; [M+H] + : no ionisation.
A.1.2 Synthesis of carboxylic acids R 1 —CH 2 —CH 2 —CO 2 H via Heck reaction
A.1.2.1 Synthesis of Aryl Bromides
5-bromo-1,3-difluoro-2-methyl-benzene
A solution of methanesulfonyl chloride (4.72 ml; 60.794 mmol) in anhydrous DCM (10 ml) was added dropwise (over 5 min.) to an ice-cooled solution of 4-bromo-2,6-difluorobenzyl alcohol (11.300 g; 50.669 mmol) and TEA (14.1 ml; 101.338 mmol) in DCM (200 ml). The resulting solution was stirred at 0° C., under nitrogen, for 30 min. The reaction mixture was diluted with EA (200 ml), and water (100 ml) was added. The organic layer was successively washed with 1N aq. hydrochloric acid (100 ml), sat. aq. NaHCO 3 (100 ml), and finally with brine (100 ml). The organic layer was then dried over magnesium sulfate, filtered, and concentrated to dryness under reduced pressure to give an orange solid which was additionally dried under HV (15.170 g; 99.5%). LC-MS for the mesylate: t R =0.92 min.; [M+H] + : no ionisation.
To an ice-cooled solution of the obtained mesylate derivative (15.170 g; 50.381 mmol) in anhydrous THF (90 ml) was added dropwise a solution of superhydride LiEt 3 BH (1N in THF; 106 ml; 106 mmol). The resulting mixture was stirred at 0° C. for 5 min., and then at rt for 30 min. The solution was cooled to 0° C. before dropwise addition of water (100 ml), and addition of ether (200 ml). The organic layer was dried over anh. MgSO 4 , filtered, and carefully concentrated under reduced pressure (CAUTION! product with low boiling point, therefore heating bath of the rotary evaporator at 30° C.!). Purification by FC (DCM) gave the pure product 5-bromo-1,3-difluoro-2-methyl-benzene as a colorless oil (6.910 g; 66%). LC-MS: t R =1.00 min.; [M+H] + : no ionisation.
1-bromo-2,5-difluoro-4-trifluoromethyl-benzene
A slightly yellow solution of 2,5-difluoro-4-(trifluoromethyl)aniline (10.0 ml; 76.708 mmol) in MeCN (90 ml) was treated with copper(II) bromide (17.133 g; 76.708 mmol), and the green heterogeneous mixture was heated to 45° C. A solution of tert-butyl nitrite (10.0 ml; 84.379 mmol) in MeCN (20 ml) was then added dropwise over 30 min., and the resulting mixture was further stirred at 45° C. for 2 h30. The dark-green heterogeneous reaction mixture was allowed to cool to rt, and was directly purified by FC (DCM). After concentration to dryness under reduced pressure, the expected product 1-bromo-2,5-difluoro-4-trifluoromethyl-benzene was obtained as an orange oil (10.290 g; 51%). LC-MS: t R =1.07 min.; [M+H] + : no ionisation.
4-bromo-2-chloro-1-trifluoromethyl-benzene
A solution of 4-amino-2-chlorobenzotrifluoride (9.780 g; 50.007 mmol) in MeCN (65 ml) was treated with copper(II) bromide (11.169 g; 50.007 mmol), and the green heterogeneous mixture was heated to 45° C. A solution of tert-butyl nitrite (6.53 ml; 55.008 mmol) in MeCN (10 ml) was then added dropwise over 30 min., and the resulting mixture was further stirred at 45° C. for 2 h20. The dark heterogeneous reaction mixture was allowed to cool to rt, and was directly purified by FC (DCM). After concentration to dryness under reduced pressure, the expected product 4-bromo-2-chloro-1-trifluoromethyl-benzene was obtained as a yellow oil (12.820 g; 50%). LC-MS: t R =1.10 min.; [M+H] + : no ionisation.
A.1.2.2 Heck Reaction Between Aryl Bromides and Butyl Acrylate
3-(3,5-difluoro-4-methyl-phenyl)-acrylic acid butyl ester [general procedure for Heck reaction (GP3)]
To a solution of 5-bromo-1,3-difluoro-2-methyl-benzene (6.910 g; 33.379 mmol) in anhydrous DMF (200 ml) were added successively butyl acrylate (7.15 ml; 50.062 mmol), DABCO (157 mg; 1.333 mmol), potassium carbonate (4.612 g; 33.379 mmol), and palladium acetate (150 mg; 0.669 mmol). The resulting brown suspension was heated to 120° C. for 1 h. The reaction mixture was allowed to cool to rt before ether (400 ml) was added. This mixture was then washed with water (2×200 ml), and the mixed aq. layers were further extracted with ether (150 ml). The combined organic layers were dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/heptane=1/1=>DCM) gave the pure product 3-(3,5-difluoro-4-methyl-phenyl)-acrylic acid butyl ester as a yellow oil which was further dried under HV (4.690 g; 55%). LC-MS: t R =1.10 min.; [M+H] + : no ionisation.
3-(3,5-difluoro-4-trifluoromethyl-phenyl)-acrylic acid butyl ester
According to the previously described general procedure (GP3), 3,5-difluoro-4-(trifluoromethyl)bromobenzene (10.000 g; 38.316 mmol) and butyl acrylate (8.2 ml; 57.474 mmol) gave after Heck reaction (120° C.; 2h30) and purification by FC (DCM/heptane=1/1) the pure product 3-(3,5-difluoro-4-trifluoromethyl-phenyl)-acrylic acid butyl ester as a slightly beige solid (10.120 g; 86%). LC-MS: t R =1.12 min.; [M+H] + : no ionisation.
3-(3,5-difluoro-4-methoxy-phenyl)-acrylic acid butyl ester
According to the previously described general procedure (GP3), 5-bromo-1,3-difluoro-2-methoxy-benzene (10.670 g; 47.849 mmol) and butyl acrylate (10.23 ml; 71.774 mmol) gave after Heck reaction (120° C.; 2 h) and purification by FC (DCM/heptane=1/1) the pure product 3-(3,5-difluoro-4-methoxy-phenyl)-acrylic acid butyl ester as a slightly beige oil (2.410 g; 19%). LC-MS: t R =1.13 min.; [M+H] + : no ionisation.
3-(4-chloro-3,5-difluoro-phenyl)-acrylic acid butyl ester
According to the previously described general procedure (GP3), 5-bromo-2-chloro-1,3-difluoro-benzene (10.000 g; 43.969 mmol) and butyl acrylate (9.40 ml; 65.953 mmol) gave after Heck reaction (120° C.; 2 h) and purification by FC (DCM/heptane=1/1) the pure product 3-(4-chloro-3,5-difluoro-phenyl)-acrylic acid butyl ester as a colorless solid (10.870 g; 90%). LC-MS: t R =1.09 min.; [M+H] + : no ionisation.
3-(3-chloro-4-trifluoromethyl-phenyl)-acrylic acid butyl ester
According to the previously described general procedure (GP3), 4-bromo-2-chloro-1-trifluoromethyl-benzene (12.820 g; 49.412 mmol) and butyl acrylate (10.56 ml; 74.118 mmol) gave after Heck reaction (120° C.; 2h30) and purification by FC (DCM/heptane=1/1) the pure product 3-(3-chloro-4-trifluoromethyl-phenyl)-acrylic acid butyl ester as a yellow solid (7.030 g; 46%). LC-MS: t R =1.19 min.; [M+H] + : no ionisation.
3-(2,5-difluoro-4-trifluoromethyl-phenyl)-acrylic acid butyl ester
According to the previously described general procedure (GP3), 1-bromo-2,5-difluoro-4-trifluoromethyl-benzene (10.290 g; 39.427 mmol) and butyl acrylate (8.43 ml; 59.141 mmol) gave after Heck reaction (120° C.; 15 h) and purification by FC (DCM/heptane=1/1) the pure product 3-(2,5-difluoro-4-trifluoromethyl-phenyl)-acrylic acid butyl ester as a beige solid (6.410 g; 53%). LC-MS: t R =1.18 min.; [M+H] + : no ionisation.
3-(2,5-difluoro-4-methoxy-phenyl)-acrylic acid butyl ester
According to the previously described general procedure (GP3), 1-bromo-2,5-difluoro-4-methoxy-benzene (16.020 g; 71.834 mmol) and butyl acrylate (15.36 ml; 107.750 mmol) gave after Heck reaction (120° C.; 16h30) and purification by FC (DCM/heptane=1/1) the pure product 3-(2,5-difluoro-4-methoxy-phenyl)-acrylic acid butyl ester as a colorless solid (6.183 g; 32%). LC-MS: t R =1.13 min.; [M+H] + : no ionisation.
A.1.2.3 3-(3,5-difluoro-4-methyl-phenyl)-propionic acid butyl ester [general procedure for hydrogenation of cinnamic esters (GP4)]
A mixture of 3-(3,5-difluoro-4-methyl-phenyl)-acrylic acid butyl ester (7.651 g; 30.089 mmol) and 10% palladium over activated charcoal (0.760 g) was placed under nitrogen before MeOH (100 ml) was carefully added. The resulting suspension was placed under vacuum, then under hydrogen (1 atm), and the reaction mixture was vigorously stirred at rt for 2 h45. The reaction mixture was filtered over a pad of celite, and concentrated under reduced pressure to give the expected product 3-(3,5-difluoro-4-methyl-phenyl)-propionic acid butyl ester as a yellow oil which was further dried under HV (6.960 g; 90%). LC-MS: t R =1.10 min; [M+H] + : no ionisation.
3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid butyl ester
According to the previously described general procedure (GP4), hydrogenation (1 atm; rt; 3h30) of 3-(3,5-difluoro-4-trifluoromethyl-phenyl)-acrylic acid butyl ester (8.849 g; 28.710 mmol) gave the expected product 3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid butyl ester as a yellow oil (8.622 g; 97%). LC-MS: t R =1.11 min; [M+H] + : no ionisation.
3-(3,5-difluoro-4-methoxy-phenyl)-propionic acid butyl ester
According to the previously described general procedure (GP4), hydrogenation (1 atm; rt; 2 h) of 3-(3,5-difluoro-4-methoxy-phenyl)-acrylic acid butyl ester (2.410 g; 8.917 mmol) gave the expected product 3-(3,5-difluoro-4-methoxy-phenyl)-propionic acid butyl ester as a colorless oil (2.410 g; 99%).
3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid butyl ester
According to the previously described general procedure (GP4), hydrogenation (1 atm; rt; 4 h) of 3-(2,5-difluoro-4-trifluoromethyl-phenyl)-acrylic acid butyl ester (6.340 g; 20.568 mmol) gave the expected product 3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid butyl ester as a yellow/green oil (6.160 g; 97%). LC-MS: t R =1.15 min.; [M+H] + : no ionisation.
3-(2,5-difluoro-4-methoxy-phenyl)-propionic acid butyl ester
According to the previously described general procedure (GP4), hydrogenation (1 atm; rt; 3 h) of 3-(2,5-difluoro-4-methoxy-phenyl)-acrylic acid butyl ester (6.180 g; 22.866 mmol) gave the expected product 3-(2,5-difluoro-4-methoxy-phenyl)-propionic acid butyl ester as a colorless oil (5.980 g; 96%). LC-MS: t R =1.10 min.; [M+H] + : no ionisation.
3-(4-chloro-3,5-difluoro-phenyl)-propionic acid butyl ester
A mixture of 3-(4-chloro-3,5-difluoro-phenyl)-acrylic acid butyl ester (5.000 g; 18.202 mmol), zinc bromide (0.819 g; 3.640 mmol), and 10% palladium over activated charcoal (0.320 g) was placed under nitrogen before EA (140 ml) was added. The resulting suspension was placed under vacuum, then under hydrogen (1 atm), and the reaction mixture was vigorously stirred at rt for 22 h. The reaction mixture was filtered over a pad of celite, and concentrated under reduced pressure to give the expected product 3-(4-chloro-3,5-difluoro-phenyl)-propionic acid butyl ester as a slightly yellow oil which was further dried under HV (5.020 g; 98%). LC-MS: t R =1.14 min.; [M+H] + : no ionisation.
3-(3-chloro-4-trifluoromethyl-phenyl)-propionic acid butyl ester
A mixture of 3-(3-chloro-4-trifluoromethyl-phenyl)-acrylic acid butyl ester (7.030 g; 22.921 mmol), zinc bromide (1.031 g; 4.584 mmol), and 10% palladium over activated charcoal (0.403 g) was placed under nitrogen before EA (150 ml) was added. The resulting suspension was placed under vacuum, then under hydrogen (1 atm), and the reaction mixture was vigorously stirred at rt for 9 h. The reaction mixture was filtered over a pad of celite, and concentrated under reduced pressure to give the expected product 3-(3-chloro-4-trifluoromethyl-phenyl)-propionic acid butyl ester as a yellow oil which was further dried under HV (8.430 g; 100%). LC-MS: t R =1.16 min.; [M+H] + : no ionisation.
A.1.2.5 3-(3,5-difluoro-4-methyl-phenyl)-propionic acid [general procedure for saponification of esters (GP5)]
To a solution of 3-(3,5-difluoro-4-methyl-phenyl)-propionic acid butyl ester (6.960 g; 27.157 mmol) in MeOH (150 ml) and water (25 ml) was added at rt aq. 1N NaOH (68 ml; 68 mmol). The resulting solution was further stirred at rt for 1 h. MeOH was then removed under reduced pressure. Water (25 ml) was added, and the mixture was acidified with aq. 1N HCl (68 ml) in order to reach pH=2. DCM (150 ml) was added, and the layers were shaken and separated. The aq. layer was further extracted with DCM (50 ml). The mixed organic layers were dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The product 3-(3,5-difluoro-4-methyl-phenyl)-propionic acid was obtained as a pale yellow solid which was further dried under HV (5.090 g; 94%). LC-MS: t R =0.86 min.; [M+H] + : no ionisation.
3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid
According to the previously described general procedure (GP5), saponification (rt; 45 min.) of 3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid butyl ester (7.658 g; 24.682 mmol) afforded the product 3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid as a colorless solid (6.216 g; 99%). LC-MS: t R =0.90 min.; [M+H] + : no ionisation.
3-(3-chloro-4-trifluoromethyl-phenyl)-propionic acid
According to the previously described general procedure (GP5), saponification (rt; 1 h) of 3-(3-chloro-4-trifluoromethyl-phenyl)-propionic acid butyl ester (7.070 g; 22.901 mmol) afforded the product 3-(3-chloro-4-trifluoromethyl-phenyl)-propionic acid as a yellow solid (5.670 g; 98%). LC-MS: t R =0.97 min.; [M+H] + : no ionisation.
3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid
According to the previously described general procedure (GP5), saponification (rt; 1 h30) of 3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid butyl ester (6.130 g; 19.758 mmol) afforded the product 3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid as a beige solid (5.011 g; 100%). LC-MS: t R =0.96 min.; [M+H] + : no ionisation.
A.2 Synthesis of alcohols R 1 —CH 2 —CH 2 —CH 2 OH
A.2.1 Synthesis of alcohols R 1 —CH 2 —CH 2 —CH 2 OH via reduction of carboxylic acids
3-(4-trifluoromethyl-phenyl)-propan-1-ol [general procedure for reduction of carboxylic acids to alcohols (GP6)]
To an ice-cooled homogeneous solution of 4-(trifluoromethyl)hydrocinnamic acid (9.800 g; 44.918 mmol) in anhydrous THF (250 ml) was added dropwise a solution of 1M BH 3 .THF (67.4 ml; 67.4 mmol) over 20 min. The resulting homogeneous solution was further stirred at 0° C., under nitrogen, for 1 h, and then at rt for 14 h. The colorless homogeneous reaction mixture was cooled to 0° C., and MeOH (100 ml) was carefully added followed by water (100 ml). MeOH and THF were then removed under vacuum. After extraction with DCM (3×100 ml), the combined organic extracts were washed with brine (100 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The crude was purified by FC (DCM/MeOH=9/1) to give the pure product 3-(4-trifluoromethyl-phenyl)-propan-1-ol as a colorless oil which was further dried under HV (9.180 g; 100%). LC-MS: t R =0.89 min.; [M+H] + : no ionisation.
3-(2,4-difluoro-3-methyl-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(2,4-difluoro-3-methyl-phenyl)-propionic acid (1.569 g; 7.838 mmol) gave after purification by FC (DCM/MeOH=12/1) the product 3-(2,4-difluoro-3-methyl-phenyl)-propan-1-ol as a pale yellow oil (1.260 g; 86%). LC-MS: t R =0.86 min.; [M+H] + : no ionisation.
3-(2,4-dimethyl-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(2,4-dimethyl-phenyl)-propionic acid (9.830 g; 55.153 mmol) gave after purification by FC (DCM/MeOH=12/1) the product 3-(2,4-dimethyl-phenyl)-propan-1-ol as a pale yellow oil (8.280 g; 91%). LC-MS: t R =0.86 min.; [M+H] + : no ionisation.
3-(2-fluoro-4-trifluoromethyl-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(2-fluoro-4-trifluoromethyl-phenyl)-propionic acid (9.609 g; 40.692 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(2-fluoro-4-trifluoromethyl-phenyl)-propan-1-ol as a pale yellow oil (7.100 g; 78.5%). LC-MS: t R =0.90 min.; [M+H] + : no ionisation.
3-(3,4-dimethyl-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(3,4-dimethyl-phenyl)-propionic acid (12.900 g; 72.378 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(3,4-dimethyl-phenyl)-propan-1-ol as a pale yellow oil (11.660 g; 98%). LC-MS: t R =0.86 min.; [M+H] + : no ionisation.
3-(3-fluoro-4-trifluoromethyl-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(3-fluoro-4-trifluoromethyl-phenyl)-propionic acid (9.430 g; 39.930 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(3-fluoro-4-trifluoromethyl-phenyl)-propan-1-ol as a pale yellow oil (8.340 g; 94%). LC-MS: t R =0.90 min.; [M+H] + : no ionisation.
3-(3,4-difluoro-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(3,4-difluoro-phenyl)-propionic acid (5.000 g; 26.859 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(3,4-difluoro-phenyl)-propan-1-ol as a colorless oil (4.490 g; 97%). LC-MS: t R =0.82 min.; [M+H] + : no ionisation.
3-p-tolyl-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-p-tolyl-propionic acid (10.200 g; 62.118 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-p-tolyl-propan-1-ol as a pale yellow oil (9.270 g; 99%). LC-MS: t R =0.82 min.; [M+H] + : no ionisation.
3-(3-fluoro-4-methyl-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(3-fluoro-4-methyl-phenyl)-propionic acid (12.679 g; 69.596 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(3-fluoro-4-methyl-phenyl)-propan-1-ol as a pale yellow oil (11.010 g; 94%). LC-MS: t R =0.85 min.; [M+H] + : no ionisation.
3-(3-chloro-phenyl)-propan-1-ol
prepared by reduction of 3-(3-chloro-phenyl)-propionic acid.
LC-MS: t R =0.84 min.; [M+H] + : no ionisation.
3-(2,4-dichloro-phenyl)-propan-1-ol
prepared by reduction of 3-(2,4-dichloro-phenyl)-propionic acid.
1 H-NMR (CDCl 3 ; 300 MHz): δ=7.38 (s, 1H), 7.18 (s, 2H), 3.67 (t, 2H), 2.81 (t, 2H), 1.92 (tt, 2H).
3-(3,4,5-trifluoro-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(3,4,5-trifluoro-phenyl)-propionic acid (8.620 g; 42.225 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(3,4,5-trifluoro-phenyl)-propan-1-ol as a yellow oil (7.130 g; 89%).
3-(3-chloro-4-trifluoromethyl-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(3-chloro-4-trifluoromethyl-phenyl)-propionic acid (3.000 g; 10.498 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(3-chloro-4-trifluoromethyl-phenyl)-propan-1-ol as a colorless oil (2.430 g; 97%). LC-MS: t R =0.98 min.; [M+H] + : no ionisation.
3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid (2.590 g; 10.191 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propan-1-ol as a slightly yellow oil (2.154 g; 88%). LC-MS: t R =0.97 min.; [M+H] + : no ionisation.
3-(4-trifluoromethoxy-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(4-trifluoromethoxy-phenyl)-propionic acid (7.000 g; 29.893 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(4-trifluoromethoxy-phenyl)-propan-1-ol as a colorless oil (5.090 g; 77%). LC-MS: t R =0.96 min.; [M+H] + : no ionisation.
3-(4-bromo-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(4-bromo-phenyl)-propionic acid (15.000 g; 64.172 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(4-bromo-phenyl)-propan-1-ol as a colorless oil (13.700 g; 99%). LC-MS: t R =0.81 min.; [M+H] + : no ionisation.
3-(2,3,5-trifluoro-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(2,3,5-trifluoro-phenyl)-propionic acid (8.019 g; 39.285 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(2,3,5-trifluoro-phenyl)-propan-1-ol as a pale yellow oil (7.470 g; 100%). LC-MS: t R =0.83 min.; [M+H] + : no ionisation.
3-(3-fluoro-4-methoxy-phenyl)-propan-1-ol
According to the previously described general procedure (GP6), reduction of 3-(3-fluoro-4-methoxy-phenyl)-propionic acid (3.820 g; 19.274 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 3-(3-fluoro-4-methoxy-phenyl)-propan-1-ol as a colorless oil (3.550 g; 100%). LC-MS: t R =0.85 min.; [M+H] + : no ionisation.
A.2.2 Synthesis of alcohols R 1 —CH 2 —CH 2 —CH 2 OH via reduction of esters
3-(3,5-difluoro-4-methyl-phenyl)-propan-1-ol [general procedure for reduction of esters to alcohols (GP7)]
To an ice-cooled solution of 3-(3,5-difluoro-4-methyl-phenyl)-propionic acid butyl ester (2.200 g; 8.584 mmol) in anhydrous THF (20 ml) was added dropwise a 1N solution of BH 3 .THF complex in THF (13 ml; 13 mmol). The resulting solution was stirred at 0° C., under nitrogen, for 1 h, and then at rt overnight. The reaction mixture was quenched by dropwise addition of MeOH (5 ml) followed by water (10 ml). The volatiles were removed under vacuum, and the product was extracted with DCM (3×20 ml). The combined organic layers were then washed with brine, dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The crude was purified by FC (DCM/MeOH=12/1) to give the pure product 3-(3,5-difluoro-4-methyl-phenyl)-propan-1-ol as a pale yellow oil (1.440 g; 90%). LC-MS: t R =0.87 min.; [M+H] + : no ionisation.
3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propan-1-ol
According to the previously described general procedure (GP7), 3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propionic acid butyl ester (4.110 g; 13.247 mmol) was reduced to 3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propan-1-ol (2.716 g; 85%; pale yellow oil). LC-MS: t R =0.91 min.; [M+H] + : no ionisation.
3-(3,5-difluoro-4-methoxy-phenyl)-propan-1-ol
According to the previously described general procedure (GP7), 3-(3,5-difluoro-4-methoxy-phenyl)-propionic acid butyl ester (2.420 g; 8.888 mmol) was reduced to 3-(3,5-difluoro-4-methoxy-phenyl)-propan-1-ol (1.573 g; 88%; colorless oil).
3-(4-chloro-3,5-difluoro-phenyl)-propan-1-ol
According to the previously described general procedure (GP7), 3-(4-chloro-3,5-difluoro-phenyl)-propionic acid butyl ester (5.020 g; 18.142 mmol) was reduced to 3-(4-chloro-3,5-difluoro-phenyl)-propan-1-ol (3.090 g; 82%; yellow oil). LC-MS: t R =0.93 min.; [M+H] + : no ionisation.
3-(2,5-difluoro-4-methoxy-phenyl)-propan-1-ol
According to the previously described general procedure (GP7), 3-(2,5-difluoro-4-methoxy-phenyl)-propionic acid butyl ester (5.980 g; 21.962 mmol) was reduced to 3-(2,5-difluoro-4-methoxy-phenyl)-propan-1-ol (4.440 g; 100%; colorless solid). LC-MS: t R =0.88 min.; [M+H] + : no ionisation.
3-(2,3-dimethyl-phenyl)-propan-1-ol
prepared by reduction of 3-(2,3-dimethyl-phenyl)-propionic acid methyl ester.
LC-MS: t R =0.86 min.; [M+H] + : no ionisation.
3-(3-fluoro-4-methoxy-phenyl)-propan-1-ol
prepared by reduction of 3-(3-fluoro-4-methoxy-phenyl)-propionic acid methyl ester.
LC-MS: t R =0.80 min.; [M+H] + : no ionisation.
3-(2,4-dimethoxy-phenyl)-propan-1-ol
prepared by reduction of 3-(2,4-dimethoxy-phenyl)-propionic acid methyl ester.
LC-MS: t R =0.81 min.; [M+H] + : no ionisation.
A.3 Synthesis of aldehydes R 1 —CH 2 —CH 2 —CHO
3-(4-trifluoromethyl-phenyl)-propionaldehyde [general procedure for the oxidation of primary alcohols to aldehydes (GP8)]
To an ice-cooled orange suspension of pyridinium chlorochromate (3.659 g; 16.896 mmol) in anhydrous DCM (20 ml) was added dropwise a solution of 3-(4-trifluoromethyl-phenyl)-propan-1-ol (2.300 g; 11.264 mmol) in anhydrous DCM (35 ml). The resulting black suspension was allowed to warm-up to rt and was stirred under nitrogen for 3 h. The reaction mixture was directly filtered over silicagel using DCM. After concentration to dryness under reduced pressure, the product 3-(4-trifluoromethyl-phenyl)-propionaldehyde was isolated as a pale yellow oil (1.970 g; 86.5%). LC-MS: t R =0.95 min.; [M+H] + : no ionisation.
3-(2,4-difluoro-3-methyl-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(2,4-difluoro-3-methyl-phenyl)-propan-1-ol (0.250 g; 1.342 mmol) gave 3-(2,4-difluoro-3-methyl-phenyl)-propionaldehyde (pale yellow oil; 0.232 g; 94%). LC-MS: t R =0.94 min.; [M+H] + : no ionisation.
3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propan-1-ol (1.730 g; 7.203 mmol) gave 3-(3,5-difluoro-4-trifluoromethyl-phenyl)-propionaldehyde (pale yellow oil; 1.180 g; 69%). LC-MS: t R =0.97 min.; [M+H] + : no ionisation.
3-(3,5-difluoro-4-methyl-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(3,5-difluoro-4-methyl-phenyl)-propan-1-ol (245 mg; 1.315 mmol) gave 3-(3,5-difluoro-4-methyl-phenyl)-propionaldehyde (pale yellow oil; 206.7 mg; 85%). LC-MS: t R =0.94 min.; [M+H] + : no ionisation.
3-(2-fluoro-4-trifluoromethyl-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(2-fluoro-4-trifluoromethyl-phenyl)-propan-1-ol (330 mg; 1.485 mmol) gave 3-(2-fluoro-4-trifluoromethyl-phenyl)-propionaldehyde (pale yellow oil; 220.2 mg; 67%). LC-MS: t R =0.97 min.; [M+H] + : no ionisation.
3-(3,4-dimethyl-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(3,4-dimethyl-phenyl)-propan-1-ol (250 mg; 1.522 mmol) gave 3-(3,4-dimethyl-phenyl)-propionaldehyde (pale yellow oil; 211.4 mg; 86%). LC-MS: t R =0.94 min.; [M+H] + : no ionisation.
3-(3,4-difluoro-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(3,4-difluoro-phenyl)-propan-1-ol (245 mg; 1.422 mmol) gave 3-(3,4-difluoro-phenyl)-propionaldehyde (pale yellow oil; 228.7 mg; 94%). LC-MS: t R =0.87 min.; [M+H] + : no ionisation.
3-(3-fluoro-4-trifluoromethyl-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(3-fluoro-4-trifluoromethyl-phenyl)-propan-1-ol (330 mg; 1.485 mmol) gave 3-(3-fluoro-4-trifluoromethyl-phenyl)-propionaldehyde (pale yellow oil; 260.4 mg; 80%). LC-MS: t R =0.97 min.; [M+H] + : no ionisation.
3-p-tolyl-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-p-tolyl-propan-1-ol (225.3 mg; 1.500 mmol) gave 3-p-tolyl-propionaldehyde (pale yellow oil; 123 mg; 55%). LC-MS: t R =0.89 min.; [M+H] + : no ionisation.
3-(2,4-dimethyl-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(2,4-dimethyl-phenyl)-propan-1-ol (492 mg; 3.000 mmol) gave 3-(2,4-dimethyl-phenyl)-propionaldehyde (pale yellow oil; 340 mg; 70%). LC-MS: t R =0.93 min.; [M+H] + : no ionisation.
3-(3-fluoro-4-methyl-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(3-fluoro-4-methyl-phenyl)-propan-1-ol (250 mg; 1.486 mmol) gave 3-(3-fluoro-4-methyl-phenyl)-propionaldehyde (pale yellow oil; 202 mg; 82%). LC-MS: t R =0.92 min.; [M+H] + : no ionisation.
3-(3-chloro-phenyl)-propionaldehyde
prepared by oxidation of 3-(3-chloro-phenyl)-propan-1-ol.
LC-MS: t R =0.84 min.; [M+H] + : no ionisation.
3-(2,3-dimethyl-phenyl)-propionaldehyde
prepared by oxidation of 3-(2,3-dimethyl-phenyl)-propan-1-ol.
LC-MS: t R =0.86 min.; [M+H] + : no ionisation.
3-(2,4-dichloro-phenyl)-propionaldehyde
prepared by oxidation of 3-(2,4-dichloro-phenyl)-propan-1-ol.
LC-MS: t R =0.91 min.; [M+H] + : no ionisation.
3-(3-fluoro-4-methoxy-phenyl)-propionaldehyde
prepared by oxidation of 3-(3-fluoro-4-methoxy-phenyl)-propan-1-ol.
LC-MS: t R =0.79 min.; [M+H] + : no ionisation.
3-(2,4-dimethoxy-phenyl)-propionaldehyde
prepared by oxidation of 3-(2,4-dimethoxy-phenyl)-propan-1-ol.
LC-MS: t R =0.80 min.; [M+H] + : no ionisation.
3-(3,4,5-trifluoro-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(3,4,5-trifluoro-phenyl)-propan-1-ol (2.500 g; 13.147 mmol) gave 3-(3,4,5-trifluoro-phenyl)-propionaldehyde (colorless oil; 1.393 g; 56%).
LC-MS: t R =0.97 min.; [M+H] + : no ionisation.
3-(3,5-difluoro-4-methoxy-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(3,5-difluoro-4-methoxy-phenyl)-propan-1-ol (1.555 g; 7.693 mmol) gave 3-(3,5-difluoro-4-methoxy-phenyl)-propionaldehyde (yellow oil; 1.034 g; 67%).
3-(4-chloro-3,5-difluoro-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(4-chloro-3,5-difluoro-phenyl)-propan-1-ol (2.500 g; 12.100 mmol) gave 3-(4-chloro-3,5-difluoro-phenyl)-propionaldehyde (pale yellow oil; 1.030 g; 42%).
LC-MS: t R =1.00 min.; [M+H] + : no ionisation.
3-(3-chloro-4-trifluoromethyl-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(3-chloro-4-trifluoromethyl-phenyl)-propan-1-ol (2.430 g; 10.183 mmol) gave 3-(3-chloro-4-trifluoromethyl-phenyl)-propionaldehyde (pale yellow oil; 1.060 g; 44%).
LC-MS: t R =1.04 min.; [M+H] + : no ionisation.
3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propan-1-ol (2.140 g; 8.910 mmol) gave 3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propionaldehyde (slightly yellow oil; 1.510 g; 71%).
3-(4-trifluoromethoxy-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(4-trifluoromethoxy-phenyl)-propan-1-ol (5.000 g; 22.708 mmol) gave 3-(4-trifluoromethoxy-phenyl)-propionaldehyde (pale yellow oil; 3.360 g; 68%).
3-(4-bromo-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(4-bromo-phenyl)-propan-1-ol (7.631 g; 35.480 mmol) gave 3-(4-bromo-phenyl)-propionaldehyde (yellow oil; 6.350 g; 84%).
3-(2,3,5-trifluoro-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(2,3,5-trifluoro-phenyl)-propan-1-ol (0.633 g; 3.330 mmol) gave 3-(2,3,5-trifluoro-phenyl)-propionaldehyde (pale yellow oil; 0.600 g; 96%).
3-(3-fluoro-4-methoxy-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(3-fluoro-4-methoxy-phenyl)-propan-1-ol (3.575 g; 19.407 mmol) gave 3-(3-fluoro-4-methoxy-phenyl)-propionaldehyde (colorless oil; 2.516 g; 71%).
LC-MS: t R =0.90 min.; [M+H] + : no ionisation.
3-(2,5-difluoro-4-methoxy-phenyl)-propionaldehyde
According to the previously described general procedure (GP8), the oxidation of 3-(2,5-difluoro-4-methoxy-phenyl)-propan-1-ol (3.000 g; 14.837 mmol) gave 3-(2,5-difluoro-4-methoxy-phenyl)-propionaldehyde (colorless oil; 2.120 g; 71%).
LC-MS: t R =0.95 min.; [M+H] + : no ionisation.
A.4 Synthesis of alcohols R 1 —O—CH 2 —CH 2 OH
2-(3-trifluoromethyl-phenoxy)-ethanol
A mixture of 3-trifluoromethyl-phenol (5.000 g; 30.843 mmol), potassium carbonate (5.328 g; 38.554 mmol), and methyl bromoacetate (3.54 ml; 38.554 mmol) in butanone (210 ml) was heated at reflux for 3 h. Filtration, concentration to dryness under reduced pressure, and purification by FC (heptane/EA, 4/1) afforded (3-trifluoromethyl-phenoxy)-acetic acid methyl ester as a pale yellow oil (7.220 g; 99%). LC-MS: t R =0.95 min.; [M+H] + : no ionisation.
A solution of (3-trifluoromethyl-phenoxy)-acetic acid methyl ester (7.220 g; 30.832 mmol) in MeOH (100 ml) was treated with aq. 1N NaOH (46.3 ml; 1.5 eq.), and the resulting mixture was further stirred at rt for 20 min. MeOH was then removed under reduced pressure, water (100 ml) was added followed by aq. 1N HCl (75 ml). Filtration of the precipitated solid, and drying under HV afforded (3-trifluoromethyl-phenoxy)-acetic acid as a colorless solid (6.020 g; 89%). LC-MS: t R =0.85 min.; [M+H] + : no ionisation.
According to the previously described general procedure (GP6), reduction of (3-trifluoromethyl-phenoxy)-acetic acid (6.020 g; 27.346 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 2-(3-trifluoromethyl-phenoxy)-ethanol as a yellow oil (5.270 g; 93%). LC-MS: t R =0.84 min.; [M+H] + : no ionisation.
2-(3,4-dimethyl-phenoxy)-ethanol
A mixture of 3,4-dimethyl-phenol (5.000 g; 40.928 mmol), potassium carbonate (7.070 g; 51.160 mmol), and methyl bromoacetate (4.70 ml; 51.160 mmol) in butanone (280 ml) was heated at reflux for 4 h. Filtration, concentration to dryness under reduced pressure, and purification by FC (heptane/EA, 4/1) afforded (3,4-dimethyl-phenoxy)-acetic acid methyl ester as a pale yellow oil (7.400 g; 93%). LC-MS: t R =0.92 min.; [M+H] + : no ionisation.
A solution of (3,4-dimethyl-phenoxy)-acetic acid methyl ester (7.399 g; 38.099 mmol) in MeOH (100 ml) was treated with aq. 1N NaOH (57 ml; 1.5 eq.), and the resulting mixture was further stirred at rt for 30 min. MeOH was then removed under reduced pressure, water (100 ml) was added followed by aq. 1N HCl (75 ml). Filtration of the precipitated solid, and drying under HV afforded (3,4-dimethyl-phenoxy)-acetic acid as a colorless solid (6.070 g; 88%). LC-MS: t R =0.81 min.; [M+H] + : no ionisation.
According to the previously described general procedure (GP6), reduction of (3,4-dimethyl-phenoxy)-acetic acid (6.770 g; 37.985 mmol) gave after purification by FC (heptane/EA=1/1) the product 2-(3,4-dimethyl-phenoxy)-ethanol as a pale yellow oil (4.510 g; 71%). LC-MS: t R =0.80 min.; [M+H] + : no ionisation.
2-(4-trifluoromethyl-phenoxy)-ethanol
A mixture of 4-trifluoromethyl-phenol (10.000 g; 61.687 mmol), potassium carbonate (9.377 g; 67.856 mmol), and methyl bromoacetate (5.67 ml; 61.687 mmol) in acetone (250 ml) was heated at reflux for 1 h30. Filtration, concentration to dryness under reduced pressure, and purification by FC (DCM) afforded (4-trifluoromethyl-phenoxy)-acetic acid methyl ester as a colorless oil (14.100 g; 98%). LC-MS: t R =0.95 min.; [M+H] + : no ionisation.
To an ice-cooled suspension of lithium aluminum hydride (0.972 g; 25.622 mmol) in anhydrous THF (60 ml) was added dropwise a solution of (4-trifluoromethyl-phenoxy)-acetic acid methyl ester (3.000 g; 12.811 mmol) in anhydrous THF (40 ml). The resulting reaction mixture was further stirred at 0° C. for 20 min. Water (1 ml), 15% aq. NaOH (1 ml), and water (3 ml) were then successively added dropwise. Filtration, concentration to dryness under reduced pressure, and purification by FC (DCM/MeOH, 19/1) afforded 2-(4-trifluoromethyl-phenoxy)-ethanol as a colorless solid (2.370 g; 90%). LC-MS: t R =0.84 min.; [M+H] + : no ionisation.
2-(4-fluoro-3-trifluoromethyl-phenoxy)-ethanol
A mixture of 4-fluoro-3-trifluoromethyl-phenol (10.000 g; 55.525 mmol), potassium carbonate (9.591 g; 69.406 mmol), and methyl bromoacetate (6.38 ml; 69.406 mmol) in butanone (380 ml) was heated at reflux for 1 h30. Filtration, concentration to dryness under reduced pressure, and purification by FC (heptane/EA, 4/1) afforded (4-fluoro-3-trifluoromethyl-phenoxy)-acetic acid methyl ester as a colorless oil (13.300 g; 95%). LC-MS: t R =0.95 min.; [M+H] + : no ionisation.
A solution of (4-fluoro-3-trifluoromethyl-phenoxy)-acetic acid methyl ester (13.300 g; 52.744 mmol) in MeOH (150 ml) was treated with aq. 1N NaOH (79 ml; 1.5 eq.), and the resulting mixture was further stirred at rt for 20 min. MeOH was then removed under reduced pressure, water (150 ml) was added followed by aq. 1N HCl (100 ml). Filtration of the precipitated solid, and drying under HV afforded (4-fluoro-3-trifluoromethyl-phenoxy)-acetic acid as a colorless solid (10.030 g; 80%). LC-MS: t R =0.85 min.; [M+H] + : no ionisation.
According to the previously described general procedure (GP6), reduction of (4-fluoro-3-trifluoromethyl-phenoxy)-acetic acid (10.030 g; 42.119 mmol) gave after purification by FC (DCM/MeOH=9/1) the product 2-(4-fluoro-3-trifluoromethyl-phenoxy)-ethanol as a colorless solid (8.900 g; 94%). LC-MS: t R =0.85 min.; [M+H] + : no ionisation.
A.5 Synthesis of aldehydes R 1 —O—CH 2 —CHO
(3-trifluoromethyl-phenoxy)-acetaldehyde [general procedure for the oxidation of primary alcohols to aldehydes according to the Swern procedure]
A cooled (−78° C.) solution of oxalyl chloride (0.49 ml; 5.821 mmol) in anhydrous DCM (25 ml) was treated dropwise with a solution of dimethyl sulfoxide (0.91 ml; 11.641 mmol) in anhydrous DCM (4 ml). After 10 min., a solution of 2-(3-trifluoromethyl-phenoxy)-ethanol (0.800 g; 3.880 mmol) in DCM (8 ml) was added dropwise, and the reaction mixture was further stirred at −78° C. for 30 min. TEA (2.70 ml; 19.402 mmol) was then added dropwise, and after 10 min. the resulting mixture was allowed to warm-up to 0° C. before a mixture of water (2.5 ml) and DCM (25 ml) was added. The aq. layer was extracted with DCM (2×25 ml), and the mixed organic layers were then washed with aq. sat. NaHCO 3 (20 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give (3-trifluoromethyl-phenoxy)-acetaldehyde as a yellow oil (0.792 g; 99%). This aldehyde was used for the next step without additional purification.
(3,4-dimethyl-phenoxy)-acetaldehyde
A cooled (−78° C.) solution of oxalyl chloride (0.76 ml; 9.000 mmol) in anhydrous DCM (40 ml) was treated dropwise with a solution of dimethyl sulfoxide (1.40 ml; 18.000 mmol) in anhydrous DCM (6 ml). After 10 min., a solution of 2-(3,4-dimethyl-phenoxy)-ethanol (0.997 g; 6.000 mmol) in DCM (12 ml) was added dropwise, and the reaction mixture was further stirred at −78° C. for 30 min. TEA (4.17 ml; 30.000 mmol) was then added dropwise, and after 10 min. the resulting mixture was allowed to warm-up to 0° C. before a mixture of water (4 ml) and DCM (40 ml) was added. The aq. layer was extracted with DCM (2×40 ml), and the mixed organic layers were then washed with aq. sat. NaHCO 3 (30 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give (3,4-dimethyl-phenoxy)-acetaldehyde as a yellow oil (0.985 g; 99%).
(4-trifluoromethyl-phenoxy)-acetaldehyde
According to the general procedure described above for the oxidation of alcohols under Swern conditions, oxidation of 2-(4-trifluoromethyl-phenoxy)-ethanol (0.800 g; 3.880 mmol) afforded the target aldehyde (4-trifluoromethyl-phenoxy)-acetaldehyde (0.792 g; 99%) as a yellow oil which was used for the next step without additional purification.
(4-fluoro-3-trifluoromethyl-phenoxy)-acetaldehyde
According to the general procedure described above for the oxidation of alcohols under Swern conditions, oxidation of 2-(4-fluoro-3-trifluoromethyl-phenoxy)-ethanol (0.450 g; 2.008 mmol) afforded the target aldehyde (4-fluoro-3-trifluoromethyl-phenoxy)-acetaldehyde (0.446 g; 100%) as a yellow oil which was used for the next step without additional purification.
B Synthesis of Substituted Imidazoles
B.1 Synthesis of Imidazoles Based on a Regioselective Deiodination
4,5-diiodo-2-ethyl-1H-imidazole
To a slightly yellow homogeneous solution of 2-ethylimidazole (15.000 g; 156.035 mmol) in dioxane (250 ml) and distilled water (250 ml) was added successively, at rt (in one portion), sodium carbonate (49.614 g; 468.104 mmol), and iodine (87.126 g; 343.276 mmol). The resulting brown heterogeneous reaction mixture was further stirred at rt, under nitrogen, for 24 h. EA (500 ml) was then added followed by an aq. solution of sodium thiosulfate (45 g Na 2 S 2 O 3 in 300 ml of water). The yellow homogeneous organic layer was separated and additionally washed with an aq. solution of sodium thiosulfate (30 g Na 2 S 2 O 3 in 300 ml of water), and finally with brine (200 ml). The yellow organic layer was then dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give the pure product 4,5-diiodo-2-ethyl-1H-imidazole as a pale yellow solid which was further dried under HV (49.76 g; 92%). LC-MS: t R =0.55 min.; [M+H] + =349.18 g/mol.
[2-(2-ethyl-4,5-diiodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
To a solution of 4,5-diiodo-2-ethyl-1H-imidazole (10.000 g; 28.743 mmol) in anhydrous DMF (140 ml) was added portionwise, at rt, 55-65% sodium hydride moistened with oil (1.379 g; 34.491 mmol). The resulting mixture was further stirred at rt, under nitrogen, for 20 min. The mixture was then heated to 100° C., and a colorless homogeneous solution of 2-(Boc-amino)-ethylbromide (7.085 g; 31.617 mmol) in anhydrous DMF (100 ml) was added dropwise, over 1 h, with an addition funnel. After completion of the addition, the resulting dark-orange homogeneous mixture was further heated at 100° C. for 1 h30. The reaction mixture was cooled to rt, and water (300 ml) was added slowly. This mixture was extracted with ether (7×100 ml). The combined organic layers were washed with brine (3×100 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give a yellow oil (13.020 g). The crude was purified by FC (DCM/MeOH=25/1) to give the pure product [2-(2-ethyl-4,5-diiodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a pale yellow solid which was further dried under HV (9.950 g; 70.5%). LC-MS: t R =0.78 min.; [M+H] + =492.33 g/mol.
[2-(2-ethyl-4-iodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
A solution of [2-(2-ethyl-4,5-diiodo-imidazol-1-yl)-ethyl]carbamic acid tert-butyl ester (22.990 g; 46.813 mmol) in anhydrous THF (280 ml), under nitrogen, was cooled to −40° C., and a solution of 3M EtMgBr in ether (15.6 ml; 46.8 mmol) was then added dropwise over 15 min. After addition, the resulting solution was stirred between −40° C. and −30° C. for 10 min. (conversion=55% according to LC-MS), and additional 3M EtMgBr in ether (10 ml; 30 mmol) was added until the reaction was finished. The reaction mixture was then treated with water (10 ml) at −40° C., and was allowed to warm-up to rt. Ether (300 ml) was added, and the resulting solution was washed with water (200 ml) and brine (200 ml). The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give a yellow solid (16.95 g). The crude was purified by FC (DCM/MeOH=20/1) to give the pure product [2-(2-ethyl-4-iodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a yellow solid (15.500 g; 91%). LC-MS: t R =0.65 min.; [M+H] + =366.39 g/mol.
2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine
To an ice-cooled solution of [2-(2-ethyl-4-iodo-imidazol-1-yl)-ethyl]carbamic acid tert-butyl ester (5.720 g; 15.662 mmol) in DCM (125 ml) was added slowly 4N HCl in dioxane (78 ml; 312 mmol). The resulting suspension was stirred at 0° C. for 15 min., then at rt for 1 h. The volatiles were removed under reduced pressure, then under HV. The product 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine was obtained as a pale beige solid (5.96 g; 100%; presence of 3 eq. of HCl). LC-MS: t R =0.14 min.; [M+H] + =266.24 g/mol.
In order to generate the free amine for Pictet-Spengler reaction, the previously dried chlorhydrate salt (5.96 g; with 3 eq. HCl) was suspended in anhydrous ethanol (20 ml) and N-ethyldiisopropylamine (12.1 ml; 70.680 mmol; 4.5 eq.) was added. The resulting homogeneous solution was then appropriate for microwave-assisted Pictet-Spengler reaction.
4,5-diiodo-2-methyl-1H-imidazole
To a slightly yellow homogeneous solution of 2-methylimidazole (15.000 g; 182.680 mmol) in dioxane (305 ml) and distilled water (305 ml) was added successively, at rt (in one portion), sodium carbonate (58.086 g; 548.040 mmol), and iodine (102.005 g; 401.896 mmol). The resulting brown heterogeneous reaction mixture was further stirred at rt, under nitrogen, for 24 h. EA (900 ml) was then added followed by an aq. solution of sodium thiosulfate (54 g Na 2 S 2 O 3 in 540 ml of water). The yellow homogeneous organic layer was separated and additionally washed with an aq. solution of sodium thiosulfate (36 g Na 2 S 2 O 3 in 300 ml of water), and finally with brine (300 ml). The yellow organic layer was then dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give the pure product 4,5-diiodo-2-methyl-1H-imidazole as a yellow solid which was further dried under HV (61.000 g; 100%). LC-MS: t R =0.52 min.; [M+H] + =335.14 g/mol.
[2-(2-methyl-4,5-diiodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
To a yellow solution of 4,5-diiodo-2-methyl-1H-imidazole (5.000 g; 14.975 mmol) in anhydrous DMF (75 ml) was added portionwise, at rt, 55-65% sodium hydride moistened with oil (719 mg; 17.975 mmol). The resulting mixture was further stirred at rt, under nitrogen, for 20 min. The mixture was then heated to 100° C., and a colorless homogeneous solution of 2-(Boc-amino)-ethylbromide (3.691 g; 16.473 mmol) in anhydrous DMF (50 ml) was added dropwise, over 1 h, with an addition funnel. After completion of the addition, the resulting dark-orange homogeneous mixture was further heated at 100° C. for 1 h15. The reaction mixture was cooled to rt, and water (300 ml) was added slowly. This mixture was extracted with ether (4×200 ml). The combined organic layers were washed with brine (100 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give an orange oil (6.570 g). The crude was purified by FC (DCM/MeOH=10/1) to give the pure product [2-(2-methyl-4,5-diiodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a yellow solid which was further dried under HV (4.400 g; 62%). LC-MS: t R =0.74 min.; [M+H] + =478.28 g/mol.
[2-(4-iodo-2-methyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
A solution of [2-(2-methyl-4,5-diiodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester (13.300 g; 27.878 mmol) in anhydrous THF (160 ml), under nitrogen, was cooled to −40° C., and a solution of 1M EtMgBr in THF (27.9 ml; 27.9 mmol) was then added dropwise over 20 min. After addition, the resulting solution was stirred between −40° C. and −30° C. for 10 min. (conversion=64% according to LC-MS), and additional 1M EtMgBr in THF (11.15 ml; 11.15 mmol) was added until the reaction was finished. The reaction mixture was then treated with water (8 ml) at −40° C., and was allowed to warm-up to rt. Ether (150 ml) was added, and the resulting solution was washed with water (100 ml) and brine (100 ml). The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give an orange oil (11.1 g). The crude was purified by FC (DCM/MeOH=15/1) to give the pure product [2-(2-methyl-4-iodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a yellow solid (7.270 g; 74%). LC-MS: t R =0.62 min.; [M+H] + =352.34 g/mol.
2-(4-iodo-2-methyl-imidazol-1-yl)-ethylamine
To an ice-cooled solution of [2-(4-iodo-2-methyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester (2.800 g; 7.973 mmol) in DCM (45 ml) was added slowly 4N HCl in dioxane (28.25 ml; 113.000 mmol). The resulting suspension was stirred at 0° C. for 15 min., then at rt for 1 h. The volatiles were removed under reduced pressure, then under HV. The product 2-(4-iodo-2-methyl-imidazol-1-yl)-ethylamine was obtained as a pale beige solid (2.880 g; 100%; presence of 3 eq. of HCl). LC-MS: t R =0.14 min.; [M+H] + =251.92 g/mol.
In order to generate the free amine for Pictet-Spengler reaction, the previously dried chlorhydrate salt (2.880 g; with 3 eq. HCl) was suspended in anhydrous ethanol (9 ml) and N-ethyldiisopropylamine (6.2 ml; 36.216 mmol; 4.5 eq.) was added. The resulting homogeneous solution was then appropriate for microwave-assisted Pictet-Spengler reaction.
4,5-diiodo-2-isopropyl-1H-imidazole
To a slightly yellow homogeneous solution of 2-isopropylimidazole (10.000 g; 90.778 mmol) in dioxane (155 ml) and distilled water (155 ml) was added successively, at rt (in one portion), sodium carbonate (28.865 g; 272.333 mmol), and iodine (50.688 g; 199.711 mmol). The resulting brown heterogeneous reaction mixture was further stirred at rt, under nitrogen, for 24 h. EA (450 ml) was then added followed by an aq. solution of sodium thiosulfate (27 g Na 2 S 2 O 3 in 270 ml of water). The yellow homogeneous organic layer was separated and additionally washed with an aq. solution of sodium thiosulfate (18 g Na 2 S 2 O 3 in 180 ml of water), and finally with brine (130 ml). The yellow organic layer was then dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give the pure product 4,5-diiodo-2-isopropyl-1H-imidazole as a yellow solid which was further dried under HV (31.810 g; 97%). LC-MS: t R =0.62 min.; [M+H] + =363.19 g/mol.
[2-(4,5-diiodo-2-isopropyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
To a yellow solution of 4,5-diiodo-2-isopropyl-1H-imidazole (10.000 g; 27.629 mmol) in anhydrous DMF (140 ml) was added portionwise, at rt, 55-65% sodium hydride moistened with oil (1.326 g; 33.154 mmol). The resulting mixture was further stirred at rt, under nitrogen, for 20 min. The mixture was then heated to 100° C., and a colorless homogeneous solution of 2-(Boc-amino)-ethylbromide (6.810 g; 30.391 mmol) in anhydrous DMF (100 ml) was added dropwise, over 1 h, with an addition funnel. After completion of the addition, the resulting mixture was further heated at 100° C. for 1 h30. The reaction mixture was cooled to 0° C., and water (300 ml) was added slowly. This mixture was extracted with ether (5×150 ml). The combined organic layers were washed with brine (100 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give an orange oil. The crude was purified by FC (DCM/MeOH=30/1) to give the pure product [2-(4,5-diiodo-2-isopropyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a yellow solid which was further dried under HV (9.720 g; 70%). LC-MS: t R =0.82 min.; [M+H] + =506.32 g/mol.
[2-(4-iodo-2-isopropyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
A solution of [2-(4,5-diiodo-2-isopropyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester (22.930 g; 45.394 mmol) in anhydrous THF (280 ml), under nitrogen, was cooled to −40° C., and a solution of 3M EtMgBr in ether (15.2 ml; 45.600 mmol) was then added dropwise over 10 min. After addition, the resulting solution was stirred between −40° C. and −30° C. for 10 min. (conversion=55% according to LC-MS), and then additional 3M EtMgBr in ether (7.6 ml; 22.800 mmol) was added. Finally in order to complete this reaction, a last addition of 3M EtMgBr in ether (2.9 ml; 8.700 mmol) was performed. The reaction mixture was then treated with water (10 ml) at −40° C., and was allowed to warm-up to rt. Ether (300 ml) was added, and the resulting solution was washed with water (200 ml) and brine (200 ml). The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give a yellow solid (16.950 g). The crude was purified by FC (DCM/MeOH=20/1) to give the pure product [2-(4-iodo-2-isopropyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a yellow solid (15.800 g; 92%). LC-MS: t R =0.67 min.; [M+H] + =380.39 g/mol.
2-(4-iodo-2-isopropyl-imidazol-1-yl)-ethylamine
To an ice-cooled solution of [2-(4-iodo-2-isopropyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester (3.011 g; 7.941 mmol) in DCM (75 ml) was added slowly 4N HCl in dioxane (40 ml; 160 mmol). The resulting suspension was stirred at 0° C. for 15 min., then at rt for 2 h45. The volatiles were removed under reduced pressure, then under HV. The product 2-(4-iodo-2-isopropyl-imidazol-1-yl)-ethylamine was obtained as a colorless solid (2.720 g; 100%; presence of 2 eq. of HCl). LC-MS: t R =0.19 min.; [M+H] + =280.17 g/mol.
In order to generate the free amine for Pictet-Spengler reaction, the previously dried chlorhydrate salt (2.720 g; with 2 eq. HCl) was suspended in anhydrous ethanol (8 ml) and N-ethyldiisopropylamine (4.0 ml; 23.300 mmol; 3 eq.) was added. The resulting homogeneous solution was then appropriate for microwave-assisted Pictet-Spengler reaction.
4,5-diiodo-2-propyl-1H-imidazole
To a slightly yellow homogeneous solution of 2-propylimidazole (10.000 g; 86.239 mmol) in dioxane (155 ml) and distilled water (155 ml) was added successively, at rt (in one portion), sodium carbonate (27.559 g; 258.716 mmol), and iodine (48.154 g; 189.725 mmol). The resulting brown heterogeneous reaction mixture was further stirred at rt, under nitrogen, for 24 h. EA (350 ml) was then added followed by an aq. solution of sodium thiosulfate (30 g Na 2 S 2 O 3 in 200 ml of water). The yellow homogeneous organic layer was separated and additionally washed with an aq. solution of sodium thiosulfate (30 g Na 2 S 2 O 3 in 200 ml of water), and finally with brine (2×200 ml). The yellow organic layer was then dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give the pure product 4,5-diiodo-2-propyl-1H-imidazole as a yellow solid which was further dried under HV (30.660 g; 98%). LC-MS: t R =0.68 min.; [M+H] + =362.73 g/mol.
[2-(4,5-diiodo-2-propyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
To a solution of 4,5-diiodo-2-propyl-1H-imidazole (15.000 g; 41.443 mmol) in anhydrous DMF (260 ml) was added portionwise, at rt, 55-65% sodium hydride moistened with oil (1.989 g; 49.732 mmol). The resulting mixture was further stirred at rt, under nitrogen, for 20 min. The mixture was then heated to 100° C., and a colorless homogeneous solution of 2-(Boc-amino)-ethylbromide (10.216 g; 45.587 mmol) in anhydrous DMF (100 ml) was added dropwise, over 1 h, with an addition funnel. After completion of the addition, the resulting dark-orange homogeneous mixture was further heated at 100° C. for 1 h30. The reaction mixture was cooled to rt, and water (300 ml) was added slowly. This mixture was extracted with ether (3×200 ml). The combined organic layers were washed with brine (2×100 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give a yellow oil. The crude was purified by FC (heptane/EA=1/1) to give the pure product [2-(4,5-diiodo-2-propyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a yellow solid which was further dried under HV (8.690 g; 42%). LC-MS: t R =0.88 min.; [M+H] + =505.77 g/mol.
[2-(4-iodo-2-propyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
A solution of [2-(4,5-diiodo-2-propyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester (8.690 g; 17.204 mmol) in anhydrous THF (100 ml), under nitrogen, was cooled to −40° C., and a solution of 1M EtMgBr in THF (20.5 ml; 20.5 mmol; 1.2 eq.) was then added dropwise over 15 min. After addition, the resulting solution was stirred between −40° C. and −30° C. for 10 min. (conversion=55% according to LC-MS), and additional 1M EtMgBr in THF (13.9 ml; 13.9 mmol; 0.8 eq.) was added in order to complete the reaction. The reaction mixture was then treated with water (5 ml) at −40° C., and was allowed to warm-up to rt. Ether (200 ml) was added, and the resulting solution was washed with brine (2×200 ml). The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The crude was purified by FC (DCM/MeOH=20/1) to give the pure product [2-(4-iodo-2-propyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a yellow oil (6.110 g; 94%). LC-MS: t R =0.74 min.; [M+H] + =380.00 g/mol.
2-(4-iodo-2-propyl-imidazol-1-yl)-ethylamine
To an ice-cooled solution of [2-(4-iodo-2-propyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester (6.110 g; 16.111 mmol) in DCM (100 ml) was added slowly 4N HCl in dioxane (80.5 ml; 322 mmol; 20 eq.). The resulting suspension was stirred at 0° C. for 15 min., and then at rt for 2 h. The volatiles were removed under reduced pressure, then under HV. The product 2-(4-iodo-2-propyl-imidazol-1-yl)-ethylamine was obtained as a colorless solid (5.620 g; 100%; presence of 2 eq. of HCl). LC-MS: t R =0.24 min.; [M+H] + =279.96 g/mol.
In order to generate the free amine 2-(4-iodo-2-propyl-imidazol-1-yl)-ethylamine for Pictet-Spengler reaction, the previously dried chlorhydrate salt (5.620 g; with 2 eq. HCl) was suspended in anhydrous ethanol (35 ml) and N-ethyldiisopropylamine (10 ml; 58.413 mmol; 3.6 eq.) was added. The resulting homogeneous solution was then appropriate for microwave-assisted Pictet-Spengler reaction.
1-trityl-1H-imidazole-2-carbaldehyde
A cooled (−78° C.) yellow solution of 1-(triphenylmethyl)imidazole (25.000 g; 80.542 mmol) in anhydrous THF (750 ml) was treated dropwise (in 55 min.) with a 1.6M solution of butyllithium in hexanes (55.35 ml; 88.560 mmol). After addition, the resulting pink homogeneous solution was further stirred at −78° C., under nitrogen, for 30 min. before a solution of anhydrous DMF (6.8 ml; 88.186 mmol) in anhydrous THF (40 ml) was added dropwise (in 40 min.). The resulting mixture was additionally stirred at −78° C., under nitrogen, for 1 h before aq. sat. NH 4 Cl (50 ml) was added dropwise. Ether (300 ml) and water (400 ml) were successively added, and this mixture was allowed to warm-up to rt. The yellow organic layer was additionally washed with water (300 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The crude was purified by FC (DCM/MeOH=30/1) to give the pure product 1-trityl-1H-imidazole-2-carbaldehyde as a pale yellow solid which was further dried under HV (20.660 g; 76%). LC-MS: t R =1.03 min.; [M+H] + : no ionisation.
(1-trityl-1H-imidazol-2-yl)-MeOH
A heterogeneous mixture of 1-trityl-1H-imidazole-2-carbaldehyde (6.310 g; 18.646 mmol) in anhydrous MeOH (150 ml) was heated to 45° C., and was treated portionwise with sodium borohydride (2.116 g; 55.938 mmol). After completion of the addition, heating at 45° C. was continued for 2 h. The reaction mixture was then allowed to cool to rt, filtered, and the discarded colorless solid was additionally washed with chloroform. The filtrate was concentrated to dryness under reduced pressure affording the expected product (1-trityl-1H-imidazol-2-yl)-MeOH as a colorless solid which was further dried under HV (6.340 g; 99%). This dried product was used for the next step without additional purification. LC-MS: t R =0.80 min.; [M+H] + : no ionisation.
2-methoxymethyl-1-trityl-1H-imidazole
A cooled (0° C.) colorless homogeneous solution of (1-trityl-1H-imidazol-2-yl)-MeOH (6.340 g; 18.624 mmol) in anhydrous THF (100 ml) was treated with sodium hydride (2.234 g; 55.871 mmol; 60% NaH moistened with oil). The resulting mixture was stirred at rt, under nitrogen, for 20 min. and was again cooled (0° C.) before a colorless homogeneous solution of iodomethane (2 ml; 32.055 mmol) in anhydrous THF (18 ml) was added dropwise. The resulting mixture was allowed to warm-up to rt, and was further stirred during 1h30. Water (50 ml) was then added dropwise followed by ether (100 ml). The aq. layer was additionally extracted with ether (2×50 ml), and the mixed organic extracts were dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH=50/1) gave the pure product 2-methoxymethyl-1-trityl-1H-imidazole as a grey solid which was further dried under HV (3.370 g; 51%). LC-MS: t R =0.84 min.; [M+H] + : no ionisation.
2-methoxymethyl-1H-imidazole
A heterogeneous mixture of 2-methoxymethyl-1-trityl-1H-imidazole (3.892 g; 10.980 mmol) in anhydrous MeOH (320 ml) was treated with acetic acid (16 ml), and the resulting mixture was heated at reflux (75° C.) for 2 h. The resulting yellow homogeneous solution was allowed to cool to rt, and was then concentrated to dryness under reduced pressure. DCM (30 ml) was added and this organic layer was extracted with water (3×10 ml). The mixed aq. layers were concentrated to dryness under reduced pressure to give the expected product 2-methoxymethyl-1H-imidazole as a yellow oil which was further dried under high vacuum (1.230 g; 99%). LC-MS: t R =0.15 min.; [M+H] + : no ionisation.
4,5-diiodo-2-methoxymethyl-1H-imidazole
A homogeneous solution of 2-methoxymethyl-1H-imidazole (1.230 g; 10.969 mmol) in dioxane (20 ml) and water (20 ml) was successively treated at rt with sodium carbonate (3.487 g; 32.908 mmol), and iodine (6.125 g; 24.132 mmol). The resulting brown heterogeneous reaction mixture was further stirred at rt, under nitrogen, for 24 h. EA (60 ml) was then added followed by an aq. solution of sodium thiosulfate (3.5 g Na 2 S 2 O 3 in 35 ml of water). The yellow homogeneous organic layer was separated and additionally washed with an aq. solution of sodium thiosulfate (2.3 g Na 2 S 2 O 3 in 23 ml of water), and finally with brine (25 ml). The yellow organic layer was then dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give the pure product 4,5-diiodo-2-methoxymethyl-1H-imidazole as a yellow solid which was further dried under HV (3.006 g; 75%). LC-MS: t R =0.66 min.; [M+H] + =365.09 g/mol.
[2-(4,5-diiodo-2-methoxymethyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butylester
To a solution of 4,5-diiodo-2-methoxymethyl-1H-imidazole (3.000 g; 8.244 mmol) in anhydrous DMF (35 ml) was added portionwise, at rt, 55-65% sodium hydride moistened with oil (395 mg; 9.895 mmol). The resulting mixture was further stirred at rt, under nitrogen, for 20 min. The mixture was then heated to 100° C., and a colorless homogeneous solution of 2-(Boc-amino)-ethylbromide (2.032 g; 9.068 mmol) in anhydrous DMF (30 ml) was added dropwise, over 15 min., with an addition funnel. After completion of the addition, the resulting dark-orange homogeneous mixture was further heated at 100° C. for 1 h45. The reaction mixture was cooled to rt, and water (175 ml) was added slowly. This mixture was extracted with ether (4×120 ml). The combined organic layers were dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The crude was purified by FC (DCM/MeOH=50/1) to give the pure product [2-(4,5-diiodo-2-methoxymethyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butylester as a pale yellow solid which was further dried under HV (3.050 g; 73%). LC-MS: t R =0.87 min.; [M+H] + =508.16 g/mol.
[2-(4-iodo-2-methoxymethyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
A solution of [2-(4,5-diiodo-2-methoxymethyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butylester (3.050 g; 6.015 mmol) in anhydrous THF (30 ml), under nitrogen, was cooled to −40° C., and a solution of 1M EtMgBr in THF (6.02 ml; 6.02 mmol) was then added dropwise over 10 min. After addition, the resulting solution was stirred between −40° C. and −30° C. for 10 min. (conversion=53% according to LC-MS), and additional 1M EtMgBr (3 ml; 3 mmol) was added. Stirring at −40° C. was continued for additional 20 min. (reaction completed). The reaction mixture was then treated with water (2 ml) at −40° C., and was allowed to warm-up to rt. Ether (40 ml) was added, and the resulting solution was washed with water (25 ml) and brine (30 ml). The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The crude was purified by FC (DCM/MeOH=50/1) to give the pure product [2-(4-iodo-2-methoxymethyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a yellow solid (1.645 g; 72%). LC-MS: t R =0.70 min.; [M+H] + =382.29 g/mol.
2-(4-iodo-2-methoxymethyl-imidazol-1-yl)-ethylamine
To an ice-cooled solution of [2-(4-iodo-2-methoxymethyl-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester (3.051 g; 8.003 mmol) in DCM (60 ml) was added slowly 4N HCl in dioxane (40 ml; 160 mmol). The resulting suspension was stirred at 0° C. for 15 min., then at rt for 2 h. The volatiles were removed under reduced pressure, then under HV. The product 2-(4-iodo-2-methoxymethyl-imidazol-1-yl)-ethylamine was obtained as a pale beige solid (2.750 g; 100%; presence of 2 eq. of HCl). LC-MS: t R =0.21 min.; [M+H] + =282.24 g/mol.
In order to generate the free amine for Pictet-Spengler reaction, the previously dried chlorhydrate salt (2.750 g; with 2 eq. HCl) was suspended in anhydrous ethanol (9 ml) and N-ethyldiisopropylamine (4.1 ml; 23.949 mmol; 3 eq.) was added. The resulting homogeneous solution was then appropriate for microwave-assisted Pictet-Spengler reaction.
2,4,5-triiodo-1H-imidazole
To a slightly yellow homogeneous solution of imidazole (5.000 g; 73.444 mmol) in dioxane (135 ml) and distilled water (135 ml) was added successively, at rt (in one portion), sodium carbonate (35.029 g; 330.500 mmol), and iodine (61.515 g; 242.366 mmol). The resulting brown heterogeneous reaction mixture was further stirred at rt, under nitrogen, for 24 h. EA (250 ml) was then added followed by an aq. solution of sodium thiosulfate (22.50 g Na 2 S 2 O 3 in 150 ml of water). The yellow homogeneous organic layer was then dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give the crude product 2,4,5-triiodo-1H-imidazole as a yellow solid which was further dried under HV (32.700 g; 100%). LC-MS: t R =0.78 min.; [M+H] + =447.03 g/mol.
[2-(2,4,5-triiodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
To a yellow solution of 2,4,5-triiodo-1H-imidazole (15.295 g; 34.313 mmol) in anhydrous DMF (200 ml) was added portionwise, at rt, 55-65% sodium hydride moistened with oil (2.058 g; 51.469 mmol). The resulting mixture was further stirred at rt, under nitrogen, for 20 min. The mixture was then heated to 100° C., and a colorless homogeneous solution of 2-(Boc-amino)-ethylbromide (11.534 g; 51.469 mmol) in anhydrous DMF (100 ml) was added dropwise, over 1 h, with an addition funnel. After completion of the addition, the resulting mixture was further heated at 100° C. for 1 h. The reaction mixture was cooled to 0° C., and water (200 ml) was added slowly. This mixture was extracted with ether (5×200 ml). The combined organic layers were washed with brine (100 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give a yellow oil. The crude was purified by FC (heptane/EA=3/2) to give the pure product [2-(2,4,5-triiodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a colorless solid which was further dried under HV (8.540 g; 42%). LC-MS: t R =0.93 min.; [M+H] + =589.89 g/mol.
[2-(4-iodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester
A solution of [2-(2,4,5-triiodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester (8.120 g; 13.787 mmol) in anhydrous THF (100 ml), under nitrogen, was cooled to −40° C., and a solution of 1M EtMgBr in THF (27.6 ml; 27.6 mmol) was then added dropwise over 15 min. After addition, the resulting milky mixture was stirred between −40° C. and −30° C. for 10 min. (reaction completed according to LC-MS). The reaction mixture was then treated with water (5 ml) at −40° C., and was allowed to warm-up to rt. Ether (100 ml) was added, and the resulting solution was washed with water (150 ml) and brine (150 ml). The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give a purple oil (5.480 g). The crude was purified by FC (DCM/MeOH=20/1) to give the pure product [2-(4-iodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester as a colorless solid (2.940 g; 63%). LC-MS: t R =0.62 min.; [M+H] + =338.07 g/mol.
2-(4-iodo-imidazol-1-yl)-ethylamine
To an ice-cooled solution of [2-(4-iodo-imidazol-1-yl)-ethyl]-carbamic acid tert-butyl ester (6.154 g; 18.253 mmol) in DCM (200 ml) was added slowly 4N HCl in dioxane (91 ml; 364 mmol). The resulting suspension was stirred at 0° C. for 15 min., then at rt for 1 h. The volatiles were removed under reduced pressure, then under HV. The product 2-(4-iodo-imidazol-1-yl)-ethylamine was obtained as a colorless solid (5.690 g; 100%; presence of 2 eq. of HCl). LC-MS: t R =0.15 min.; [M+H] + =238.14 g/mol.
In order to generate the free amine for Pictet-Spengler reaction, the previously dried chlorhydrate salt (5.690 g; with 2 eq. HCl) was suspended in anhydrous ethanol (80 ml) and N-ethyldiisopropylamine (9.37 ml; 54.759 mmol; 3 eq.) was added. The resulting homogeneous solution was then appropriate for microwave-assisted Pictet-Spengler reaction.
B.2 Synthesis of Imidazoles Starting with Disubstituted Imidazoles
Synthesis of 2-imidazol-1-yl-ethylamine derivatives by N-alkylation of disubstituted imidazoles [general procedure (GP9)]
Sodium hydroxide (180 mmol; powder) and tetrabutylammonium hydrogensulfate (1.80 mmol) were successively added to a solution of the respective imidazole derivative (45.00 mmol) in MeCN (100 ml). After 30 min., 2-chloroethylamine hydrochloride (54.00 mmol) was added and the reaction mixture was stirred for 24 h at reflux. The obtained suspension was filtered and the filtrate was concentrated in vacuo to give a crude oil which was used without further purification.
2-(2,4-dimethyl-imidazol-1-yl)-ethylamine
Prepared by N-alkylation of 2,4-dimethyl-1H-imidazole according to the previously described general procedure (GP9).
1 H-NMR (CDCl 3 ; 300 MHz): δ=6.50 (s; 1H), 3.76 (t, J=6.2 Hz, 2H), 2.91 (t, J=6.2 Hz, 2H), 2.28 (s, 3H), 2.09 (s, 3H).
2-(2-ethyl-4-methyl-imidazol-1-yl)-ethylamine
Prepared by N-alkylation of 2-ethyl-4-methyl-1H-imidazole according to the previously described general procedure (GP9).
1 H-NMR (CDCl 3 ; 300 MHz): δ=6.43 (s; 1H), 3.70 (t, J=6.2 Hz, 2H), 2.84 (t, J=6.2 Hz, 2H), 2.52 (q, J=7.5 Hz, 2H), 2.04 (s, 3H), 1.17 (t, J=7.5 Hz, 3H).
C Synthesis of 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives
C.1 Synthesis of 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives via microwave-assisted Pictet-Spengler reaction followed by Boc-protection
3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester [general procedure for microwave-assisted Pictet-Spengler reaction (GP10)]
A homogeneous solution of 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (518 mg; 1.954 mmol) in anhydrous ethanol (2.5 ml) was treated with a solution of 3-(4-trifluoromethyl-phenyl)-propionaldehyde (395 mg; 1.954 mmol) in anhydrous ethanol (2.5 ml). The mixture was sealed and put in the microwave oven (70 W; 110° C.; 13 bars; 10 min.). This microwave-assisted Pictet-Spengler reaction was repeated three additional times with the same amount of starting material. The resulting crude reaction mixtures were finally mixed and concentrated to dryness under reduced pressure giving the crude 3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (brown oil; 5.370 g). LC-MS: t R =0.72 min.; [M+H] + =450.28 g/mol.
The crude 3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (theoretical amount: 7.815 mmol) was dissolved in anhydrous DCM (10 ml), and N-ethyldiisopropylamine (2.67 ml; 15.630 mmol) was added. The resulting mixture was then cooled to 0° C., and a solution of di-tert-butyl dicarbonate Boc 2 O (2.046 g; 9.378 mmol) in anhydrous DCM (5 ml) was added in one portion. After completion of the addition, the reaction mixture was further stirred at 0° C. for 15 min., and at rt overnight. The resulting mixture was then washed with brine (2×100 ml), and the organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The crude was purified by FC (DCM/MeOH=25/1) to give the pure product 3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid which was further dried under HV (2.820 g; 66%). LC-MS: t R =0.93 min.; [M+H] + =550.41 g/mol.
8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP10), the microwave-assisted Pictet-Spengler reaction affording 8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (LC-MS: t R =0.75 min.; [M+H] + =486.38 g/mol) was performed in three experiments (70 W; 110° C.; 11 bars; 10 min.) with the same amount of starting material 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (439 mg; 1.656 mmol).
After Boc-protection and purification by FC (DCM/MeOH=30/1), pure 8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.450 g; 84%) was obtained as a yellow solid. LC-MS: t R =0.96 min.; [M+H] + =586.29 g/mol.
8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 100° C.; 8 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (355.2 mg; 1.340 mmol) and 3-(3,4-difluoro-phenyl)-propionaldehyde (228.7 mg; 1.340 mmol) afforded 8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by HPLC.
The pure product 8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (387.2 mg; 0.748 mmol; 56%). LC-MS: t R =0.92 min.; [M+H] + =518.08 g/mol.
8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 100° C.; 8 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (296.9 mg; 1.120 mmol) and 3-(3,5-difluoro-4-methyl-phenyl)-propionaldehyde (206.7 mg; 1.120 mmol) afforded 8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by HPLC.
The pure product 8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (349.3 mg; 0.657 mmol; 59%). LC-MS: t R =0.95 min.; [M+H] + =532.10 g/mol.
3-ethyl-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 100° C.; 8 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (265.1 mg; 1.000 mmol) and 3-(2-fluoro-4-trifluoromethyl-phenyl)-propionaldehyde (220.2 mg; 1.000 mmol) afforded 3-ethyl-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by HPLC.
The pure product 3-ethyl-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (396.3 mg; 0.698 mmol; 70%). LC-MS: t R =0.95 min.; [M+H] + =568.32 g/mol.
3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 100° C.; 8 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (320.7 mg; 1.210 mmol) and 3-(3-fluoro-4-methyl-phenyl)-propionaldehyde (202 mg; 1.210 mmol) afforded 3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by HPLC.
The pure product 3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (394.8 mg; 0.769 mmol; 64%). LC-MS: t R =0.91 min.; [M+H] + =514.37 g/mol.
8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 100° C.; 8 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (344.6 mg; 1.300 mmol) and 3-(3,4-dimethyl-phenyl)-propionaldehyde (211.4 mg; 1.300 mmol) afforded 8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by HPLC.
The pure product 8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (393.5 mg; 0.772 mmol; 59%). LC-MS: t R =0.91 min.; [M+H] + =510.39 g/mol.
3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 100° C.; 8 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (312.8 mg; 1.180 mmol) and 3-(3-fluoro-4-trifluoromethyl-phenyl)-propionaldehyde (260.4 mg; 1.180 mmol) afforded 3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by HPLC.
The pure product 3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (365.3 mg; 0.643 mmol; 54.5%). LC-MS: t R =0.93 min.; [M+H] + =568.32 g/mol.
8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 100° C.; 8 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (334.0 mg; 1.260 mmol) and 3-(2,4-difluoro-3-methyl-phenyl)-propionaldehyde (232.7 mg; 1.260 mmol) afforded 8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by HPLC.
The pure product 8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (403.8 mg; 0.759 mmol; 60%). LC-MS: t R =0.89 min.; [M+H] + =532.33 g/mol.
1-iodo-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 110° C.; 8 bars; 10 min.) between 2-(4-iodo-2-methyl-imidazol-1-yl)-ethylamine (373.8 mg; 1.489 mmol) and 3-(4-trifluoromethyl-phenyl)-propionaldehyde (301 mg; 1.489 mmol) afforded 1-iodo-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by FC (DCM/MeOH=25/1).
The pure product 1-iodo-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (389 mg; 0.726 mmol; 49%). LC-MS: t R =0.95 min.; [M+H] + =536.11 g/mol.
8-[2-(3,4-dimethyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 110° C.; 6 bars; 10 min.) between 2-(4-iodo-2-methyl-imidazol-1-yl)-ethylamine (758 mg; 3.020 mmol) and 3-(3,4-dimethyl-phenyl)-propionaldehyde (490 mg; 3.020 mmol) afforded 8-[2-(3,4-dimethyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by FC (DCM/MeOH=25/1).
The pure product 8-[2-(3,4-dimethyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (1.177 g; 2.375 mmol; 79%). LC-MS: t R =0.94 min.; [M+H] + =496.17 g/mol
8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 110° C.; 5 bars; 10 min.) between 2-(4-iodo-2-methyl-imidazol-1-yl)-ethylamine (696 mg; 2.774 mmol) and 3-(3,5-difluoro-4-methyl-phenyl)-propionaldehyde (510 mg; 2.774 mmol) afforded 8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by FC (DCM/MeOH=25/1).
The pure product 8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (582 mg; 1.124 mmol; 41%). LC-MS: t R =0.94 min.; [M+H] + =518.12 g/mol.
1-iodo-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (60 W; 95° C.; 9 bars; 10 min.) between 2-(4-iodo-2-methoxymethyl-imidazol-1-yl)-ethylamine (596 mg; 2.119 mmol) and 3-(4-trifluoromethyl-phenyl)-propionaldehyde (428 mg; 2.119 mmol) afforded 1-iodo-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by FC (DCM/MeOH=30/1).
The pure product 1-iodo-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (720 mg; 1.273 mmol; 60%). LC-MS: t R =1.03 min.; [M+H] + =566.31 g/mol.
1-Iodo-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A homogeneous solution of 2-(4-iodo-2-isopropyl-imidazol-1-yl)-ethylamine (541 mg; 1.938 mmol) in anhydrous ethanol (2 ml) was treated with a solution of 3-(4-trifluoromethyl-phenyl)-propionaldehyde (481 mg; 2.379 mmol) in anhydrous ethanol (2.5 ml). The mixture was sealed and put in the microwave oven (60 W; 100° C.; 8 bars; 10 min.). This microwave-assisted Pictet-Spengler reaction was repeated three additional times with the same amount of starting material. The resulting crude reaction mixtures were finally mixed and concentrated to dryness under reduced pressure giving the crude 1-iodo-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a brown oil. LC-MS: t R =0.75 min.; [M+H] + =464.27 g/mol.
The crude 1-iodo-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (theoretical amount: 7.752 mmol) was dissolved in anhydrous DCM (20 ml), and N-ethyldiisopropylamine (2.65 ml; 15.510 mmol) was added. The resulting mixture was then cooled to 0° C., and a solution of di-tert-butyl dicarbonate Boc 2 O (2.030 g; 9.306 mmol) in anhydrous DCM (10 ml) was added in one portion. After completion of the addition, the reaction mixture was further stirred at 0° C. for 15 min., and at rt overnight. After reaction, the resulting mixture was washed with brine (2×100 ml), the organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure.
The crude was purified by FC (DCM/MeOH=25/1) to give the pure product 1-iodo-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a pale yellow solid which was further dried under HV (3.580 g; 82%). LC-MS: t R =0.95 min.; [M+H] + =564.45 g/mol.
1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), the microwave-assisted Pictet-Spengler reaction (70 W; 130° C.; 10 bars; 10 min.) between 2-(4-iodo-imidazol-1-yl)-ethylamine (4.326 g; 18.253 mmol) and 3-(4-trifluoromethyl-phenyl)-propionaldehyde (3.690 g; 18.253 mmol) afforded 1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine which was Boc-protected and finally purified by FC (DCM/MeOH=25/1).
The pure product 1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was isolated as a yellow solid (3.720 g; 7.135 mmol; 39%). LC-MS: t R =0.89 min.; [M+H] + =522.15 g/mol.
3-ethyl-1-iodo-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (7.394 mmol) and 3-(3,4,5-trifluoro-phenyl)-propionaldehyde (1.391 g; 7.394 mmol) afforded 3-ethyl-1-iodo-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.74 min.; [M+H] + =435.86 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=25/1) allowed the isolation of the pure product 3-ethyl-1-iodo-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a colorless solid (2.010 g; 51%). LC-MS: t R =0.97 min.; [M+H] + =535.87 g/mol.
8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(4-iodo-2-methyl-imidazol-1-yl)-ethylamine (51.840 mmol) and 3-(3-fluoro-4-trifluoromethyl-phenyl)-propionaldehyde (13.125 g; 59.616 mmol) afforded 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.76 min.; [M+H] + =453.93 g/mol. Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=20/1) allowed the isolation of the pure product 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a pale yellow solid (15.450 g; 54%). LC-MS: t R =0.97 min.; [M+H] + =554.84 g/mol.
8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (5.168 mmol) and 3-(3,5-difluoro-4-methoxy-phenyl)-propionaldehyde (1.034 g; 5.168 mmol) afforded 8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.73 min.; [M+H] + =448.42 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=25/1) allowed the isolation of the pure product 8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (1.440 g; 62%). LC-MS: t R =0.96 min.; [M+H] + =547.97 g/mol.
8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (4.012 mmol) and 3-(4-chloro-3,5-difluoro-phenyl)-propionaldehyde (1.030 g; 5.034 mmol) afforded 8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.78 min.; [M+H] + =451.76 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=25/1) allowed the isolation of the pure product 8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (1.790 g; 81%). LC-MS: t R =0.99 min.; [M+H] + =551.80 g/mol.
8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (4.497 mmol) and 3-(3-chloro-4-trifluoromethyl-phenyl)-propionaldehyde (1.064 g; 4.497 mmol) afforded 8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.81 min.; [M+H] + =483.73 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=20/1) allowed the isolation of the pure product 8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a pale yellow solid (2.070 g; 79%). LC-MS: t R =1.00 min.; [M+H] + =583.70 g/mol.
8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (6.340 mmol) and 3-(2,5-difluoro-4-trifluoromethyl-phenyl)-propionaldehyde (1.509 g; 6.340 mmol) afforded 8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.79 min.; [M+H] + =485.87 g/mol. Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=50/1) allowed the isolation of the pure product 8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a slightly beige solid (1.890 g; 51%). LC-MS: t R =0.99 min.; [M+H] + =585.78 g/mol.
3-ethyl-1-iodo-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (5.621 mmol) and 3-(4-trifluoromethoxy-phenyl)-propionaldehyde (1.206 g; 5.528 mmol) afforded 3-ethyl-1-iodo-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.78 min.; [M+H] + =465.87 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=40/1) allowed the isolation of the pure product 3-ethyl-1-iodo-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (1.680 g; 53%). LC-MS: t R =0.97 min.; [M+H] + =565.80 g/mol.
8-[2-(4-bromo-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (26.610 mmol) and 3-(4-bromo-phenyl)-propionaldehyde (6.350 g; 29.803 mmol) afforded 8-[2-(4-bromo-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.74 min.; [M+H] + =460.01 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=15/1) allowed the isolation of the pure product 8-[2-(4-bromo-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a slightly beige solid (7.610 g; 51%). LC-MS: t R =0.96 min.; [M+H] + =562.09 g/mol.
1-iodo-3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(4-iodo-2-propyl-imidazol-1-yl)-ethylamine (9.260 mmol) and 3-(4-trifluoromethyl-phenyl)-propionaldehyde (2.730 g; 13.503 mmol) afforded 1-iodo-3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.80 min.; [M+H] + =463.88 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=25/1) allowed the isolation of the pure product 1-iodo-3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (4.540 g; 87%). LC-MS: t R =1.00 min.; [M+H] + =563.79 g/mol.
8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(4-iodo-2-propyl-imidazol-1-yl)-ethylamine (6.840 mmol) and 3-(3-fluoro-4-trifluoromethyl-phenyl)-propionaldehyde (2.195 g; 9.970 mmol) afforded 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-3-propyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.81 min.; [M+H] + =481.75 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=25/1) allowed the isolation of the pure product 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (3.500 g; 88%). LC-MS: t R =1.01 min.; [M+H] + =581.87 g/mol.
3-ethyl-1-iodo-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (2.331 mmol) and 3-(2,3,5-trifluoro-phenyl)-propionaldehyde (0.600 g; 3.189 mmol) afforded 3-ethyl-1-iodo-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.69 min.; [M+H] + =436.23 g/mol.
Subsequent protection of the secondary amine, and purification by FC (heptane/EA=2/3) allowed the isolation of the pure product 3-ethyl-1-iodo-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a colorless solid (0.917 g; 90%). LC-MS: t R =0.92 min.; [M+H] + =536.12 g/mol.
3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (11.500 mmol) and 3-(3-fluoro-4-methoxy-phenyl)-propionaldehyde (2.514 g; 13.800 mmol) afforded 3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.70 min.; [M+H] + =429.88 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=25/1) allowed the isolation of the pure product 3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (3.870 g; 64%). LC-MS: t R =0.94 min.; [M+H] + =529.88 g/mol.
8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (9.700 mmol) and 3-(2,5-difluoro-4-methoxy-phenyl)-propionaldehyde (2.135 g; 10.670 mmol) afforded 8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.72 min.; [M+H] + =447.67 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=25/1) allowed the isolation of the pure product 8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (3.850 g; 73%). LC-MS: t R =0.95 min.; [M+H] + =547.79 g/mol.
3-ethyl-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (1.540 mmol) and (4-fluoro-3-trifluoromethyl-phenoxy)-acetaldehyde (0.342 g; 1.540 mmol) afforded 3-ethyl-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=60/1) allowed the isolation of the pure product 3-ethyl-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (0.412 g; 47%). LC-MS: t R =0.93 min.; [M+H] + =570.37 g/mol.
3-ethyl-1-iodo-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (3.880 mmol) and (4-trifluoromethyl-phenoxy)-acetaldehyde (0.792 g; 3.880 mmol) afforded 3-ethyl-1-iodo-8-(4-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.73 min.; [M+H] + =452.12 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=90/1) allowed the isolation of the pure product 3-ethyl-1-iodo-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (0.890 g; 42%). LC-MS: t R =0.93 min.; [M+H] + =552.13 g/mol.
8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (6.000 mmol) and (3,4-dimethyl-phenoxy)-acetaldehyde (0.985 g; 6.000 mmol) afforded 8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-1-iodo-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine. LC-MS: t R =0.70 min.; [M+H] + =412.12 g/mol.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=60/1) allowed the isolation of the pure product 8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (0.919 g; 30%). LC-MS: t R =0.90 min.; [M+H] + =512.18 g/mol.
3-ethyl-1-iodo-8-(3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP10), microwave-assisted Pictet-Spengler reaction (60 W; 140° C.; 6.5 bars; 10 min.) between 2-(2-ethyl-4-iodo-imidazol-1-yl)-ethylamine (3.880 mmol) and (3-trifluoromethyl-phenoxy)-acetaldehyde (0.792 g; 3.880 mmol) afforded 3-ethyl-1-iodo-8-(3-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine.
Subsequent protection of the secondary amine, and purification by FC (DCM/MeOH=80/1) allowed the isolation of the pure product 3-ethyl-1-iodo-8-(3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as an orange solid (1.272 g; 59%). LC-MS: t R =0.92 min.; [M+H] + =552.30 g/mol.
C.2 Synthesis of 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives via Pictet-Spengler reaction with isomeric 2-imidazol-1-yl-ethylamine derivatives [second general procedure for microwave-assisted Pictet-Spengler reaction (GP11)]
A mixture of the respective 2-imidazol-1-yl-ethylamine (2.200 mmol) and the respective aldehyde (2.500 mmol) in toluene (4 ml) was heated in a microwave oven for 7 min. to 120° C. (135-150 W). The solvent was removed in vacuo and the residue was either purified by preparative HPLC or used without further purification.
1,3-dimethyl-8-(2-p-tolyl-ethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
Prepared according to the previously described general procedure (GP11) by reaction of 2-(2,4-dimethyl-imidazol-1-yl)-ethylamine with 3-p-tolyl-propionaldehyde. LC-MS: t R =0.57 min.; [M+H] + =270 g/mol.
1,3-dimethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
Prepared according to the previously described general procedure (GP11) by reaction of 2-(2,4-dimethyl-imidazol-1-yl)-ethylamine with 3-(4-trifluoromethyl-phenyl)-propionaldehyde. LC-MS: t R =0.64 min.; [M+H] + =324 g/mol.
8-[2-(3-chloro-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
Prepared according to the previously described general procedure (GP11) by reaction of 2-(2,4-dimethyl-imidazol-1-yl)-ethylamine with 3-(3-chloro-phenyl)-propionaldehyde. LC-MS: t R =0.59 min.; [M+H] + =290 g/mol.
8-[2-(2,3-dimethyl-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
Prepared according to the previously described general procedure (GP11) by reaction of 2-(2,4-dimethyl-imidazol-1-yl)-ethylamine with 3-(2,3-dimethyl-phenyl)-propionaldehyde. LC-MS: t R =0.61 min.; [M+H] + =284 g/mol.
8-[2-(2,4-dimethyl-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
Prepared according to the previously described general procedure (GP11) by reaction of 2-(2,4-dimethyl-imidazol-1-yl)-ethylamine with 3-(2,4-dimethyl-phenyl)-propionaldehyde. LC-MS: t R =0.62 min.; [M+H] + =284 g/mol.
8-[2-(3,4-difluoro-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
Prepared according to the previously described general procedure (GP11) by reaction of 2-(2,4-dimethyl-imidazol-1-yl)-ethylamine with 3-(3,4-difluoro-phenyl)-propionaldehyde. LC-MS: t R =0.57 min.; [M+H] + =292 g/mol.
8-[2-(2,4-dichloro-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
Prepared according to the previously described general procedure (GP11) by reaction of 2-(2,4-dimethyl-imidazol-1-yl)-ethylamine with 3-(2,4-dichloro-phenyl)-propionaldehyde. LC-MS: t R =0.64 min.; [M+H] + =324 g/mol.
8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
Prepared according to the previously described general procedure (GP11) by reaction of 2-(2,4-dimethyl-imidazol-1-yl)-ethylamine with 3-(3-fluoro-4-methoxy-phenyl)-propionaldehyde. LC-MS: t R =0.57 min.; [M+H] + =304 g/mol.
8-[2-(2,4-dimethoxy-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
Prepared according to the previously described general procedure (GP11) by reaction of 2-(2,4-dimethyl-imidazol-1-yl)-ethylamine with 3-(2,4-dimethoxy-phenyl)-propionaldehyde. LC-MS: t R =0.59 min.; [M+H] + =316 g/mol.
3-ethyl-1-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
Prepared according to the previously described general procedure (GP11) by reaction of 2-(2-ethyl-4-methyl-imidazol-1-yl)-ethylamine with 3-(4-trifluoromethyl-phenyl)-propionaldehyde. LC-MS: t R =0.65 min.; [M+H] + =338 g/mol.
D Functionalization and derivatization of 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives
D.1 Chlorination
1-chloro-3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester [first general procedure for chlorination of the imidazole ring (GP12)]
A cooled (−78° C.) solution of 3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (300 mg; 0.546 mmol) in anhydrous THF (4 ml) was treated dropwise with a solution of 1.6M n-BuLi in hexanes (0.34 ml; 0.546 mmol). The resulting solution was additionally stirred at −78° C. for 10 min., and was then treated dropwise with a solution of hexachloroethane (517 mg; 2.184 mmol; 4 eq.) in anhydrous THF (1 ml). The reaction mixture was further stirred at −78° C. for 1 h. The mixture was then quenched with water (0.2 ml), diluted with ether (30 ml), and was allowed to warm-up to rt. The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The crude was purified by FC (DCM/MeOH=100/3) to give the pure product 1-chloro-3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (143 mg; 57%). LC-MS: t R =1.02 min.; [M+H] + =458.49 g/mol.
1-chloro-8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (500 mg; 0.854 mmol) and purification by FC (DCM/MeOH=100/3) gave the product 1-chloro-8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (179 mg; 42%). LC-MS: t R =1.05 min.; [M+H] + =494.37 g/mol.
1-chloro-8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (387.2 mg; 0.748 mmol) and purification by FC (heptane/EA=2/3) gave the product 1-chloro-8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (143 mg; 45%). LC-MS: t R =0.99 min.; [M+H] + =426.28 g/mol.
1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (349.3 mg; 0.657 mmol) and purification by FC (heptane/EA=2/3) gave the product 1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (136.8 mg; 47%). LC-MS: t R =1.03 min.; [M+H] + =440.36 g/mol.
1-chloro-3-ethyl-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 3-ethyl-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (396.3 mg; 0.698 mmol) and purification by FC (heptane/EA=2/3) gave the product 1-chloro-3-ethyl-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (153.6 mg; 46%). LC-MS: t R =1.04 min.; [M+H] + =476.32 g/mol.
1-chloro-3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (394.8 mg; 0.769 mmol) and purification by FC (heptane/EA=2/3) gave the product 1-chloro-3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (191.4 mg; 59%). LC-MS: t R =1.01 min.; [M+H] + =422.32 g/mol.
1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (393.5 mg; 0.772 mmol) and purification by FC (heptane/EA=2/3) gave the product 1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (225 mg; 70%). LC-MS: t R =1.02 min.; [M+H] + =418.34 g/mol.
1-chloro-3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (365.3 mg; 0.643 mmol) and purification by FC (heptane/EA=2/3) gave the product 1-chloro-3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (135.3 mg; 44%). LC-MS: t R =1.04 min.; [M+H] + =476.32 g/mol.
1-chloro-8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (403.8 mg; 0.759 mmol) and purification by FC (heptane/EA=2/3) gave the product 1-chloro-8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (213.9 mg; 64%). LC-MS: t R =1.02 min.; [M+H] + =440.35 g/mol.
1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (582 mg; 1.125 mmol) and purification by FC (DCM/MeOH=40/1) gave the product 1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (49 mg; 0.115 mmol). LC-MS: t R =1.02 min.; [M+H] + =426.45 g/mol.
1-chloro-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 1-iodo-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (389 mg; 0.727 mmol) and purification by FC (DCM/MeOH=20/1) gave the product 1-chloro-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as an orange oil (33 mg; 0.074 mmol). LC-MS: t R =1.02 min.; [M+H] + =444.44 g/mol.
1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 8-[2-(3,4-dimethyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.061 g; 2.142 mmol) and purification by FC (DCM/MeOH=40/1) gave the product 1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as an orange oil (157 mg; 0.388 mmol). LC-MS: t R =1.01 min.; [M+H] + =404.50 g/mol.
1-chloro-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 1-iodo-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (720 mg; 1.274 mmol) and purification by FC (DCM/MeOH=60/1) gave the expected product 1-chloro-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as an orange oil (254 mg; 42%). LC-MS: t R =1.09 min.; [M+H] + =474.42 g/mol.
3-Methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (177 mg) was also isolated after FC in order to be converted into the target product (chlorination with N-chlorosuccinimide).
1-chloro-3-ethyl-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 3-ethyl-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (844 mg; 1.482 mmol), and purification by FC (DCM/MeOH=60/1) gave the expected product 1-chloro-3-ethyl-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as an orange solid (186 mg; 26%). LC-MS: t R =1.04 min.; [M+H] + =478.39 g/mol.
1-chloro-3-ethyl-8-(3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 3-ethyl-1-iodo-8-(3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.272 g; 2.307 mmol), and purification by FC (DCM/MeOH=60/1) gave the expected product 1-chloro-3-ethyl-8-(3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (0.403 g; 38%). LC-MS: t R =1.03 min.; [M+H] + =460.37 g/mol.
1-chloro-8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester [second general procedure for chlorination of the imidazole ring (GP12B)]
A mixture of 8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.890 g; 3.229 mmol), 10% palladium on activated charcoal (567 mg), and anhydrous potassium carbonate (1.115 g; 8.072 mmol; 2.5 eq.) in anhydrous MeOH (75 ml) was stirred at rt, under hydrogen (1 atm), for 3 h15. Filtration over a pad of celite, and subsequent concentration to dryness afforded a crude heterogeneous residue which was dissolved in DCM (100 ml), and water (50 ml). The organic layer was then dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give 8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (1.400 g; 94%). LC-MS: t R =0.94 min.; [M+H] + =460.04 g/mol.
To a yellow homogeneous solution of 8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.400 g; 3.047 mmol) in anhydrous MeCN (50 ml) was added dropwise, at rt, a solution of N-chlorosuccinimide (0.407 g; 3.047 mmol; 1 eq.) in anhydrous MeCN (25 ml). The resulting solution was then heated to 70° C., under nitrogen, for 3 h30. Concentration to dryness afforded a yellow oily residue which was dissolved in EA (150 ml), and this organic layer was successively washed with aq. sat. NaHCO 3 (2×50 ml), and brine (50 ml), and was then dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH=50/1) gave the expected 1-chloro-8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (0.711 g; 47%). LC-MS: t R =1.10 min.; [M+H] + =493.93 g/mol.
1-chloro-3-ethyl-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 1 h) of 3-ethyl-1-iodo-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.010 g; 3.755 mmol) afforded 3-ethyl-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a pale yellow oil (1.530 g; 97%). LC-MS: t R =0.95 min.; [M+H] + =410.14 g/mol.
Subsequent chlorination (70° C.; 3h30) of 3-ethyl-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.070 g; 5.056 mmol), and purification by FC (DCM/MeOH=25/1) afforded 1-chloro-3-ethyl-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (1.220 g; 54%). LC-MS: t R =1.06 min.; [M+H] + =444.00 g/mol.
1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 1h30) of 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (10.910 g; 19.717 mmol) afforded 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (8.280 g; 98%). LC-MS: t R =0.93 min.; [M+H] + =428.07 g/mol.
Subsequent chlorination (70° C.; 4h30) of 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (8.080 g; 18.903 mmol), and purification by FC (DCM/MeOH=50/1) afforded 1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (4.730 g; 54%). LC-MS: t R =1.08 min.; [M+H] + =461.98 g/mol.
1-chloro-8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 1 h) of 8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.440 g; 2.631 mmol) afforded 8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.050 g; 95%). LC-MS: t R =0.91 min.; [M+H] + =422.04 g/mol.
Subsequent chlorination (70° C.; 3h30) of 8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.330 g; 3.156 mmol), and purification by FC (DCM/MeOH=25/1) afforded 1-chloro-8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (0.730 g; 51%). LC-MS: t R =1.04 min.; [M+H] + =456.05 g/mol.
1-chloro-3-ethyl-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 4 h) of 3-ethyl-1-iodo-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.680 g; 2.972 mmol) afforded 3-ethyl-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.200 g; 92%). LC-MS: t R =0.93 min.; [M+H] + =440.03 g/mol.
Subsequent chlorination (70° C.; 4h30) of 3-ethyl-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.200 g; 2.731 mmol), and purification by FC (DCM/MeOH=50/1) afforded 1-chloro-3-ethyl-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (0.810 g; 63%). LC-MS: t R =1.08 min.; [M+H] + =473.97 g/mol.
1-chloro-3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 1 h) of 1-iodo-3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (5.450 g; 9.673 mmol) afforded 3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.940 g; 69%). LC-MS: t R =0.96 min.; [M+H] + =438.05 g/mol.
Subsequent chlorination (70° C.; 3h30) of 3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.940 g; 6.720 mmol), and purification by FC (DCM/MeOH=25/1) afforded 1-chloro-3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (1.550 g; 49%). LC-MS: t R =1.09 min.; [M+H] + =472.00 g/mol.
1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 1 h) of 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (3.500 g; 6.020 mmol) afforded 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.310 g; 84%). LC-MS: t R =0.97 min.; [M+H] + =456.02 g/mol.
Subsequent chlorination (70° C.; 3h30) of 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.310 g; 5.071 mmol), and purification by FC (DCM/MeOH=50/1) afforded 1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (1.130 g; 45%). LC-MS: t R =1.10 min.; [M+H] + =489.94 g/mol.
1-chloro-3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 1 h) of 3-ethyl-1-iodo-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.917 g; 1.713 mmol) afforded 3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.570 g; 81%). LC-MS: t R =0.88 min.; [M+H] + =410.40 g/mol.
Subsequent chlorination (70° C.; 3h30) of 3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.570 g; 1.392 mmol), and purification by FC (heptane/EA=2/3) afforded 1-chloro-3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a pale yellow solid (0.373 g; 60%). LC-MS: t R =1.01 min.; [M+H] + =444.35 g/mol.
1-chloro-3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 1 h) of 3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (3.870 g; 7.310 mmol) afforded 3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.920 g; 99%). LC-MS: t R =0.89 min.; [M+H] + =404.01 g/mol.
Subsequent chlorination (70° C.; 4h30) of 3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.920 g; 7.237 mmol), and purification by FC (heptane/EA=2/3) afforded 1-chloro-3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (1.790 g; 56%). LC-MS: t R =1.02 min.; [M+H] + =438.01 g/mol.
1-chloro-8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 1 h) of 8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.470 g; 4.512 mmol) afforded 8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.830 g; 96%). LC-MS: t R =0.90 min.; [M+H] + =422.05 g/mol.
Subsequent chlorination (70° C.; 3h45) of 8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.640 g; 6.264 mmol), and purification by FC (heptane/EA=1/1) afforded 1-chloro-8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (1.601 g; 56%). LC-MS: t R =1.04 min.; [M+H] + =456.00 g/mol.
1-chloro-3-ethyl-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 14 h) of 3-ethyl-1-iodo-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.890 g; 1.614 mmol) afforded 3-ethyl-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.664 g; 97%). LC-MS: t R =0.88 min.; [M+H] + =426.24 g/mol.
Subsequent chlorination (70° C.; 3 h) of 3-ethyl-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.664 g; 1.561 mmol), and purification by FC (DCM/MeOH=80/1) afforded 1-chloro-3-ethyl-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (0.381 g; 53%). LC-MS: t R =1.04 min.; [M+H] + =460.23 g/mol.
1-chloro-8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12B), hydrogenation (rt; 4 h) of 8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.919 g; 1.797 mmol) afforded 8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.600 g; 87%). LC-MS: t R =0.88 min.; [M+H] + =386.43 g/mol.
Subsequent chlorination (70° C.; 5 h) of 8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.600 g; 1.556 mmol), and purification by FC (heptane/EA=2/3) afforded 1-chloro-8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a pale yellow solid (0.328 g; 50%). LC-MS: t R =1.02 min.; [M+H] + =420.38 g/mol.
1-chloro-8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester [third general procedure for chlorination of the imidazole ring (GP12C)]
A cooled (−30° C.) solution of 8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.790 g; 3.244 mmol) in anhydrous THF (90 ml) was treated dropwise with a solution of 1-Methylmagnesium bromide in THF (14.6 ml; 14.6 mmol; 4.5 eq.) until complete removal of the iodine substituent. The mixture was then quenched with water (10 ml), diluted with ether (100 ml), and was allowed to warm-up to rt. This solution was washed with brine (2×150 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The crude was purified by FC (DCM/MeOH=15/1) to give the pure product 8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (1.150 g; 83%). LC-MS: t R =0.95 min.; [M+H] + =426.01 g/mol.
To a yellow homogeneous solution of 8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.150 g; 2.700 mmol) in anhydrous MeCN (40 ml) was added dropwise, at rt, a solution of N-chlorosuccinimide (0.367 g; 2.700 mmol; 1 eq.) in anhydrous MeCN (10 ml). The resulting solution was then heated to 70° C., under nitrogen, for 3 h30. Concentration to dryness afforded a yellow oily residue which was dissolved in EA (80 ml), and this organic layer was washed with aq. sat. NaHCO 3 (2×120 ml), was then dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. Purification by FC (heptane/EA=2/3) gave the expected 1-chloro-8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (0.724 g; 58%). LC-MS: t R =1.08 min.; [M+H] + =461.94 g/mol.
1-chloro-8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the previously described general procedure (GP12C), treatment of 8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.070 g; 3.546 mmol) with 1M ethylmagnesium bromide in THF (15.6 ml; 15.6 mmol; 4.4 eq.) afforded 8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.170 g; 72%) as a pale yellow oil. LC-MS: t R =0.95 min.; [M+H] + =457.98 g/mol.
Subsequent chlorination (70° C.; 3h30) of 8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.170 g; 2.555 mmol), and purification by FC (heptane/EA=1/1) afforded 1-chloro-8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (0.684 g; 54%). LC-MS: t R =1.10 min.; [M+H] + =491.95 g/mol.
1-chloro-8-[2-(4-cyano-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A cooled (−30° C.) solution of 8-[2-(4-bromo-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (2.200 g; 3.927 mmol) in anhydrous THF (90 ml) was treated dropwise with a solution of 1-Methylmagnesium bromide in THF (10.25 ml; 10.25 mmol; 2.6 eq.) until complete removal of the iodine substituent. The mixture was then quenched with water (5 ml), diluted with ether (100 ml), and was allowed to warm-up to rt. This solution was washed with brine (2×150 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. The crude was purified by FC (DCM/MeOH=15/1) to give the pure product 8-[2-(4-bromo-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (1.570 g; 92%). LC-MS: t R =0.93 min.; [M+H] + =435.98 g/mol.
To a mixture of potassium cyanide (0.482 g; 4.075 mmol), calcium hydroxide (0.207 g; 2.717 mmol), palladium diacetate (91 mg; 0.407 mmol), and triphenylphosphine (0.213 g; 0.815 mmol) was added a solution of 8-[2-(4-bromo-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.180 g; 2.717 mmol) in anhydrous DMF (12 ml). The resulting pale yellow suspension was stirred at 120° C., under nitrogen, for 1 h45. Ether (100 ml) was then added, and this solution was successively washed with aq. sat. NaHCO 3 (100 ml), and with brine (100 ml). The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure.
Purification by FC (DCM/MeOH, 25/1) afforded the pure target compound 8-[2-(4-cyano-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (0.700 g; 68%). LC-MS: t R =0.87 min.; [M+H] + =381.07 g/mol.
To a solution of 8-[2-(4-cyano-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.700 g; 1.840 mmol) in anhydrous MeCN (20 ml) was added dropwise, at rt, a solution of N-chlorosuccinimide (0.250 g; 1.840 mmol; 1 eq.) in anhydrous MeCN (5 ml). The resulting solution was then heated to 70° C., under nitrogen, for 4 h. Concentration to dryness afforded an oily residue which was dissolved in EA (80 ml), and this organic layer was washed with aq. sat. NaHCO 3 (2×100 ml), was then dried over anh. MgSO 4 , filtered, and finally concentrated to dryness under reduced pressure. Purification by FC (heptane/EA=2/3) gave the expected 1-chloro-8-[2-(4-cyano-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (0.417 g; 55%). LC-MS: t R =1.00 min.; [M+H] + =414.94 g/mol.
3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A cooled (−78° C.) solution of 1-iodo-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (379 mg; 0.673 mmol) in anhydrous THF (6 ml) was treated dropwise with a 1.6N butyllithium solution in hexanes (1.05 ml; 1.680 mmol). The resulting mixture was additionally stirred at −78° C., under nitrogen, for 15 min. Water (0.2 ml) was then added and the reaction mixture was allowed to warm-up to rt. The resulting solution was diluted with ether (30 ml), the organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH=25/1) gave the pure product 3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (229 mg; 78%). LC-MS: t R =0.92 min.; [M+H] + =438.43 g/mol.
1-chloro-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
To a solution of N-chlorosuccinimide (87.3 mg; 0.628 mmol) in chloroform (1 ml) was added a solution of 3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (229 mg; 0.523 mmol) in chloroform (2 ml) and the resulting solution was heated to 70° C. for 5 h30. The reaction mixture was allowed to cool to rt, diluted with DCM (20 ml) and washed with water (3×10 ml). The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. Purification by preparative HPLC gave the pure product 1-chloro-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (97 mg; 39%). LC-MS: t R =1.04 min.; [M+H] + =472.51 g/mol.
3-chloro-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
To a solution of 1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.000 g; 1.918 mmol) in chloroform (30 ml) was added N-chlorosuccinimide (307 mg; 2.298 mmol; 1.2 eq.), and the resulting mixture was heated to reflux (70° C.) for 2 h30. Additional N-chlorosuccinimide (120 mg; 0.898 mmol; 0.46 eq.) was then added and the resulting mixture was additionally refluxed for 2 h30. The reaction mixture was allowed to cool to rt, diluted with DCM (50 ml), and washed with brine (80 ml). The organic layer was dried over magnesium sulfate, filtered, and concentrated to dryness under reduced pressure. Purification by FC (heptane/EA=1/1) afforded the expected product 3-chloro-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (475 mg; 45%). LC-MS: t R =1.13 min.; [M+H] + =556.24 g/mol.
1,3-dichloro-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
According to the general procedure (GP12), chlorination of 3-chloro-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (522 mg; 0.939 mmol) and purification by FC (heptane/EA=1/1) gave the expected product 1,3-dichloro-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (185.7 mg; 43%). LC-MS: t R =1.13 min.; [M+H] + =464.22 g/mol.
D.2 Alkoxylation
8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A solution of 8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.500 g; 2.944 mmol) in anhydrous MeOH (30 ml) was treated successively with copper(I) iodide (56 mg; 0.294 mmol), 1,10-phenanthroline (116.7 mg; 0.589 mmol), and cesium carbonate (1.535 g; 4.711 mmol). The resulting brown suspension was sealed and put in the microwave oven (150 W; 150° C.; 13 bars; 1h30). The resulting brown suspension was concentrated to dryness under reduced pressure and the crude was purified by FC (EA/heptane: 2/3 to 3/2]. The expected product 8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was obtained as a yellow oil (260.6 mg; 21%). LC-MS: t R =0.91 min.; [M+H] + =414.35 g/mol.
3-isopropyl-1-methoxy-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A solution of 1-iodo-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (150 mg; 0.266 mmol) in anhydrous MeOH (3 ml) was treated successively with copper(I) iodide (5 mg; 0.026 mmol), 1,10-phenanthroline (10.5 mg; 0.053 mmol), and cesium carbonate (138.8 mg; 0.426 mmol). The resulting brown suspension was sealed and put in the microwave oven (35 W; 100° C.; 6 bars; 1 h). This microwave-assisted methoxylation was repeated two additional times with the same amount of starting material. The resulting mixed brown suspension was concentrated to dryness under reduced pressure and the crude was purified by preparative HPLC. The expected product 3-isopropyl-1-methoxy-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester was obtained as a yellow oil (107.5 mg; 29%). LC-MS: t R =0.94 min.; [M+H] + =468.55 g/mol.
D.3 Derivatization Via Stille Cross-Coupling Reactions
3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A slightly yellow homogeneous solution of 3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (619.7 mg; 1.128 mmol) in anhydrous DMF (6 ml) was treated successively at rt with tris(dibenzylideneacetone)dipalladium(0) (33 mg; 0.036 mmol), triphenylphosphine (37 mg; 0.141 mmol), and finally with tributyl(vinyl)tin (0.66 ml; 2.256 mmol). The resulting mixture was heated to 90° C., under nitrogen, for 20 h. The reaction mixture was cooled to rt, EA (75 ml) was added, and the resulting solution was washed with water (2×50 ml). The resulting yellow organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give an orange oil (1.230 g). Purification by FC (DCM/MeOH=40/1) gave the pure product 3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (384 mg; 76%). LC-MS: t R =0.93 min.; [M+H] + =450.22 g/mol.
3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A slightly yellow homogeneous solution of 1-iodo-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.500 g; 2.802 mmol) in anhydrous DMF (15 ml) was treated successively at rt with tris(dibenzylideneacetone)dipalladium(0) (82 mg; 0.090 mmol), triphenylphosphine (91 mg; 0.350 mmol), and finally with tributyl(vinyl)tin (1.63 ml; 5.604 mmol). The resulting mixture was heated to 90° C., under nitrogen, for 20 h. The reaction mixture was cooled to rt, EA (200 ml) was added, and the resulting solution was washed with water (2×125 ml). The resulting yellow organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give an orange oil. Purification by FC (DCM/MeOH=40/1) gave the pure product 3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow solid (0.936 g; 77%). LC-MS: t R =0.88 min.; [M+H] + =436.48 g/mol.
D.4 Trifluoromethylation
3-ethyl-1-trifluoromethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A slightly yellow homogeneous solution of 3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (500 mg; 0.910 mmol) in anhydrous DMF (25 ml) was treated successively at rt with copper(I) iodide (866.6 mg; 4.551 mmol), hexamethylphosphoramide (1.58 ml; 9.101 mmol), and finally with methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (0.75 ml; 5.916 mmol). The resulting beige heterogeneous mixture was heated to 80° C., under nitrogen, for 6 h30. The reaction mixture was cooled to rt, water (100 ml), and ether (150 ml) were then added. The organic layer was additionally washed with water (3×75 ml), dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure to give a yellow oil (438 mg). Purification by FC (DCM/MeOH=40/1) gave the pure product 3-ethyl-1-trifluoromethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (253.6 mg; 57%). LC-MS: t R =1.09 min.; [M+H] + =492.46 g/mol.
D.5 Formylation
3-ethyl-1-formyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A cooled (−30° C.) solution of 3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.000 g; 1.820 mmol) in anhydrous THF (10 ml) was treated dropwise with 1-Methylmagnesium bromide in THF (4.0 ml; 4.0 mmol), and the resulting suspension was then allowed to warm-up to rt in 10 min. After cooling to −35° C., a mixture of anhydrous DMF (2.0 ml; 25.831 mmol) and anhydrous THF (2 ml) was added dropwise, and the resulting mixture was then allowed to warm-up to rt (in 30 min.), and was further stirred at rt for 16 h. Water (2 ml) and EA were then successively added, and this mixture was washed with aq. sat. NH 4 Cl. The organic extract was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure (yellow oil; 950 mg). Purification by FC (EA/heptane=1/9 to 1/1) gave the pure product 3-ethyl-1-formyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a colorless oil (640 mg; 78%). LC-MS: t R =1.01 min.; [M+H] + =452.12 g/mol.
D.6 Introduction of Cyano Substituent
1-cyano-3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
To a solution of 3-ethyl-1-formyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (6.000 g; 13.289 mmol) in pyridine (100 ml) was added hydroxylamine hydrochloride (1.015 g; 14.618 mmol). The resulting mixture was first stirred at rt (4 h), and was then heated to 60° C. for 1 h before acetic anhydride (1.9 ml; 20.099 mmol; 1.5 eq.) was added at this temperature. After further heating at 60° C. (30 min.), the reaction mixture was then heated at 80° C. for 16 h. A second addition of acetic anhydride (0.3 ml; 3.173 mmol) was performed at 60° C., and the resulting mixture was additionally stirred at 80° C. for 10 h. The resulting yellow solution was then allowed to cool to rt before water was added. Extractions with DCM, washing with aq. 2N HCl, drying of the organic layer over magnesium sulfate, filtration, and concentration to dryness under reduced pressure afforded the crude product (yellow oil; 7.50 g). Purification by FC (EA/heptane=4/1) gave the expected pure product 1-cyano-3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a yellow oil (5.000 g; 84%). LC-MS: t R =1.09 min.; [M+H] + =449.40 g/mol.
1-cyano-3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A cooled (−78° C.) solution of 3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.040 g; 1.833 mmol) in anhydrous THF (50 ml) was treated dropwise with 1.6M n-BuLi in hexanes (1.6 ml; 2.560 mmol). The resulting reaction mixture was further stirred at −78° C., under nitrogen, for 3 min., and a solution of para-toluenesulfonyl cyanide (0.576 g; 3.025 mmol) in anhydrous THF (5 ml) was then added dropwise. Stirring at −78° C. was continued for 20 min. before aq. sat. NH 4 Cl (2 ml) was added. The resulting mixture was allowed to warm-up to rt, and water (50 ml), followed by ether (50 ml) were added. The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH, 25/1) afforded 1-cyano-3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a pale yellow solid (0.233 g; 27%). LC-MS: t R =1.12 min.; [M+H] + =467.23 g/mol.
1-cyano-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
A cooled (−78° C.) solution of 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-1-iodo-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.666 g; 1.204 mmol) in anhydrous THF (20 ml) was treated dropwise with 1.6M n-BuLi in hexanes (0.76 ml; 1.204 mmol). The resulting reaction mixture was further stirred at −78° C., under nitrogen, for 15 min., and a solution of para-toluenesulfonyl cyanide (0.379 g; 1.987 mmol) in anhydrous THF (5 ml) was then added dropwise. Stirring at −78° C. was continued for 20 min. before aq. sat. NH 4 Cl (2 ml) was added. The resulting mixture was allowed to warm-up to rt, and water (50 ml), followed by ether (50 ml) were added. The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH, 50/1) afforded 1-cyano-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester as a pale yellow solid (0.271 g; 50%). LC-MS: t R =0.96 min.; [M+H] + =453.31 g/mol.
D.7 Introduction of Hydroxymethyl Substituent
3-ethyl-1-hydroxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
To a cooled (−78° C.) colorless solution of 3-ethyl-1-formyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (19.9 mg; 0.044 mmol) in anhydrous toluene (2 ml) was added dropwise 1M DIBAL in THF (88 μl; 2 eq.). The resulting yellow homogeneous solution was further stirred at −78° C. for 10 min., and then at rt for 1 h. The resulting crude mixture was purified by preparative HPLC to give the pure product 3-ethyl-1-hydroxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (16 mg; 0.035 mmol; 80%). LC-MS: t R =0.91 min.; [M+H] + =454.27 g/mol.
D.8 Introduction of Amide Substituent
3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-1,7-dicarboxylic acid 7-tert-butyl ester
To a cooled (−30° C.) solution of 3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (500 mg; 0.910 mmol) in anhydrous THF (10 ml) was added dropwise 1M ethylmagnesium bromide in THF (2.0 ml; 2 mmol). The resulting colorless suspension was allowed to warm-up to rt in 30 min., and was again cooled to −35° C. before continuous injection of carbon dioxide during 2 h. Water and EA were then added, and the resulting reaction mixture was allowed to warm-up to rt. The organic layer was further washed with aq. sat. NH 4 Cl, dried over magnesium sulfate, filtered, and concentrated to dryness under reduced pressure to give the expected product 3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-1,7-dicarboxylic acid 7-tert-butyl ester as a colorless foam (350 mg; 0.748 mmol; 82%).
3-ethyl-1-methylcarbamoyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester
To a solution of 3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-1,7-dicarboxylic acid 7-tert-butyl ester (47 mg; 0.100 mmol) in anhydrous DMF (1 ml) was added successively TBTU (35 mg; 0.110 mmol), DIPEA (51 μl; 0.300 mmol), and finally 2M methylamine in THF (0.15 ml; 0.300 mmol). The resulting reaction mixture was further stirred at rt, under nitrogen, for 16 h, and was then purified by preparative HPLC to give the pure product 3-ethyl-1-methylcarbamoyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (27.8 mg; 0.057 mmol; 58%).
D.9 Cyclopropanation
1-cyclopropyl-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
To an ice-cooled solution of 1M diethylzinc in hexane (37.0 ml; 37.000 mmol) in anhydrous DCM (40 ml) was added dropwise a solution of TFA (2.82 ml; 36.924 mmol) in anhydrous DCM (20 ml). After 30 min., a solution of methylene iodide (2.97 ml; 36.924 mmol) in anhydrous DCM (20 ml) was added dropwise to the reaction mixture, and stirring at 0° C. was continued for 10 min. A solution of 3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.536 g; 1.231 mmol) in anhydrous DCM (5 ml) was then added dropwise, and the resulting mixture was further stirred at 0° C. for 1 h, and finally at rt for 6 h. The reaction mixture was then treated dropwise with TEA (7 ml), and with an aq. sat. solution of NaHCO 3 (50 ml). The organic layer was dried over anh. MgSO 4 , filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH/25% aq. NH 4 OH, 200/10/1) afforded the target compound 1-cyclopropyl-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow solid (0.186 g; 34%). LC-MS: t R =0.68 min.; [M+H] + =350.42 g/mol.
E Boc-deprotection of 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazines
1-chloro-3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine [general procedure for Boc-deprotection (GP13)]
To an ice-cooled solution of 1-chloro-3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (226 mg; 0.494 mmol) in DCM (5 ml) was added 4N HCl in dioxane (2.5 ml; 10 mmol; 20 eq.). The resulting suspension was further stirred at 0° C. for 10 min., and at rt for 2 h. The volatiles were removed under vacuum and the resulting pale yellow chlorhydrate salt (240 mg) was purified by preparative HPLC in basic conditions leading to the pure product 1-chloro-3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (89.6 mg; 51%). LC-MS: t R =0.77 min.; [M+H] + =358.36 g/mol.
3-ethyl-1-trifluoromethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 3h15) of 3-ethyl-1-trifluoromethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (250 mg; 0.509 mmol) gave after HPLC-purification the expected product 3-ethyl-1-trifluoromethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a slightly beige solid (138.6 mg; 70%). LC-MS: t R =0.80 min.; [M+H] + =392.39 g/mol.
8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 1h30; rt, 2h30) of 8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (260.6 mg; 0.630 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a pale yellow solid (189.2 mg; 96%). LC-MS: t R =0.68 min.; [M+H] + =314.27 g/mol.
3-isopropyl-1-methoxy-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 4 h) of 3-isopropyl-1-methoxy-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (107.5 mg; 0.230 mmol) gave after HPLC-purification the expected product 3-isopropyl-1-methoxy-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a pale yellow solid (45.6 mg; 54%). LC-MS: t R =0.73 min.; [M+H] + =368.26 g/mol.
1-chloro-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 4 h) of 1-chloro-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (97.1 mg; 0.206 mmol) gave after HPLC-purification the expected product 1-chloro-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a pale yellow oil (39.6 mg; 0.106 mmol; 52%). LC-MS: t R =0.79 min.; [M+H] + =372.20 g/mol.
1-chloro-8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 2 h) of 1-chloro-8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (143 mg; 0.335 mmol) gave after HPLC-purification the expected product 1-chloro-8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (44 mg; 0.135 mmol; 40%). LC-MS: t R =0.72 min.; [M+H] + =326.24 g/mol.
1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 2 h) of 1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (136.8 mg; 0.310 mmol) gave after HPLC-purification the expected product 1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (45.9 mg; 0.135 mmol; 44%). LC-MS: t R =0.76 min.; [M+H] + =340.27 g/mol.
1-chloro-8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 4 h) of 1-chloro-8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (179.7 mg; 0.364 mmol) gave after HPLC-purification the expected product 1-chloro-8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a pale yellow solid (70 mg; 0.177 mmol; 49%). LC-MS: t R =0.77 min.; [M+H] + =394.27 g/mol.
1-chloro-3-ethyl-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 2 h) of 1-chloro-3-ethyl-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (153.6 mg; 0.322 mmol) gave after HPLC-purification the expected product 1-chloro-3-ethyl-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (77.8 mg; 0.207 mmol; 64%). LC-MS: t R =0.78 min.; [M+H] + =376.29 g/mol.
1-chloro-3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 2 h) of 1-chloro-3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (191.4 mg; 0.453 mmol) gave after HPLC-purification the expected product 1-chloro-3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (68.2 mg; 0.211 mmol; 47%). LC-MS: t R =0.75 min.; [M+H] + =322.25 g/mol.
1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 2 h) of 1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (225 mg; 0.538 mmol) gave after HPLC-purification the expected product 1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (88 mg; 0.276 mmol; 51%). LC-MS: t R =0.76 min.; [M+H] + =318.29 g/mol.
1-chloro-3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 2 h) of 1-chloro-3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (135.3 mg; 0.284 mmol) gave after HPLC-purification the expected product 1-chloro-3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a colorless solid (71.1 mg; 0.189 mmol; 67%). LC-MS: t R =0.78 min.; [M+H] + =376.20 g/mol.
1-chloro-8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 2 h) of 1-chloro-8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (213.9 mg; 0.486 mmol) gave after HPLC-purification the expected product 1-chloro-8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a colorless solid (90.1 mg; 0.265 mmol; 55%). LC-MS: t R =0.75 min.; [M+H] + =340.21 g/mol.
1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 4 h) of 1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (259 mg; 0.641 mmol) gave after HPLC-purification the expected product 1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a pale yellow oil (61 mg; 0.200 mmol; 31%). LC-MS: t R =0.74 min.; [M+H] + =304.38 g/mol.
1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 4 h) of 1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (191 mg; 0.448 mmol) gave after HPLC-purification the expected product 1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a pale yellow oil (68.3 mg; 0.209 mmol; 47%). LC-MS: t R =0.74 min.; [M+H] + =326.38 g/mol.
1-chloro-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 4 h) of 1-chloro-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (52 mg; 0.117 mmol) gave after HPLC-purification the expected product 1-chloro-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a pale yellow oil (15.4 mg; 0.044 mmol; 38%). LC-MS: t R =0.75 min.; [M+H] + =344.40 g/mol.
3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection of 3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester gave the expected product 3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (15 mg; 0.042 mmol). LC-MS: t R =0.66 min.; [M+H] + =350.32 g/mol.
3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carbonitrile
According to the general procedure (GP13), Boc-deprotection of 1-cyano-3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (5.000 g; 11.148 mmol) gave the expected product 3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carbonitrile as a yellow solid (3.300 g; 9.472 mmol; 85%). LC-MS: t R =0.75 min.; [M+H] + =349.2 g/mol.
1-chloro-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (rt; 4 h) of 1-chloro-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (350 mg; 0.739 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=200/10/1] the expected product 1-chloro-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as an orange oil (190 mg; 0.508 mmol; 69%). LC-MS: t R =0.76 min.; [M+H] + =374.34 g/mol.
{3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazin-1-yl}-MeOH
According to the general procedure (GP13), Boc-deprotection of 3-ethyl-1-hydroxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (16 mg; 0.035 mmol) gave the expected product {3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazin-1-yl}-MeOH as a yellow oil (12 mg; 0.033 mmol; 96%). LC-MS: t R =0.61 min.; [M+H] + =354.32 g/mol.
3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carboxylic acid methylamide
According to the general procedure (GP13), Boc-deprotection of 3-ethyl-1-methylcarbamoyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (27.8 mg; 0.057 mmol) gave the expected product 3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carboxylic acid methylamide as a yellow oil (22 mg; 0.057 mmol). LC-MS: t R =0.74 min.; [M+H] + =381.3 g/mol.
1,3-dichloro-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection of 1,3-dichloro-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (185.7 mg; 0.400 mmol) and purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) gave the expected product 1,3-dichloro-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (121 mg; 0.332 mmol; 83%). LC-MS: t R =0.79 min.; [M+H] + =364.11 g/mol.
1-chloro-3-ethyl-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 1h30) of 1-chloro-3-ethyl-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.283 g; 2.891 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 1-chloro-3-ethyl-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (0.939 g; 94%). LC-MS: t R =0.79 min.; [M+H] + =344.03 g/mol.
1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 1h30) of 1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (6.980 g; 15.112 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (5.450 g; 100%). LC-MS: t R =0.79 min.; [M+H] + =361.99 g/mol.
1-chloro-8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 1h30) of 1-chloro-8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.730 g; 1.601 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 1-chloro-8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (0.569 g; 100%). LC-MS: t R =0.77 min.; [M+H] + =355.94 g/mol.
1-chloro-8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 1h30) of 1-chloro-8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.724 g; 1.574 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 1-chloro-8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (0.567 g; 100%). LC-MS: t R =0.81 min.; [M+H] + =359.96 g/mol.
1-chloro-8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2 h) of 1-chloro-8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.684 g; 1.390 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 1-chloro-8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (0.508 g; 93%). LC-MS: t R =0.84 min.; [M+H] + =391.90 g/mol.
1-chloro-8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 5 min.; rt, 3h15) of 1-chloro-8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.700 g; 1.417 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=250/10/1) the expected product 1-chloro-8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (0.528 g; 95%). LC-MS: t R =0.82 min.; [M+H] + =393.93 g/mol.
1-chloro-3-ethyl-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 5 min.; rt, 3h30) of 1-chloro-3-ethyl-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.288 g; 0.608 mmol) gave the expected product 1-chloro-3-ethyl-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (0.225 g; 99%). LC-MS: t R =0.82 min.; [M+H] + =374.05 g/mol.
4-[2-(1-chloro-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazin-8-yl)-ethyl]-benzonitrile
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 1h30) of 1-chloro-8-[2-(4-cyano-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.506 g; 1.219 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 4-[2-(1-chloro-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazin-8-yl)-ethyl]-benzonitrile as a yellow oil (0.383 g; 100%). LC-MS: t R =0.73 min.; [M+H] + =315.08 g/mol.
3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carbonitrile
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2 h) of 1-cyano-3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.186 g; 0.399 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carbonitrile as a yellow oil (0.141 g; 98%).
8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carbonitrile
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2 h) of 1-cyano-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.271 g; 0.599 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carbonitrile as a pale yellow solid (0.195 g; 92%). LC-MS: t R =0.81 min.; [M+H] + =353.35 g/mol.
1-chloro-3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2 h) of 1-chloro-3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.550 g; 3.284 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 1-chloro-3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (1.220 g; 100%). LC-MS: t R =0.84 min.; [M+H] + =372.00 g/mol.
1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2 h) of 1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.130 g; 2.306 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (0.899 g; 100%). LC-MS: t R =0.85 min.; [M+H] + =390.01 g/mol.
1-chloro-3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2 h) of 1-chloro-3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.373 g; 0.840 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 1-chloro-3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a pale yellow oil (0.277 g; 96%). LC-MS: t R =0.83 min.; [M+H] + =344.41 g/mol.
1-chloro-3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2 h) of 1-chloro-3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.790 g; 4.087 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 1-chloro-3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (1.380 g; 100%). LC-MS: t R =0.75 min.; [M+H] + =338.06 g/mol.
1-chloro-8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2 h) of 1-chloro-8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (1.601 g; 3.511 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=250/10/1) the expected product 1-chloro-8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (1.240 g; 99%). LC-MS: t R =0.80 min.; [M+H] + =356.06 g/mol.
1-chloro-3-ethyl-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 8 h) of 1-chloro-3-ethyl-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.245 g; 0.513 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=600/10/1) the expected product 1-chloro-3-ethyl-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (0.117 g; 60%). LC-MS: t R =0.76 min.; [M+H] + =378.32 g/mol.
1-chloro-3-ethyl-8-(4-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2h30) of 1-chloro-3-ethyl-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.381 g; 0.828 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=500/10/1) the expected product 1-chloro-3-ethyl-8-(4-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (0.257 g; 86%). LC-MS: t R =0.75 min.; [M+H] + =360.17 g/mol.
1-chloro-8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2 h) of 1-chloro-8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.328 g; 0.781 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=150/10/1) the expected product 1-chloro-8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a pale yellow solid (0.240 g; 96%). LC-MS: t R =0.73 min.; [M+H] + =320.18 g/mol.
1-chloro-3-ethyl-8-(3-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine
According to the general procedure (GP13), Boc-deprotection (0° C., 10 min.; rt, 2h30) of 1-chloro-3-ethyl-8-(3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester (0.403 g; 0.876 mmol) gave after purification by FC (DCM/MeOH/25% aq. NH 4 OH=600/10/1) the expected product 1-chloro-3-ethyl-8-(3-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine as a yellow oil (0.182 g; 58%). LC-MS: t R =0.74 min.; [M+H] + =360.33 g/mol.
F Synthesis of electrophiles Z—CHPh-C(O)NHR 4
F.1 Synthesis of toluene-4-sulfonic acid (S)-methyl carbamoyl-phenyl-methyl ester
(S)-2-hydroxy-N-methyl-2-phenyl-acetamide
Methyl (S)-(+)-mandelate (17.000 g; 102.304 mmol) was dissolved in a 2.0 M solution of methylamine in MeOH (230 ml; 460 mmol) and kept at rt for 1 day. Another portion of methylamine in MeOH (10 ml; 20 mmol) was added. A third portion of methylamine in MeOH (10 ml; 20 mmol) was added one day later. After additional 24 h the reaction mixture was concentrated to dryness under reduced pressure to give the desired amide (S)-2-hydroxy-N-methyl-2-phenyl-acetamide as pale yellow crystals which were used without further purification.
LC-MS: t R =0.52 min.; [M+H] + =166 g/mol.
toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester
DIPEA (2.74 ml; 16.005 mmol) and DMAP (145 mg; 1.186 mmol) were successively added at rt to a solution of (S)-2-hydroxy-N-methyl-2-phenyl-acetamide (2.400 g; 14.528 mmol) in DCM (50 ml). The mixture was treated portionwise with p-toluenesulfonyl chloride (2.770 g; 14.529 mmol) and stirred at rt for 2 h. The solvent was removed in vacuo and the residue was dissolved in EA. The organic solution was then washed twice with an aq. sat. NaHCO 3 solution and once with brine. The solvents were removed in vacuo and the residue was recrystallized from EA/tert.-butylmethylether to give the expected tosylate derivative toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester as colorless crystals. LC-MS: t R =0.93 min.; [M+H] + =320 g/mol.
G Synthesis of Compounds of Formula (I)
N-alkylation of 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives with tosylates [general procedure for N-alkylation with electrophiles (GP14)]
To a solution of the respective 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivative (1 mmol) in 2-butanone (6 ml) was added successively N-ethyldiisopropylamine (2 mmol), and the respective tosylate (1.1 mmol). The resulting mixture was heated at the indicated temperature for the given reaction time.
Example 1
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide;
Prepared by reaction (80° C.; 48 h) of 1-chloro-3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (89.6 mg; 0.250 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (87.9 mg; 0.275 mmol) and subsequent separation of diastereoisomers by preparative HPLC. Yellow solid. LC-MS: t R =0.91 min.; [M+H] + =505.40 g/mol.
Example 2
(R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 3 days) of 1-chloro-8-[2-(3,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (70 mg; 0.178 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (62.4 mg; 0.196 mmol) and subsequent separation of diastereoisomers by preparative HPLC. Pale yellow solid. LC-MS: t R =0.95 min.; [M+H] + =541.35 g/mol.
Example 3
(R)-2′-{1-chloro-(S)-8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-8-[2-(2,4-difluoro-3-methyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (90.1 mg; 0.265 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (93 mg; 0.291 mmol) and subsequent separation of diastereoisomers by preparative HPLC. Colorless solid. LC-MS: t R =0.90 min.; [M+H] + =487.54 g/mol.
Example 4
(R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide and (R)-2′-{1-chloro-(R)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (45.9 mg; 0.135 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (47.4 mg; 0.148 mmol) and subsequent separation of diastereoisomers by preparative HPLC.
(R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.90 min.; [M+H] + =487.54 g/mol.
(R)-2′-{1-chloro-(R)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.92 min.; [M+H] + =487.55 g/mol.
Example 5
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide and (R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (71.1 mg; 0.189 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (66.4 mg; 0.207 mmol) and subsequent separation of diastereoisomers by preparative HPLC.
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.92 min.; [M+H] + =523.52 g/mol.
(R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.94 min.; [M+H] + =523.52 g/mol.
Example 6
(R)-2′-{1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (88 mg; 0.276 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (97 mg; 0.303 mmol). Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. Colorless solid. LC-MS: t R =0.89 min. and t R =0.91 min.; [M+H] + =465.59 g/mol.
Example 7
(R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide and (R)-2′-{1-chloro-3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (68.2 mg; 0.212 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (74.4 mg; 0.232 mmol) and subsequent separation of diastereoisomers by preparative HPLC.
(R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.90 min.; [M+H] + =469.53 g/mol.
Mixture of 2 diastereoisomers (R)-2′-{1-chloro-3-ethyl-8-[2-(3-fluoro-4-methyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.88 min. and t R =0.90 min.; [M+H] + =469.53 g/mol.
Example 8
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide and (R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-3-ethyl-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (77.8 mg; 0.207 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (72.7 mg; 0.227 mmol) and subsequent separation of diastereoisomers by preparative HPLC.
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.92 min.; [M+H] + =523.52 g/mol.
(R)-2′-{1-chloro-3-ethyl-(R)-8-[2-(2-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.94 min.; [M+H] + =523.52 g/mol.
Example 9
(R)-2′-{1-chloro-8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-8-[2-(3,4-difluoro-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (44 mg; 0.135 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (47.4 mg; 0.148 mmol). Purification by preparative HPLC afforded the mixture of 2 diastereoisomers: colorless solid. LC-MS: t R =0.87 min. and t R =0.89 min.; [M+H] + =473.54 g/mol.
Example 10
(R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide and (R)-2′-{1-chloro-(R)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 3 days) of 1-chloro-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (68 mg; 0.209 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (73.3 mg; 0.230 mmol) and subsequent separation of diastereoisomers by preparative HPLC.
(R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.88 min.; [M+H] + =473.53 g/mol.
(R)-2′-{1-chloro-(R)-8-[2-(3,5-difluoro-4-methyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.90 min.; [M+H] + =473.54 g/mol.
Example 11
(R)-2′-{1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 3 days) of 1-chloro-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (61 mg; 0.201 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (70.5 mg; 0.221 mmol). Purification by preparative HPLC afforded the mixture of 2 diastereoisomers: slightly beige solid. LC-MS: t R =0.88 min. and t R =0.89 min.; [M+H] + =451.60 g/mol.
Example 12
(R)-2′-{1-chloro-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 3 days) of 1-chloro-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (15 mg; 0.044 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (15.3 mg; 0.048 mmol). Purification by preparative HPLC afforded the mixture of 2 diastereoisomers: slightly beige solid. LC-MS: t R =0.88 min. and t R =0.89 min.; [M+H] + =491.16 g/mol.
Example 13
(R)-2′-{1-chloro-3-isopropyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide and (R)-2′-{1-chloro-3-isopropyl-(R)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-3-isopropyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (39.6 mg; 0.106 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (37.4 mg; 0.117 mmol) and subsequent separation of diastereoisomers by preparative HPLC.
(R)-2′-{1-chloro-3-isopropyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.93 min.; [M+H] + =519.55 g/mol.
(R)-2′-{1-chloro-3-isopropyl-(R)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.95 min.; [M+H] + =519.55 g/mol.
Example 14
(R)-2′-{3-isopropyl-1-methoxy-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 3-isopropyl-1-methoxy-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (45.6 mg; 0.124 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (43.6 mg; 0.136 mmol) and subsequent separation of diastereoisomers by preparative HPLC. Colorless solid. LC-MS: t R =0.87 min.; [M+H] + =515.58 g/mol.
Example 15
(R)-2′-{3-ethyl-1-trifluoromethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide and (R)-2′-{3-ethyl-1-trifluoromethyl-(R)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 4 days) of 3-ethyl-1-trifluoromethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (121.6 mg; 0.311 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (109.2 mg; 0.342 mmol) and subsequent separation of diastereoisomers by preparative HPLC.
(R)-2′-{3-ethyl-1-trifluoromethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: slightly beige solid. LC-MS: t R =1.00 min.; [M+H] + =539.44 g/mol.
(R)-2′-{3-ethyl-1-trifluoromethyl-(R)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: slightly beige solid. LC-MS: t R =1.02 min.; [M+H] + =539.47 g/mol.
Example 16
(R)-2′-{1-chloro-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 4 days) of 1-chloro-3-methoxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (190 mg; 0.508 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (178.5 mg; 0.559 mmol). Purification by preparative HPLC afforded the mixture of 2 diastereoisomers: slightly beige solid. LC-MS: t R =0.98 min., [M+H] + =521.31 g/mol. and t R =1.00 min., [M+H] + =521.29 g/mol.
Example 17
(R)-2′-[1,3-dimethyl-8-(2-p-tolyl-ethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 1,3-dimethyl-8-(2-p-tolyl-ethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.83 min., [M+H] + =417 g/mol.
Example 18
(R)-2′-{1,3-dimethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 1,3-dimethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.85 min., [M+H] + =471 g/mol.
Example 19
(R)-2′-{8-[2-(3-chloro-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 8-[2-(3-chloro-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.84 min., [M+H] + =437 g/mol.
Example 20
(R)-2′-{8-[2-(2,3-dimethyl-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 8-[2-(2,3-dimethyl-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.85 min., [M+H] + =431 g/mol.
Example 21
(R)-2′-{8-[2-(2,4-dimethyl-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 8-[2-(2,4-dimethyl-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.85 min., [M+H] + =431 g/mol.
Example 22
(R)-2′-{(S)-8-[2-(3,4-difluoro-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 8-[2-(3,4-difluoro-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the pure stereoisomer. LC-MS: t R =0.82 min., [M+H] + =439 g/mol.
Example 23
(R)-2′-{8-[2-(2,4-dichloro-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 8-[2-(2,4-dichloro-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.86 min., [M+H] + =471 g/mol.
Example 24
(R)-2′-{8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.81 min., [M+H] + =451 g/mol.
Example 25
(R)-2′-{8-[2-(2,4-dimethoxy-phenyl)-ethyl]-1,3-dimethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 8-[2-(2,4-dimethoxy-phenyl)-ethyl]-1,3-dimethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.81 min., [M+H] + =463 g/mol.
Example 26
(R)-2′-{3-ethyl-1-methyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 3-ethyl-1-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Separation of diastereoisomers by preparative HPLC. LC-MS: t R =0.85 min., [M+H] + =485 g/mol.
Example 27
(R)-2′-{(S)-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide and (R)-2′-{(R)-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 4 days) of 8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (189.2 mg; 0.604 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (212 mg; 0.664 mmol) and subsequent separation of diastereoisomers by preparative HPLC.
(R)-2′-{(S)-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.85 min.; [M+H] + =461.33 g/mol.
(R)-2′-{(R)-8-[2-(3,4-dimethyl-phenyl)-ethyl]-3-ethyl-1-methoxy-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.86 min.; [M+H] + =461.35 g/mol.
Example 28
(R)-2′-{3-ethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction of 3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-1-vinyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester and subsequent separation of diastereoisomers by preparative HPLC. LC-MS: t R =0.88 min., [M+H] + =497.47 g/mol.
Example 29
(R)-2′-{3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by Boc-deprotection of 3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazine-7-carboxylic acid tert-butyl ester and subsequent reaction of 3-ethyl-1-iodo-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.87 min., [M+H] + =597 g/mol.
Example 30
(R)-2′-{1-cyano-3-ethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide and (R)-2′-{1-cyano-3-ethyl-(R)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 16 h) of 3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carbonitrile (2.000 g; 5.741 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (1.833 g; 5.741 mmol) and subsequent separation of diastereoisomers by preparative HPLC.
(R)-2′-{1-cyano-3-ethyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =0.99 min.; [M+H] + =496.43 g/mol.
(R)-2′-{1-cyano-3-ethyl-(R)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: colorless solid. LC-MS: t R =1.01 min.; [M+H] + =496.49 g/mol.
Example 31
(R)-2′-{3-ethyl-1-hydroxymethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction of {3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazin-1-yl}-methanol with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.84 min., [M+H] + =501.52 g/mol.
Example 32
3-ethyl-7-(methylcarbamoyl-phenyl-methyl)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carboxylic acid methylamide
Prepared by reaction of 3-ethyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carboxylic acid methylamide (22 mg; 0.057 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by preparative HPLC afforded the mixture of 2 diastereoisomers. LC-MS: t R =0.86 min., [M+H] + =528.45 g/mol.
Example 33
(R)-2′-{1,3-dichloro-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 4 days) of 1,3-dichloro-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (122 mg; 0.335 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (117 mg; 0.368 mmol). Purification by preparative HPLC afforded the mixture of 2 diastereoisomers.
(R)-2′-{1,3-dichloro-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: yellow solid. LC-MS: t R =1.04 min. and t R =1.06 min.; [M+H] + =511.19 g/mol.
Example 34
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 4 days) of 1-chloro-3-ethyl-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (939 mg; 2.731 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by FC (DCM/MeOH, 25/1) afforded the target compound.
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3,4,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: yellow solid. LC-MS: t R =0.94 min.; [M+H] + =491.05 g/mol.
Example 35
(R)-2′-{1-chloro-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 2 days) of 1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (5.450 g; 15.065 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (5.292 g; 16.571 mmol). Purification by FC (DCM/MeOH, 50/1) afforded the target compound.
(R)-2′-{1-chloro-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: beige solid. LC-MS: t R =0.95 min.; [M+H] + =508.96 g/mol.
Example 36
(R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 4 days) of 1-chloro-8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.569 g; 1.599 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by FC (DCM/MeOH, 25/1) afforded the target compound.
(R)-2′-{1-chloro-(S)-8-[2-(3,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: yellow solid. LC-MS: t R =0.92 min.; [M+H] + =503.00 g/mol.
Example 37
(R)-2′-{1-chloro-(S)-8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 3 days) of 1-chloro-8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.567 g; 1.574 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by FC (DCM/MeOH, 25/1) afforded the target compound.
(R)-2′-{1-chloro-(S)-8-[2-(4-chloro-3,5-difluoro-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: yellow solid. LC-MS: t R =0.96 min.; [M+H] + =506.97 g/mol.
Example 38
(R)-2′-{1-chloro-(S)-8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.508 g; 1.295 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by FC (DCM/MeOH, 50/1) afforded the target compound.
(R)-2′-{1-chloro-(S)-8-[2-(3-chloro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: slightly beige solid. LC-MS: t R =0.98 min.; [M+H] + =538.96 g/mol.
Example 39
(R)-2′-{1-chloro-(S)-8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (75° C.; 91h30) of 1-chloro-8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.518 g; 1.315 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (0.462 g; 1.447 mmol). Purification by FC (DCM/MeOH, 50/1) afforded the target compound.
(R)-2′-{1-chloro-(S)-8-[2-(2,5-difluoro-4-trifluoromethyl-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: slightly beige solid. LC-MS: t R =0.98 min.; [M+H] + =540.91 g/mol.
Example 40
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (75° C.; 70h30) of 1-chloro-3-ethyl-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.215 g; 0.575 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (0.202 g; 0.633 mmol). Purification by FC (DCM/MeOH, 50/1) afforded the target compound.
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(4-trifluoromethoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: slightly beige solid. LC-MS: t R =0.96 min.; [M+H] + =520.94 g/mol.
Example 41
(R)-2′-{1-chloro-(S)-8-[2-(4-cyano-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 4 days) of 4-[2-(1-chloro-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazin-8-yl)-ethyl]benzonitrile (0.383 g; 1.217 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by FC (DCM/MeOH, 50/1) afforded the target compound.
(R)-2′-{1-chloro-(S)-8-[2-(4-cyano-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: slightly beige solid. LC-MS: t R =0.84 min.; [M+H] + =462.16 g/mol.
Example 42
(R)-2′-{1-cyano-3-ethyl-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 6 days) of 3-ethyl-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carbonitrile (0.141 g; 0.387 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (0.135 g; 0.426 mmol. Purification by preparative HPLC afforded the target compound.
(R)-2′-{1-cyano-3-ethyl-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: beige solid. LC-MS: t R =1.04 min.; [M+H] + =514.19 g/mol.
Example 43
(R)-2′-{1-cyano-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 6 days) of 8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carbonitrile (0.195 g; 0.553 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (0.194 g; 0.609 mmol. Purification by preparative HPLC afforded the target compound.
(R)-2′-{1-cyano-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-methyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: yellow solid. LC-MS: t R =0.85 min.; [M+H] + =500.39 g/mol.
Example 44
(R)-2′-{1-chloro-3-propyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-3-propyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (1.220 g; 3.281 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by FC (DCM/MeOH, 50/1) afforded the target compound.
(R)-2′-{1-chloro-3-propyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: yellow solid. LC-MS: t R =0.98 min.; [M+H] + =518.91 g/mol.
Example 45
(R)-2′-{1-chloro-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 3 days) of 1-chloro-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.899 g; 2.306 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by FC (DCM/MeOH, 50/1) afforded the target compound.
(R)-2′-{1-chloro-(S)-8-[2-(3-fluoro-4-trifluoromethyl-phenyl)-ethyl]-3-propyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: yellow solid. LC-MS: t R =0.99 min.; [M+H] + =536.93 g/mol.
Example 46
(R)-2′-{1-cyclopropyl-3-methyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 4 days) of 1-cyclopropyl-3-methyl-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.186 g; 0.532 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (0.187 g; 0.586 mmol). Purification by preparative HPLC afforded the target compound.
(R)-2′-{1-cyclopropyl-3-methyl-(S)-8-[2-(4-trifluoromethyl-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: slightly beige solid. LC-MS: t R =0.88 min.; [M+H] + =497.45 g/mol.
Example 47
(R)-2′-{1-chloro-3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 4 days) of 1-chloro-3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.277 g; 0.806 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (0.283 g; 0.886 mmol). Purification by preparative HPLC afforded the mixture of epimers.
(R)-2′-{1-chloro-3-ethyl-8-[2-(2,3,5-trifluoro-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: pale yellow solid. LC-MS: t R =0.87 min., and t R =0.90 min.; [M+H] + =491.27 g/mol.
Example 48
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 3 days) of 1-chloro-3-ethyl-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (1.380 g; 4.085 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by FC (DCM/MeOH, 25/1) afforded the target compound.
(R)-2′-{1-chloro-3-ethyl-(S)-8-[2-(3-fluoro-4-methoxy-phenyl)-ethyl]-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: yellow solid. LC-MS: t R =0.89 min.; [M+H] + =485.02 g/mol.
Example 49
(R)-2′-{1-chloro-(S)-8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 3 days) of 1-chloro-8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (1.240 g; 3.485 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester. Purification by FC (DCM/MeOH, 100/1) afforded the target compound.
(R)-2′-{1-chloro-(S)-8-[2-(2,5-difluoro-4-methoxy-phenyl)-ethyl]-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl}-N-methyl-2′-phenyl-acetamide: yellow solid. LC-MS: t R =0.91 min.; [M+H] + =502.94 g/mol.
Example 50
(R)-2′-[1-chloro-3-ethyl-(R)-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 4 days) of 1-chloro-3-ethyl-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.117 g; 0.310 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (0.108 g; 0.341 mmol). Purification by FC (DCM/MeOH, 50/1) afforded the target compound.
(R)-2′-[1-chloro-3-ethyl-(R)-8-(4-fluoro-3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide: slightly beige solid. LC-MS: t R =0.92 min.; [M+H] + =525.22 g/mol.
Example 51
(R)-2′-[1-chloro-3-ethyl-(R)-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 4 days) of 1-chloro-3-ethyl-8-(4-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.257 g; 0.714 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (0.250 g; 0.786 mmol). Purification by preparative HPLC afforded the target compound.
(R)-2′-[1-chloro-3-ethyl-(R)-8-(4-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide: slightly beige solid. LC-MS: t R =0.90 min.; [M+H] + =507.25 g/mol.
Example 52
(R)-2′-[1-chloro-(R)-8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide
Prepared by reaction (80° C.; 4.5 days) of 1-chloro-8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.240 g; 0.750 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (0.263 g; 0.825 mmol). Purification by preparative HPLC afforded the target compound.
(R)-2′-[1-chloro-(R)-8-(3,4-dimethyl-phenoxymethyl)-3-ethyl-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide: pale yellow solid. LC-MS: t R =0.88 min.; [M+H] + =467.41 g/mol.
Example 53
(R)-2′-[1-chloro-3-ethyl-(R)-8-(3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide
Prepared by reaction (70° C.; 4 days) of 1-chloro-3-ethyl-8-(3-trifluoromethyl-phenoxymethyl)-5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine (0.182 g; 0.506 mmol) with toluene-4-sulfonic acid (S)-methylcarbamoyl-phenyl-methyl ester (0.177 g; 0.556 mmol). Purification by preparative HPLC afforded the target compound.
(R)-2′-[1-chloro-3-ethyl-(R)-8-(3-trifluoromethyl-phenoxymethyl)-5,6-dihydro-8H-imidazo[1,5-a]pyrazin-7-yl]-N-methyl-2′-phenyl-acetamide: slightly beige solid. LC-MS: t R =0.91 min.; [M+H] + =507.25 g/mol.
II. BIOLOGICAL ASSAYS
In Vitro Assay
The orexin receptor antagonistic activity of the compounds of formula (I) and formula (II) is determined in accordance with the following experimental method.
Experimental Method
Intracellular Calcium Measurements:
Chinese hamster ovary (CHO) cells expressing the human orexin-1 receptor and the human orexin-2 receptor, respectively, are grown in culture medium (Ham F-12 with L-Glutamine) containing 300 μg/ml G418, 100 U/ml penicillin, 100 μg/ml streptomycin and 10% inactivated fetal calf serum (FCS). The cells are seeded at 80,000 cells/well into 96-well black clear bottom sterile plates (Costar) which have been precoated with 1% gelatine in Hanks' Balanced Salt Solution (HBSS). All reagents are from Gibco BRL. The seeded plates are incubated overnight at 37° C. in 5% CO 2 .
Human orexin-A as an agonist is prepared as 1 mM stock solution in MeOH:water (1:1), diluted in HBSS containing 0.1% bovine serum albumin (BSA) and 2 mM HEPES for use in the assay at a final concentration of 10 nM.
Antagonists are prepared as 10 mM stock solution in DMSO, then diluted in 96-well plates, first in DMSO, then in HBSS containing 0.1% bovine serum albumin (BSA) and 2 mM HEPES.
On the day of the assay, 100 μl of loading medium (HBSS containing 1% FCS, 2 mM HEPES, 5 mM probenecid (Sigma) and 3 μM of the fluorescent calcium indicator fluo-3 AM (1 mM stock solution in DMSO with 10% pluronic acid) (Molecular Probes) is added to each well.
The 96-well plates are incubated for 60 min at 37° C. in 5% CO 2 . The loading solution is then aspirated and cells are washed 3 times with 200 μl HBSS containing 2.5 mM probenecid, 0.1% BSA, 2 mM HEPES. 100 μl of that same buffer is left in each well.
Within the Fluorescent Imaging Plate Reader (FLIPR, Molecular Devices), antagonists are added to the plate in a volume of 50 μl, incubated for 20 min and finally 100 μl of agonist is added. Fluorescence is measured for each well at 1 second intervals, and the height of each fluorescence peak is compared to the height of the fluorescence peak induced by 10 nM orexin-A with buffer in place of antagonist. For each antagonist, IC 50 value (the concentration of compound needed to inhibit 50% of the agonistic response) is determined. Antagonistic activities (IC 50 values) of all exemplified compounds are below 1000 nM with respect to the OX 1 and/or the OX 2 receptor. IC 50 values of 51 exemplified compounds are in the range of 5-8671 nM with an average of 691 nM with respect to the OX 1 receptor. IC 50 values of all exemplified compounds are in the range of 2-396 nM with an average of 42 nM with respect to the OX 2 receptor. Antagonistic activities of selected compounds are displayed in Table 1.
TABLE 1
Antagonistic activities of compounds with respect to OX 1 and
OX 2 receptors.
Compound of Example
OX 1 IC 50
(absolute configuration)
(in nM)
OX 2 IC 50 (in nM)
10 (8R; 2′R)
72
14
11 (8S; 2′R)/(8R; 2′R)
36
11
15 (8S; 2′R)
807
15
16 (8S; 2′R)/(8R; 2′R)
2064
33
25 (8S; 2′R)/(8R; 2′R)
10000
115
27 (8S; 2′R)
5
4
28 (8S; 2′R)
176
29
33 (8S; 2′R)/(8R; 2′R)
279
11
36 (8S; 2′R)
17
14
43 (8S; 2′R)
538
14
46 (8S; 2′R)
762
21
53 (8R; 2′R)
412
2 | The invention relates to 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine derivatives of formula (I), wherein X represents CH 2 or O; R 1 represents a phenyl group, which group is independently mono-, di-, or tri-substituted wherein the substituents are independently selected from the group consisting of (C 1-4 )alkyl, (C 1-4 )alkoxy, halogen, cyano, trifluoromethoxy and trifluoromethyl; R 2 represents (C 1-4 )alkyl, (C 1-4 )alkoxy, (C 2-4 )alkenyl, halogen, cyano, hydroxymethyl, trifluoromethyl, C(O)NR 5 R 6 or cyclopropyl; R 3 represents (C 1-4 )alkyl, (C 1-4 )alkoxy-methyl or halogen; R 4 represents (C 1-4 )alkyl; R 5 represents hydrogen or (C 1-4 )alkyl; and R 6 represents hydrogen or (C 1-4 )alkyl. The invention also relates to pharmaceutically acceptable salts of such compounds; and to the use of such compounds as medicaments; especially as orexin receptor antagonists. | 2 |
[0001] This is a continuation-in-part application of U.S. patent application Ser. No. 11/380,123 filed on Apr. 25, 2006.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a mechanical seal, and, particularly, to a mechanical seal with a retainer holding two compression rings by engaging blocks and engaging with two rotating seal rings by a plurality of slide legs.
[0004] 2. Description of the Related Art
[0005] Referring initially to FIG. 1 , a conventional rotary machine such as a pump system has a shaft 9 , which may be used to stir liquids contained in a housing such as a liquid tank. In rotating operation, the rotary machine functions as a stirring apparatus of the housing for example. The rotary machine generally includes a mechanical seal for keeping the stirred liquids within the housing.
[0006] Typically, the mechanical seal includes a gland 7 and a rotating assembly 8 . The gland 7 permits extension of the shaft 9 and mounts the shaft 9 on equipments such as the said housing. The rotating assembly 8 is securely mounted on and rotated with the shaft 9 while being received in the gland 7 . The gland 7 includes a shaft bore 70 , a fluid inlet 71 , and a fluid outlet 72 . The shaft bore 70 longitudinally extends through the body of the gland 7 for the rotating assembly 8 and shaft 9 to pass through. The fluid inlet 71 and fluid outlet 72 both communicate the outside of the gland 7 and the shaft bore 70 for gas or a coolant to be guided into and out of the shaft bore 70 through the fluid inlet 71 and the fluid outlet 72 . Besides, two stationary seal rings 73 are oppositely received in the shaft bore 70 at two ends thereof, and longitudinally sandwiched between the gland 7 and rotating assembly 8 , with both of the stationary seal rings 73 being able to move longitudinally.
[0007] The rotating assembly 8 includes a retainer 81 , a pair of compression rings 82 , a pair of O-rings 83 , a pair of rotating seal rings 84 and a shaft sleeve 85 . The retainer 81 , the compression rings 82 , the O-rings 83 and the rotating seal rings 84 are mounted and assembled on an outer periphery of the shaft sleeve 85 . There are a series of spring members 810 provided on each of two longitudinally opposite sides of the retainer 81 for bias forces of the spring members 810 to oppositely push the two compression rings 82 outwards relative to the retainer 81 . Besides, a plurality of pins 811 are also sandwiched between the retainer 81 and the compression rings 82 for preventing the compression rings 82 from revolving about the shaft 9 . Two side surfaces of each compression rings 82 are respectively in contact with the corresponding spring members 810 and the corresponding rotating seal ring 84 . The O-rings 83 are disposed between the compression rings 82 and the rotating seal rings 84 for providing sealing effects therebetween. Each of the rotating seal rings 84 closely abuts one of the stationary seal rings 73 . Furthermore, the shaft sleeve 85 is mounted on the shaft 9 and rotated therewith.
[0008] When the shaft 9 rotates, the stationary seal rings 73 in the shaft bore 70 of the gland 7 elastically abut against the rotating seal rings 84 of the rotating assembly 8 . In long-term use, there are abrasions occurring between the stationary seal rings 73 and the rotating seal rings 84 of the rotating assembly 8 . The bias forces of the spring members 810 ensure no gap existing between the stationary seal rings 73 and the rotating seal rings 84 by successively pushing the rotating seal rings 84 through the corresponding compression rings 82 . Consequently, the bias forces of the spring members 810 can reduce the possibilities of liquid leakage in the interior of the mechanical seal.
[0009] The conventional mechanical seal has several drawbacks in manufacture. In the installing process, the spring members 810 must be disposed between each side of the retainer 81 and the corresponding rotating seal rings 84 without any positioning member before the whole rotating assembly 8 is completely fixed on the shaft 9 . The primary problem in such a structure is the difficulty in assembling or maintaining due to the fact that the spring members 810 may be easily fallen off from the retainer 81 . Disadvantageously, this may result in a low efficiency in assembly of the above-mentioned elements of the mechanical seal. Moreover, convenience in assembly is especially important for repair or replacement of the rotating seal rings 84 due to the said abrasions thereof.
[0010] Another problem naturally occurring during use of such a mechanical seal is due to the fact that liquids contained in the housing may permeate through a clearance existing between the compression ring 82 and the rotating seal rings 84 . With the structure shown in FIG. 1 , because the spring members 810 for pushing the rotating seal rings 84 at two sides of the retainer 81 are isolated, there is no assistant effect provided by the spring members 810 to prevent the compression rings 82 from revolving about the shaft 9 . In this circumstance, the liquid pressure can press the O-ring 83 and the compression ring 82 to be moved backward to the retainer 81 , and thus can further compress the spring members 810 to be retracted. Consequently, the rotating seal rings 84 cannot exactly abut against the corresponding stationary seal rings 73 . Disadvantageously, the possibility of leakage in such a mechanical seal is increased.
[0011] Another conventional mechanical seal in U.S. Pat. No. 5,375,853 and titled “SECONDARY CONTAINMENT SEAL” discloses a retainer with a cylindrical outer circumferential and an inner wall, and an annular disk element with several apertures is arranged along a central portion of the inner wall. Therefore, a plurality of springs can be inserted in the apertures and sandwiched between a pair of discs disposed on two sides of the annular disk element, with the said springs oppositely pushing two rotating seal rings to respectively abut two stationary seal rings through the said pair of discs. However, in order to retain the discs and rotating seal rings within the retainer, there should be an internal groove adjacent to each end of the retainer for receiving a snap ring with a radially extending wall. As a result, the invention disclosed in the said cited patent provides a complex structure and an assembly process that are still inconvenient for processing the repair or replacement of the rotating seal rings. Furthermore, in operation, the retainer of this cited structure has to suffer a large torque and a revolving movement of the discs. Besides, still another conventional mechanical seal disclosed by U.S. Pat. No. 3,888,495, titled “DUAL-COOLED SLIDE RING SEAL,” provides a structure similar to the last cited patent and also has the same problem of inconvenience in assembly.
[0012] Another US patent titled “SELF-CONTAINED ROTARY MECHANICAL SEALS” and U.S. Pat. No. 4,213,618 shows another conventional mechanical seal mounted on a shaft for rotating therewith and including a lug holder, a plurality of lugs, a plurality of belleville washers, a contact washer, and a carbon seal washer. The lug holder is radially fixed around the shaft, with the lugs extending from the lug holder and parallel to the shaft. The belleville washers are radially surrounded by the lugs and axially compressed between the lug holder and the contact washer to create a spring force urging the carbon seal washer forwards into abutting against a seal seat. Regarding to this conventional invention, what is characterized is that a plurality of tines extending from the lugs in a direction perpendicular to the lugs and concentric to the shaft is provided while several shoulders radially extend from the carbon seal washer. Besides, the shoulders are dimensioned for engagement with the lugs and tines. In detail, a distance of a gap between two adjacent tines of two different lugs is not smaller than a length of the shoulder, so that the shoulder can pass through the gap and received between the said two different lugs. Although convenience in assembly for mechanical seal is improved by this conventional invention, the belleville washers and contact washer are still easy to fall out of the space defined by the lugs once the carbon seal washer is removed. And this is inconvenient for repair or replacement of the carbon seal washer as well. Furthermore, because the carbon seal washer directly abuts against the tines, the shoulders may be easily damaged due to axially pushing force of the belleville washers. Hence, there is a need for a further improvement over the conventional mechanical seal.
SUMMARY OF THE INVENTION
[0013] The primary objective of this invention is to provide a mechanical seal with a retainer and two compression rings for easily maintaining a plurality of spring members between the two compression rings and in a plurality of spring holes of the retainer while two rotating seal rings are axially released from the retainer, with the retainer further providing a plurality of engaging blocks for retaining the compression rings and spring members in the retainer. And, the mechanical seal is used as a dual cartridge seal with two-way-pushing spring members to provide a balanced structure. As a result, the release of the rotating seal rings are completed without disengagement between the spring members, retainer, and compression rings, and only stationary seal rings and rotating seal rings have to be routinely replaced.
[0014] The secondary objective of this invention is to provide the mechanical seal, which has a shaft sleeve with a positioning flange disposed at an outer periphery thereof to limit an axial movement of an O-ring or one of the rotating seal rings. Accordingly, the positioning flange of the shaft sleeve can enhance the sealing effect of the rotating assembly.
[0015] Another objective of this invention is to provide the mechanical seal with a reduced area of the said interface. Accordingly, the mechanical seal is suitable for use in viscous liquid stir.
[0016] Further another objective of this invention is to provide the mechanical seal with a stirring unit that forms an end of the shaft sleeve and faces the said interface. Consequently, suspended impurities in the liquid are unable to accumulate in the said interface.
[0017] The mechanical seal in accordance with an aspect of the present invention includes an gland for being mounted on a housing, a rotating assembly for being passed through by a shaft, and two stationary seal rings separately installed on the gland, with the rotating assembly being arranged between the gland and the stationary seal rings. An inner wall of the gland defines a shaft bore for the rotating assembly as well as the shaft to pass through. And the rotating assembly comprises a retainer, a first compression ring, a second compression ring, a plurality of spring members, a first rotating seal ring, a second rotating seal ring, an a shaft sleeve. The retainer has a primary ring, a plurality of first slide legs, and a plurality of second slide legs. The primary ring is coaxial with the shaft bore and defines a first axial surface and a second axial surface at two axial ends thereof, and a plurality of spring holes communicate the said first and second axial surfaces. The first slide legs are formed on the first axial surface and axially extend outwards while an free end of each first slide leg has a first engaging block protruding to an axial line of the shaft bore. The second slide legs are formed on the second axial surface and axially extend outwards while an free end of each second slide leg has a second engaging block protruding to the said axial line. The first compression ring is coaxial with the shaft bore and formed with at least one cutaway portion at an outer periphery thereof. And the first compression ring is movably positioned between the first axial surface and the first engaging block in axial direction and is radially surrounded by the first slide legs. The second compression ring is also coaxial with the shaft bore and formed with at least one cutaway portion at an outer periphery thereof. And the second compression ring is movably positioned between the second axial surface and the second engaging block in axial direction and is radially surrounded by the second slide legs. The spring members are separately received in the spring holes and oppositely abut against the first and second compression rings with two ends. The first rotating seal ring has one end being abutted by the first compression ring, and a plurality of first notches are formed in a outer periphery of the first rotating seal ring. And an amount of the first notches is not less than an amount of the first slide legs for each first slide leg to be received in and engaged with one of the first notches. The second rotating seal ring has one end being abutted by the second compression ring, and a plurality of second notches are formed in a outer periphery of the second rotating seal ring. And an amount of the second notches is not less than an amount of the second slide legs for each second slide leg to be received in and engaged with one of the second notches. The shaft sleeve for mounted on the shaft sequentially passes through one of the stationary seal rings, the first rotating seal ring, first compression ring, primary ring of the retainer, second compression ring, second rotating seal ring, and the other stationary seal ring. The spring members oppositely push the first and second rotating seal rings through the first and second compression rings. And thus the first and second rotating seal rings respectively abut against the two stationary seal rings to form an interface between the first rotating seal ring and one of the stationary seal rings and another interface between the second rotating seal ring and the other stationary seal ring. A smallest distance form the axial line of the shaft bore to each cutaway portion is not larger than a distance from the said axial line to each first or second engaging block, and radiuses of the outer peripheries of the two compression rings out of the at least one cutaway portion are larger than the said distance between the said axial line and each first or second engaging block, but are not larger than a smallest distance form the said axial line to each slide leg excluded the engaging blocks. The at least one cutaway portion of the first compression ring is mis-aligned with each first slide leg for the first compression ring to be limited between the first engaging blocks and the first axial surface, and the at least one cutaway portion of the second compression ring is mis-aligned with each second slide leg for the second compression ring to be limited between the second engaging blocks and the second axial surface.
[0018] In a separate aspect of the present invention, an end of the shaft sleeve adjacent to the first rotating seal ring forms at least one helical groove facing the said interface between the first rotating seal ring and the corresponding stationary seal ring, with a circular extending direction of each helical groove or helical blade being opposite to a rotating direction of the shaft.
[0019] In a further separate aspect of the present invention, at least one untaken notch is inclined relative to the first or second slide leg when the number of the notches of the first or second rotating seal ring is larger than the number of the first or second slide leg.
[0020] Further scope of the applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] The present invention will become more fully understood from the detailed description given hereinafter and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
[0022] FIG. 1 is a cross-sectional view of a conventional mechanical seal in accordance with the prior art;
[0023] FIG. 2 is an exploded, perspective view of a rotating assembly and a fluid guiding member of a mechanical seal in accordance with a first embodiment of the present invention;
[0024] FIG. 3 is an assembled, cross-sectional view of the mechanical seal in accordance with the first embodiment of the present invention;
[0025] FIG. 4 is a cross-sectional view, taken along line 4 - 4 in FIG. 3 , of a gland of the mechanical seal in accordance with the first embodiment of the present invention;
[0026] FIG. 5 is a partial, perspective view of a primary ring, slide legs, and compression rings before a fore-step in assembly is processed;
[0027] FIG. 6 is a partial, cross-sectional view of the primary ring, slide legs, and compression rings before the fore-step in assembly is processed;
[0028] FIG. 7 is a partial, perspective view of the primary ring, slide legs, and compression rings after a later step in assembly is processed;
[0029] FIG. 8 is a partial, cross-sectional view of the primary ring, slide legs, and compression rings after the later step in assembly is processed;
[0030] FIG. 9 is an exploded, perspective view of a rotating assembly and a fluid guiding member of a mechanical seal in accordance with a second embodiment of the present invention;
[0031] FIG. 10 is an assembled, cross-sectional view of the mechanical seal in accordance with the second embodiment of the present invention;
[0032] FIG. 11 a is a partial, perspective view of a blade-formed stirring unit of the mechanical seal in accordance with the second embodiment of the present invention;
[0033] FIG. 11 b is a partial, perspective view of a groove-formed stirring unit of the mechanical seal in accordance with the second embodiment of the present invention;
[0034] FIG. 12 is a perspective view of a blade-formed helical guiding unit of the mechanical seal in accordance with the second embodiment of the present invention;
[0035] FIG. 13 is an assembled, cross-sectional view of a mechanical seal in accordance with a third embodiment of the present invention; and
[0036] FIG. 14 is a perspective view of a fluid guiding member of the mechanical seal in accordance with the third embodiment of the present invention.
[0037] In the various figures of the drawings, the same numerals designate the same or similar parts. Furthermore, when the term “first”, “second”, “inner”, “outer” “axial”, “radial” and similar terms are used hereinafter, it should be understood that these terms are reference only to the structure shown in the drawings as it would appear to a person viewing the drawings and are utilized only to facilitate describing the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0038] Referring now to FIGS. 2 through 4 , views of a mechanical seal in accordance with a first embodiment of the present invention are shown, which includes a gland designated numeral 1 , a rotating assembly designated numeral 2 and a fluid guiding member designated numeral 3 . In the illustrated embodiment, the mechanical seal is installed between a rotary machine and a housing such as a liquid tank or the like for mechanically linking them.
[0039] Still referring to FIG. 3 , construction of the gland 1 shall be described in detail. In the first embodiment, the gland 1 is firmly mounted on the housing and includes a shaft bore 10 , a fluid inlet 11 , and a fluid outlet 12 . The shaft bore 10 , through which the rotating assembly 2 and a shaft 9 extends, is penetratingly arranged along an axial direction of the gland 1 and defined by an inner wall of the gland 1 . The fluid inlet 11 and fluid outlet 12 both communicate the outside of the gland 1 and the shaft bore 10 , so that a fluid such as gas or a coolant can be guided into and out of the shaft bore 10 through the fluid inlet 11 and the fluid outlet 12 . Preferably, the said fluid inlet 11 and fluid outlet 12 radially extend in the same axial level relative to the shaft bore 10 . In operation, the fluid provides a heat exchange function, such as heat dissipation or heat absorption, to maintain a suitable operational temperature of the gland 1 and the rotating assembly 2 . Besides, two stationary seal rings 13 are received in the shaft bore 10 at two opposite ends thereof, and axially compressed between the gland 1 and rotating assembly 2 , with both of the stationary seal rings 13 being able to move along an axial direction of the gland 1 .
[0040] Referring again to FIGS. 2 and 3 , the construction of the rotating assembly 2 is described in detail as the following. In the first embodiment, the rotating assembly 2 is connected with the shaft 9 and includes a retainer 21 , a pair of compression rings 22 , a shaft sleeve 23 , a first rotating seal ring 24 , a second rotating seal ring 25 and a collar 26 . Extending through the retainer 21 are a series of spring holes to receive spring members identified as “a”. The compression rings 22 are located at either side of the retainer 21 and are in contact with ends of the spring members “a” received in the spring holes. In assembling, each of the compression rings 22 pushes the corresponding rotating seal ring 24 or 25 by spring forces of the spring members “a”. The retainer 21 , the compression rings 22 , the first rotating seal ring 24 and the second rotating seal ring 25 are assembled on the shaft sleeve 23 . The collar 26 securely connects with the shaft sleeve 23 on the shaft 9 such that the rotating assembly 2 may rotate with the shaft 9 .
[0041] Preferably, the rotating seal rings 24 , 25 may be made of wear resisting silicon carbide, carbon steel for example, and closely abut against the stationary seal rings 13 mounted in the gland 1 . Besides, the first rotating seal ring 24 is at a side of the mechanical seal facing the inner of the housing, and the second rotating seal ring 25 is at another side of the mechanical seal adjacent to the atmospheric side. Constructions of the retainer 21 , the compression rings 22 , the shaft sleeve 23 , the first rotating seal ring 24 and the second rotating seal ring 25 will be further described in greater detail below.
[0042] The construction of the fluid guiding member 3 shall be described in detail, still referring to FIGS. 2 through 4 . In the first embodiment, the fluid guiding member 3 is mounted on the inner wall of the gland 1 , adjacent to at least one of the fluid inlet and outlet 11 , 12 , and provided with an axial hole 30 , a stepped portion 31 and a channel 32 . Preferably, the fluid guiding member 3 is in a ring shape and coaxial with the shaft bore 10 of the gland 1 . A diameter of the axial hole 30 allows the passage of any section of the rotating assembly 2 passed through by the shaft 9 , as best shown in FIG. 3 . An O-ring identified as “b 1 ” rests on a side of the stepped portion 31 to seal a clearance existing between the inner wall of the gland 1 and the fluid guiding member 3 such that any possible leakage of liquid is prevented. The channel 32 is radially extended, connects an outer periphery and an inner periphery of the fluid guiding member 3 , and aligns with both of the fluid inlet 11 and fluid outlet 12 . Preferably, each of two opposite edges defining the channel 32 provides a guiding surface 321 , and the two guiding surfaces 321 are adjacent to and obliquely face the fluid inlet 11 and fluid outlet 12 as best shown in FIG. 4 . Therefore, each of the guiding surface 321 guides the incoming fluid from a direction along the fluid inlet 11 into a peripheral direction of the shaft bore 10 , or guides the outgoing fluid from the peripheral direction of the shaft bore 10 into a direction along the fluid outlet 12 .
[0043] Preferably, the retainer 21 is a monolithic one-piece member provided with a primary ring 211 , a plurality of first slide legs 212 , and a plurality of second slide legs 213 . The primary ring 211 is coaxial with the shaft bore 10 and has a first axial surface 214 , a second axial surface 215 , and the series of spring holes, which are previously described and used for receiving the spring members “a”, identified as “ 216 .” The first and second axial surfaces 214 , 215 respectively form two axial ends of the primary ring 210 while the spring holes 215 communicate the two axial surfaces 213 , 214 . Furthermore, in assembly, the primary ring 210 radially surrounds the shaft sleeve 23 . The first slide legs 211 are formed on the first axial surface 214 and axially extend outwards, and an free end of each first slide leg 211 has a first engaging block 217 protruding to an axial line of the shaft bore 1 of the gland 1 . Similarly, The second slide legs 213 are formed on the second axial surface 215 and axially extend outwards, and an free end of each second slide leg 213 has a second engaging block 218 protruding to the axial line of the shaft bore 1 . Preferably, the first and second engaging blocks 217 , 218 are formed on inner surfaces of the first and second slide legs 212 , 213 , which directly face the axial line of the shaft bore 1 .
[0044] Particularly referring to the FIGS. 2 and 5 through 8 , a structure of each compression ring 22 and a relationship between the retainer 21 and the compression rings 22 are illustrated as the following. Each of the compression rings 22 is formed with at least one cutaway portion 221 at an outer periphery thereof. Besides, both of the compression rings 22 are also coaxial with the shaft bore 1 . In order to clearly describe the precise relationship between the retainer 21 and the compression rings 22 , the compression ring 22 faced by the first axial surface 214 of the retainer 21 is renamed and designated as “first compression ring 22 a ,” and the compression ring 22 faced by the second axial surface 215 of the retainer 21 is renamed and designated as “second compression ring 22 b .” The first compression ring 22 a is movably positioned between the first axial surface 214 and the first engaging blocks 217 in axial direction, and radially surrounded by the first slide legs 212 . Similarly, The second compression ring 22 b is movably positioned between the second axial surface 215 and the second engaging blocks 218 in axial direction, and radially surrounded by the second slide legs 213 .
[0045] Specifically, please refer to FIGS. 5 and 6 , which show schematic, partial views of the retainer 21 and the first and second compression rings 22 a , 22 b before the two compression rings 22 a , 22 b being assembled into the retainer 21 . The two compression rings 22 a , 22 b with the at least one cutaway portion 221 are characterized in that a smallest distance D 1 form the axial line of the shaft bore 1 to each cutaway portion 221 is not larger than a distance D 2 from the said axial line to each first or second engaging block 217 or 218 . Besides, if there are plural cutaway portions 221 utilized in the compression rings 22 a , 22 b , each of the plural cutaway portions 221 corresponds to one of the slide legs 212 , 213 . Therefore, regarding to a fore-step in assembly, taking the first engaging block 217 and the first compression ring 22 a for example, the at least one cutaway portion 221 initially aligns with at least one of the first slide legs 212 for the first compression rings 22 a to be pressed into a space between the first engaging blocks 217 and the first axial surface 214 of the retainer 21 . Please be noted that the pressing of the first compression ring 22 a can be completed with the first compression ring 22 a being parallel to the first axial surface 214 when the numbers of the first slide legs 212 and the at least one cutaway portion 221 are the same. Alternatively, the insertion of the first compression ring 22 a is completed with the first compression ring 22 a being inclined relative to the first axial surface 214 for passing the first engaging blocks 217 . The insertion of the second compression ring 22 b is complete in the same way to place the second compression ring 22 b in a space between the second engaging blocks 218 and the second axial surface 215 of the retainer 21 .
[0046] Please further refer to FIGS. 7 and 8 , which show schematic, partial views of the retainer 21 and the first and second compression rings 22 a , 22 b after the said fore-step in assembly is finished. The two compression rings 22 a , 22 b with the at least one cutaway portion 221 are further characterized in that radiuses R of the outer peripheries of the two compression rings 22 a , 22 b out of the at least one cutaway portion 221 are larger than the said distance D 2 but not larger than a smallest distance D 3 form the axial line of the shaft bore 1 to each slide leg 212 or 213 excluded the engaging blocks 217 or 218 . Therefore, regarding to a later step in assembly, taking the first slide leg 212 and the first compression ring 22 a for example, the first compression ring 22 a is turned about the said axial line for the at least one cutaway portion 221 of the first compression ring 22 a to be mis-aligned with each first slide leg 212 . And thus the first compression ring 22 a is exactly limited in the space between the first engaging blocks 217 and the first axial surface 214 . Alternatively, the second compression ring 22 b is also turned for being exactly limited in the space between the second engaging blocks 218 and the second axial surface 215 of the retainer 21 . Therefore, an assembly of the retainer 21 and compression rings 22 a , 22 b can be easily completed by the following steps: firstly pressing or inserting the first compression ring 22 a into the space between the first engaging blocks 217 and the first axial surface 214 through the said fore-step; turning the first compression ring 22 a about the said axial line to complete the misalignment between the at least one cutaway portion 221 of the first compression ring 22 a and each first slide leg 212 through the later step; placing the spring members “a” into the spring holes 216 of the retainer 21 ; pressing or inserting the second compression ring 22 b into the space between the second engaging blocks 218 and the second axial surface 215 through the said fore-step; and turning the second compression ring 22 b about the said axial line to complete the misalignment between the at least one cutaway portion 221 of the second compression ring 22 b and each second slide leg 213 through the later step at last. As a result, the spring members “a” can be always maintained between the two compression rings 22 a , 22 b and in the spring holes 216 .
[0047] Referring again to FIGS. 2 and 3 , the shaft sleeve 23 is a monolithic body and includes a shaft-assembling hole 230 , a positioning flange 231 , and an annular groove 232 . The shaft-assembling hole 230 is penetratingly arranged along an axial direction of the shaft sleeve 23 and coaxial with the gland 1 for the shaft 9 to extend through. The positioning flange 231 is disposed at an outer periphery of the shaft sleeve 23 , and used to limit an axial movement of an O-ring identified as “b 2 ” rested on the outer periphery of the shaft sleeve 23 , as best shown in FIG. 3 , so as to provide a greater sealing effect. Alternatively, the positioning flange 231 can also be used to limit an axial movement of the first rotating seal ring. In rotating operation, the O-ring “b 2 ” functions to prevent any possible leakage of liquids contained in the housing via a clearance existing between the shaft sleeve 23 and the first rotating seal ring 24 . Provided on an inner periphery of the shaft sleeve 23 is the annular groove 232 in which receives another O-ring identified as “b 3 ”. Similarly, the O-ring “b 3 ” functions to prevent any possible leakage of liquids contained in the housing via a clearance existing between the shaft sleeve 23 and the shaft 9 . Besides, the retainer 21 is firmly mounted around the shaft sleeve 23 , preferably, by means of screw connection as shown in FIGS. 2 and 3 .
[0048] Still referring to FIGS. 2 and 3 , the first rotating seal ring 24 is provided with an axial hole 240 , a first stepped portion 241 , a second stepped portion 242 and a plurality of notches 243 , and is abutted by the first compression ring 22 a and pushed by the spring members “a” through the first compression ring 22 a . The axial hole 240 connects between two opposite sides of the first rotating seal ring 24 . In assembling, the axial hole 240 permits the shaft sleeve 23 to extend through. The first stepped portion 241 and the second stepped portion 242 are formed on an inner periphery of the first rotating seal ring 24 . Formed between the first stepped portion 241 and the positioning flange 231 is a space to receive the O-ring “b 2 ”. Formed on an outer periphery of the first rotating seal ring 24 are the notches 243 arranged on an annular flange (unlabeled), extending in a direction parallel to the first slide legs 212 , and preferably being spaced out evenly. The number of the notches 243 is not less than that of the first slide legs 212 for the first slide legs 212 to be received in and engage with the notches 243 .
[0049] Still referring to FIGS. 2 and 3 , the second rotating seal ring 25 is provided with an axial hole 250 , a stepped portion 251 and a plurality of notches 252 , and is arranged to face the second axial surface 215 and pushed by the spring members “a” through the second compression ring 22 a . The axial hole 250 connects between two opposite sides of the second rotating seal ring 25 . In assembling, the axial hole 250 also permits the shaft sleeve 23 to extend through. The stepped portion 251 is formed on an inner periphery of the second rotating seal ring 25 . An O-ring identified as “b 4 ” is received in the stepped portion 251 . Formed on an outer periphery of the second rotating seal ring 25 are the notches 252 , which are also arranged on an annular flange (unlabeled). The number of the notches 252 is not less than that of the second slide legs 213 for the slide legs 211 to be received in and engage with the notches 252 .
[0050] Accordingly, the first rotating seal ring 24 , the retainer 21 and the second rotating seal ring 25 are mounted on the shaft sleeve 23 in order. And the repair or replacement of the rotating seal rings 24 , 25 can surely be simply completed by axially taking off the rotating seal rings 24 , 25 from the retainer 21 without a disengagement between the spring members “a,” retainer 21 , and compression rings 22 . Please be noted that, when the number of the notches 243 or 252 is larger than that of the slide legs 212 or 213 , those of the notches 243 or 252 that are untaken by the slide legs 212 , 213 function as an impeller to drive the fluid in the gland 1 when the shaft 9 is rotated. Moreover, the first and second rotating seal rings 24 , 25 are oppositely pushed by the spring members “a” to closely abut against the two stationary seal rings 13 . Furthermore, a limiting member 14 may firmly engaged on the inner wall of the gland 1 , adjacent to the stationary seal ring 13 abutted by the first rotating seal ring 24 , and radially protruding inwards, so as to prevent failure of sealing due to a large axial movement of the said stationary seal ring 13 . And the limiting member 14 is preferably formed in a ring shape and coaxial with the shaft bore 10 of the gland 1 , with a plurality of through holes 141 extending between two axial faces of the limiting member 14 .
[0051] Now further referring to FIGS. 9 and 10 , views of a mechanical seal in accordance with a second embodiment of the present invention are shown. Differences between the mechanical seals of the first and second embodiments are that a stirring unit 233 forms an end of the shaft sleeve 23 and an auxiliary guiding unit 219 is formed on an outer periphery of the primary ring 211 . Regarding the stirring unit 233 , the end of the shaft sleeve 23 provides the stirring unit 233 is adjacent to the first rotating seal ring 24 and also facing the inner of the housing. Particularly, the stirring unit 233 radially faces the said interface between the first rotating seal ring 24 and the corresponding stationary seal ring 13 outwards. Specifically, please further referring to FIGS. 11 a and 11 b , the stirring unit 233 can be formed by at least one helical groove 233 a , or by at least one helical blade 233 b . Preferably, form a middle part of the shaft sleeve 23 to the said end thereof, a circular extending direction of each helical groove 233 a or helical blade 233 b is opposite to a rotating direction of the shaft 9 . Thereby, when the shaft 9 turns, the stirring unit 233 can drive the liquid received and stirred in the housing to flow beside the said interface, so as to prevent suspended impurities in the liquid from accumulating in the said interface.
[0052] Regarding the auxiliary guiding unit 219 , referring to FIG. 12 , the auxiliary guiding unit 219 is preferably provided with at least one radially outwards formed helical blade 219 a . Therefore, the auxiliary guiding unit 219 can assist the flowing of the fluid received in the shaft bore 10 .
[0053] Moreover, please refer to FIG. 9 again. In order to further enhancing efficiency in driving of the fluid, those untaken ones of the notches 243 or 252 can be inclined relative to the slide legs 212 or 213 .
[0054] Now, please refer to FIGS. 13 and 14 . Views of a mechanical seal in accordance with a third embodiment of the present invention are shown. Differences between the mechanical seals of the second and third embodiments are that the fluid inlet 11 and fluid outlet 12 radially extend in different axial levels relative to the shaft bore 10 . Besides, the said fluid guiding member 3 is arranged adjacent to the fluid outlet 12 , with the channel 32 aligning with the fluid outlet 12 . Furthermore, another fluid guiding member 3 ′ is also mounted on the inner wall of the gland 1 but adjacent to the fluid inlet 11 . The fluid guiding member 3 ′ is in a tube shape that is coaxial with the shaft bore 1 and has a first axial end providing a plurality of radial grooves 33 and a second axial end providing a radial extended annular protrusion 34 . Particularly, an inner opening of each radial groove 33 faces first rotating seal ring 24 , preferably the interface between the first rotating seal ring 24 and the stationary seal ring 13 , inwards. The annular protrusion 34 connects with the inner wall of the gland 1 by an outer periphery thereof, and provides a curved surface 341 smoothly linking a surface of the fluid inlet 11 and an outer periphery of the fluid guiding member 3 ′ out of the annular protrusion 34 . Accordingly, the fluid guiding member 3 ′ smoothly guides the fluid inputted from the fluid inlet 11 to pass through the radial grooves 33 and directly cooling down or heating up the first rotating seal ring 24 and stationary seal ring 13 close to the said interface.
[0055] As has been discussed above, base on the design of the retainer 21 and the compression rings 22 , assembly and repair of the mechanical seal of the present invention without a disengagement of the spring members “a” is easy to be completed, which is absolutely unachievable for those sited prior arts.
[0056] Although the invention has been described in detail with reference to its presently preferred embodiment, it will be understood by one of ordinary skill in the art that various modifications can be made without departing from the spirit and the scope of the invention, as set forth in the appended claims. | A rotating assembly of a mechanical seal includes a retainer, a pair of compression rings, a shaft sleeve, a first rotating seal ring and a second rotating seal ring. The retainer includes a plurality of spring members and a plurality of slide legs longitudinally extended in opposite directions to define limiting spaces where the compression rings are correspondingly restricted. The compression rings are located at opposite sides of the retainer between which the spring members are arranged. In assembling, the retainer, the compression rings, the first rotating seal ring and the second rotating seal ring are assembled on the shaft sleeve. Spring forces of the spring members can actuate the compression rings to push the first rotating seal ring and the second rotating seal ring in the opposite directions. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to a pending provisional patent application entitled “Methods and Apparatus for Severing Concentric Strings of Tubulars,” filed on Mar. 20, 2001. That application carries Serial Prov. No. 60/277,439.
[0002] This application is also a continuation-in-part of U.S. patent application Ser. No. 09/355,439, filed Nov. 29, 1999. That application is entitled “Apparatus for Positioning a Tong, and Drilling Rig Provided with Such an Apparatus.”The parent application was the National Stage of International Application No. PCT/GB97/03174, filed Nov. 19, 1997 and published under PCT Article 21(2) in English, and claims priority of United Kingdom Application No. 9701790.9 filed on Jan. 29, 1997. Each of the aforementioned related patent applications is herein incorporated in its entirety by reference.
BACKGROUND OF THE INVENTION
[0003] Field of the Invention
[0004] The present invention generally relates to plugging and abandonment of oil and gas wells. More particularly, the present invention relates to the removal of a tubular from a wellbore in order to satisfy various environmental regulations. More particularly still, the invention relates to severing nested strings of tubulars that are cemented together in order to more easily handle the tubulars as they are removed from a wellbore during or subsequent to a plugging and abandonment operation.
[0005] In the completion of oil and gas wells, boreholes are formed in the earth and thereafter are lined with steel pipe known as casing. An annular area formed between the outside of the casing and the wall of the borehole is typically filled with cement in order to secure the casing in the borehole and to facilitate the isolation of certain areas of the wellbore for the collection of hydrocarbons. In most instances, because of the depth of a wellbore, concentric strings of tubulars are disposed in the wellbore with each lower string of tubulars being necessarily smaller in diameter than the previous string. In some cases, especially in offshore oil and gas wells, the strings are run in a nested fashion from the surface of the well. In other words, a first string of casing is cemented into the wellbore and, subsequently, a second smaller string of casing is cemented into the first string to permit the borehole to be lined to a greater depth. This process is typically repeated with additional casing strings until the well has been drilled to total depth. In this manner, wells are typically formed with two or more strings of casing of an ever-decreasing diameter.
[0006] When a decision is made to no longer operate a hydrocarbon well, the wellbore is typically plugged to prevent formation fluids from migrating towards the surface of the well or into a different zone. Various environmental laws and regulations govern the plugging and abandonment of wellbores. These regulations typically require that the wellbore be filled with some amount of cement. In some instances, the cement must be squeezed into the annular area around the cemented casing in order to prevent fluids from migrating up towards the surface of the well on the outside of the casing through any cement gaps. In offshore wells, regulations typically require not only the foregoing steps, but also that a certain amount of wellbore casing be completely removed from the wellbore. For example, in some instances, the upper 1,000 feet of casing extending downward from the ocean floor into the wellbore must be removed to complete a plugging and abandonment operation.
[0007] Various methods and techniques have been developed and are currently utilized in order to remove casing from an offshore wellbore. Most often, some type of cutting device is run into the wellbore on a wireline or string of tubulars. The cutting device is actuated in order to sever the casing at a predetermined depth, creating separate upper and lower strings of casing. Thereafter, the upper string is pulled and brought to the surface.
[0008] Because of the great length and weight of the upper string of casing being removed, it is necessary to further sever the upper casing string as it is retrieved at the surface. Accordingly, the casing is further severed into predetermined lengths. This makes handling and disposal of the removed casing more efficient.
[0009] In some instances, the severed upper string of casing includes more than one set of tubulars. In other words, there is a first outer string of casing, and then a second smaller string of casing nested therein. In one example, the outer casing string is 13⅜ inches in diameter, and the smaller casing nested therein is 9⅝ inches in diameter. These two strings of severed casing will typically be joined by a layer of cement within the annular area. This cement layer adds to the weight of the severed casing string, making it even more desirable to cut the retrieved pipe into manageable sections.
[0010] A casing string is typically comprised of a series of joints that are 30 feet in length. The pipe joints are connected by threaded male-to-female connections. When retrieving a severed casing string during a plug and abandonment procedure, it is desirable to break the pipe string by unthreading the connected joints. However, this process is difficult where the severed string consists of outer and inner pipe strings cemented together. Further, there is little incentive to incur the time necessary to break the joints apart at the threads, as the pipe joints from an abandoned well will typically not be re-used. For these reasons, the severed casing is typically broken into smaller joints by cutting through the inner and outer strings at the surface of the well. The severed pipe sections are then recycled or otherwise disposed of.
[0011] In a conventional plug and abandonment operation, casing strings are severed generally as follows:
[0012] First, the casing string is severed within the wellbore. Typically, severance is accomplished at a depth of around 1,000 feet. Thereafter, the severed portion of casing is “jacked” out of the wellbore and raised to the surface of the rig platform using a platform-mounted elevator. As the upper end of the severed casing section reaches the floor of the platform, it is lifted to a predetermined height above a set of slips. The slips are then set, suspending the severed string of casing above the rig floor. A drilling machine then drills a hole completely through the casing, including any cement layer and smaller diameter casing which is cemented within the larger diameter casing. Thereafter, a pin or other retainer is inserted through the drilled hole to ensure that the smaller string of casing is anchored to the larger string. This method of drilling a hole through the casing and inserting a retainer pin is necessary to ensure that the smaller string of casing does not become dislodged from the larger string due to some failure of the cement layer there between.
[0013] After the inner casing string and cement therearound is anchored to the larger outer string, a band saw is used to cut the severed tubular into a predetermined length. The band saw operates with coolant to avoid the use of high temperature cutters or the production of sparks. Typically, a length of between fifteen and thirty feet is selected, with the cut being made above the retention pin. The newly severed, ten-foot portion of string is then transported to a barge or other transportation means for disposal or salvage.
[0014] With the slips disengaged, the elevator then raises the severed string of casing another length of approximately ten feet. The slips are then re-engaged and the drilling, anchoring and cutting procedure takes place again.
[0015] While the foregoing apparatus and method are adequate to dispose of strings of concentrically cemented casing, the operation necessarily requires personnel to be at the drilling mechanism and the band saw during the operation. The presence of personnel on a platform inherently carries risk. The risk is magnified when the personnel must be in close contact with the operating machinery.
[0016] There is a need, therefore, for a method and apparatus of disposing of concentric strings of tubular during a plugging and abandonment operation which does not require personnel to be located directly at the machinery performing the cutting operations. There is a further need for a method and apparatus which can be operated remotely by well platform personnel. There is yet a further need for an apparatus and method that can more safely and effectively sever strings of casing at a well site.
SUMMARY OF THE INVENTION
[0017] The present invention generally provides an apparatus and method for severing predetermined lengths of nested casing above a drilling rig or workover rig platform. The apparatus includes a clamp assembly, a drill assembly and a cutting assembly. In one aspect, the clamp assembly, the drilling assembly and the cutting assembly are disposed at the end of a telescopic arm, and are remotely operated by personnel using a control panel. In accordance with the present invention, the clamp assembly is positioned adjacent a section of casing to be severed, and then clamped thereto. Thereafter, the drilling assembly is actuated so as to drill a hole completely through the casing strings. A retention pin is then inserted through the newly formed aperture. Finally, the cutting assembly, such as a band saw, is actuated so as to severe the casing above the pin. The newly severed portion of casing above the pin may then be disposed of.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] So that the manner in which the features of the present invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0019] [0019]FIG. 1 is a perspective view of the tubular severing apparatus of the present invention, in one arrangement.
[0020] [0020]FIG. 2 is a side, schematic view of the tubular severing apparatus of FIG. 1.
[0021] [0021]FIG. 3 is a perspective view of a cross-sectional cut of a casing section. The pipe section is comprised of an outer casing string, an inner casing string and a layer of cement there between.
[0022] [0022]FIG. 4 is a side view illustrating a drilling assembly of the present invention. The drilling assembly is shown drilling a hole through a casing section.
[0023] [0023]FIG. 5 a is a top view showing an alternate embodiment of a drill assembly of the present invention. FIG. 5 b presents a side view illustrating the drill assembly of FIG. 5 a.
[0024] [0024]FIG. 6 is a perspective view illustrating the tubular severing apparatus of FIG. 1. In this view, the clamping assembly is more clearly seen. The clamping assembly is shown clamping a casing section. Also visible is the band saw being used to cut through the casing section.
[0025] [0025]FIG. 7 is also a perspective view illustrating the tubular severing apparatus of FIG. 1. In this view, features of an exemplary band saw are more clearly. The band saw is again shown cutting a casing section.
[0026] [0026]FIG. 8 is an enlarged view of the band saw of FIG. 7.
[0027] [0027]FIG. 9 is a perspective view of a control panel as might be used to control various portions of the severing apparatus of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0028] The present invention provides a method and apparatus for severing casing that has been removed from a wellbore.
[0029] [0029]FIG. 1 provides a perspective view of a novel tubular cutting apparatus 100 of the present invention, in one embodiment. The apparatus 100 comprises a clamp assembly 130 , a drill assembly 150 and a cutting assembly 120 . The apparatus 100 is selectively movable. In one aspect, the apparatus 100 is disposed at the end of an extendable structure. In FIG. 1, the extendable structure is shown as a cantilevered arm 110 . The exemplary arm 110 defines an outer barrel 110 having at least one telescoping section 112 extending therefrom. An intermediate telescoping section (not shown) may also be incorporated. In such an arrangement, the end telescoping section 112 is slidably mounted in the intermediate telescoping section which is, in turn, slidably mounted in the outer barrel 110 .
[0030] The arm 110 is supported by a base 114 secured to the floor of a rig platform (not shown). The arm 110 is disposed along a vertical support beam 116 vertically extending above the base 114 . In the parent application, the outer barrel of the arm 110 is described as being attached to the support beam 116 by means of a clamp (not shown in FIG. 1) bolted to the top of the beam 116 . The clamp maintains the arm 110 in position with respect to the beam 116 . In one aspect, the arm 110 is pivotally attached to the support beam 116 to permit the tubular severing apparatus 100 to pivot about a vertical axis and, alternatively or in addition, a horizontal axis. In one aspect, the clamp is releasably attached to the support beam 116 .
[0031] An additional feature of the arm 110 described more fully in the parent application is that the outer barrel 110 of the arm itself may be selectively moved with respect to the support beam 116 . This means that the entire arm 110 may be retracted away from the casing section 200 ′. When the telescoping sections 112 are fully contracted, the free end of the arm 110 lies closely adjacent the support beam 116 . This retracting feature is shown in FIG. 4 of the parent application with respect to a tong, but may also be employed in the present application with respect to a tubular severing assembly 100 .
[0032] In the arrangement of FIG. 1, the apparatus 100 is further supported by an overhead hoisting system. Cables 160 from the hoisting system are visible in FIG. 1. In one aspect, the hoisting system maneuvers the tubular severing apparatus 100 , with the telescoping section 112 of the arm 110 moving in response. In another aspect, the telescoping section 112 of the arm 110 is hydraulically powered, causing the apparatus 100 and the supporting cables 160 to advance and recede in response to movement of the arm 110 . Alternatively, the arm 110 and the hoisting system may be independently powered.
[0033] Further details concerning the operation of a suitable telescoping arm are found in the pending application entitled “Apparatus for Positioning a Tong.” That application bears Ser. No. 09/355,439, and was filed on Nov. 29, 1999. That application is incorporated by reference herein, in its entirety.
[0034] Also visible in FIG. 1 is a section of casing 200 ′. Casing section 200 ′ represents an upper, severed string of casing that is being retrieved from a wellbore (not shown in FIG. 1). The casing 200 ′ is being further severed into smaller portions for ease of manipulation and disposal. The exemplary casing string 200 ′ houses a smaller, inner string of casing 205 nested within an outer casing string 200 . The inner string 205 has been cemented into the outer string 200 in connection with earlier wellbore completion operations.
[0035] [0035]FIG. 2 is a schematic view of the apparatus 100 , adjacent a section of casing 200 ′. Visible again in FIG. 2 is the clamp assembly 130 , the drill assembly 150 and the cutting assembly 120 . In this arrangement, the assembly 100 is again disposed at the distal end of the telescopic arm 110 and is suspended from above with cables 160 . The telescopic arm 110 again has at least one telescoping section 112 .
[0036] In FIG. 2, the clamp assembly 130 is radially disposed about the section of casing 200 ′ so as to secure the casing section 200 ′ for severing. The casing 200 ′ is shown in FIG. 2 in cross-section. Visible in this view are the outer casing string 200 , the inner casing string 205 and a matrix of cured cement 210 in the annular region between the two casing strings 200 , 205 .
[0037] [0037]FIG. 3 is a perspective view showing a cross-section of the casing 200 ′ after it has been severed using the apparatus 100 of FIG. 2. As previously described, casing section 200 ′ defines an outer string of casing 200 which houses a smaller diameter casing 205 . A matrix of cement 210 is disposed in an annular area between the two casing strings 200 , 205 . In this view, inner casing string 205 is eccentric relative to the surrounding outer casing string 200 , as is typical in a completed wellbore.
[0038] Referring back to FIG. 2, the tubular string 200 ′ is shown being held above a floor member 170 by a set of slips 172 . The slips 172 permit the tubular string 200 ′ to be raised from below the surface of the platform to some height. Typically, elevators (not shown) are provided on a rig for maneuvering pipe relative to the wellbore. The slips 172 hold the casing 200 ′ so that it can be clamped and severed by the apparatus 100 after positioning of the casing 200 ′ by the elevators.
[0039] As noted, the apparatus 100 includes a drill assembly 150 . The purpose of the drill assembly 150 is to form an aperture through the casing strings 200 , 205 for insertion of a retention member 165 . Preferably, the retention member 165 defines a pin configured to be received within the formed aperture. Various pin types may be used, including, for example, a cylindrical bar, a cotter pin, or a cotter and key. In FIG. 2, a simple tubular pin is shown. The pin 165 serves to anchor any nested casing string 205 and cement 210 to the outer casing string 200 . Preferably, the aperture is formed completely through both the front and back walls of the outer casing string 200 , and the pin 165 is inserted completely through the outer casing string 200 .
[0040] In the arrangement of FIG. 2, the drill assembly 150 is disposed below the band saw 120 . The drill assembly 150 is constructed and arranged to insert a rotating drill bit 151 essentially perpendicular to the longitudinal axis of the casing string 200 ′. In this way, a suitable aperture is formed. Any known drilling device may be employed for boring a through-opening into the casing section 200 ′. The drill assembly 150 of FIG. 2 utilizes a rotary motor (not shown) inside of a housing 153 to rotate a single drill bit 151 . A positioning device is further provided for selectively advancing the drill bit 151 towards and away from the casing section 200 . In one aspect, a hydraulic cylinder 156 is used to advance the drill bit 151 towards and away from the casing section 200 ′ by adjusting flow and pressure of hydraulic fluid.
[0041] An enlarged perspective view of a drill assembly 150 in operation is shown in FIG. 4. The drill bit 151 can be more clearly seen penetrating the wall of the outer section of casing 200 . The drill assembly 150 typically operates with a source of coolant and advances forward towards the casing 200 by means of a telescoping positioning device, shown in FIG. 4 as a cylinder 156 . In one aspect, the drill assembly 150 is operated remotely from a control panel 125 as is shown in FIG. 2. The remote control panel 125 will be more fully described, infra.
[0042] An alternative arrangement for a drill assembly is presented in FIGS. 5 a and 5 b . FIG. 5 a is a top view of an alternate embodiment of a drilling assembly for the present invention. FIG. 5 b is a side view thereof. In this arrangement, a pair of opposing boring devices 155 are urged inwardly towards the center of the casing section 200 ′. Again, it is within the spirit of the present invention to employ any drilling assembly 150 capable of boring an aperture through the casing section 200 ′ for insertion of an anchoring pin 165 .
[0043] Referring again to FIG. 2, it can be seen that the drill assembly 150 has been actuated to form an aperture through both casings strings 200 , 205 . The pin 165 has been inserted through the formed aperture to anchor the inner casing 205 to the outer casing 200 .
[0044] [0044]FIG. 6 is a perspective view of the apparatus 100 of FIG. 1. In this view, the clamp assembly 130 is more clearly seen. The clamp assembly 130 includes a frame 134 that selectively radially encompasses the casing section 200 ′ in order to secure the apparatus 100 to the casing section 200 ′. The clamp assembly 130 further comprises at least two clamp members 140 for frictionally engaging the casing 200 ′. In the arrangement of FIG. 6, the clamp members 140 each define a pair of angled support blocks which are moved into contact with the casing 200 ′. However, other arrangements may be employed, such as a single block having a concave surface.
[0045] The clamp assembly 130 includes a gate member 135 that swivels about a hinge 133 mounted on the frame 134 . The hinge 133 permits the gate member 135 to be selectively opened and closed for receiving and for clamping the casing 200 ′. In the view of FIG. 6, the gate member 135 is closed about the casing 200 ′ while the casing section 200 ′ is being severed. The gate member 135 includes at least one clamp member 140 for engaging the casing 200 ′ in its closed position. The gate 135 preferably operated with hydraulic power, and is remotely operated from control panel 125 . A hydraulic arm 136 is shown to aid in remotely opening and closing the gate 135 .
[0046] [0046]FIG. 7 presents the apparatus 100 of FIG. 1 in still greater detail. In this perspective view, the cutting assembly 120 is more clearly seen. The cutting assembly 120 is shown as a band saw. The band saw 120 first comprises a housing 122 . The housing 122 houses a pair of wheels (not seen in FIG. 7) about which a band saw blade 121 is tracked. The band saw blade 121 includes a plurality of teeth. The blade 121 is fed through pairs of roller members 123 which guide the blade 121 to cut in a direction substantially perpendicular to the longitudinal axis of the outer casing 200 . One pair of roller members 123 is preferably provided at the housing outlet for the blade 121 . In this respect, the blade 121 is fed through this first pair of roller members 123 . A second pair of roller members 123 is disposed at the opening in the housing 122 through which the blade 121 is received back into the housing 122 . The roller members 123 are more clearly seen in the enlarged view of FIG. 8.
[0047] It is within the spirit of the present invention to utilize any cutting device 120 known for severing casing, so long as the cutting device 120 may be adapted to operate in conjunction with a clamp assembly 130 and a drill assembly 150 . In the exemplary arrangement for a cutting assembly 120 of FIG. 7, the cutting assembly defines a band saw 120 . Further, the band saw 120 includes a housing 122 that is offset from the angle of cutting by the blade 121 . In other words, the angle of the housing 122 of the band saw 120 is offset from the angle at which the teeth of the blade 121 engage the outer casing 200 during the cutting operation. The angle shown is approximately 30 degrees, though other angles may be used. In addition, an enlarged spacing 129 is provided in the housing 122 between the wheels. These features accommodate placement of and access to the drill assembly 150 and clamp assembly 130 . The spacing 129 in the housing 122 is more importantly sized to receive the casing 200 ′ as the blade 121 of the saw 120 advances through the casing 200 ′ during a cutting operation
[0048] In the drawings of FIG. 7 and FIG. 8, the blade 121 of the band saw 120 has been actuated. In addition, the blade 121 is engaging the casing section 200 ′, and has advanced partway through the casing 200 ′ to form a cut that is substantially perpendicular to the longitudinal axis of the outer casing 200 .
[0049] Referring again to FIG. 2, the band saw 120 , the clamp assembly 130 , and the drill assembly 150 are preferably controlled in an automated fashion from a control panel 125 . Control lines 126 are provided from the control panel 125 to control the assembly 100 , e.g., parts 120 , 130 , 150 , 154 , etc. FIG. 9 is a more detailed perspective view showing a typical control panel 125 to be utilized with a tubular severing apparatus 100 . The illustrated control panel 125 in one aspect includes separate controls to operate the clamp assembly 130 , the drilling assembly 150 , and the band saw 120 .
[0050] The band saw 120 and the drill assembly 150 are typically operated with similar controls. For example, the drill assembly 150 and saw 120 each require an on/off control and a rotational speed control to manipulate the rotation of the saw blade 121 or the drill bit 151 . Corresponding gauges illustrating the rotational movement of the drill bit 151 and the band saw 121 as shown in revolutions per minute may optionally be provided. In addition, a tool advancing control is provided to control the speed of advance of the drill bit 151 into the casing 200 ′ and the blade 121 of the band saw 120 into the casing 200 ′. Corresponding positioning devices 127 (shown in FIG. 1) and 156 (shown in FIG. 4) are provided for the band saw 121 and the drill assembly 150 . These positioning devices, 126 , 156 , in one aspect, represent telescoping hydraulic cylinders. These devices permit the drill bit 151 of the drill assembly 150 and the blade 121 of the band saw 120 to be independently, selectively advanced towards the casing 200 ′ during the respective drilling and cutting operations and then withdrawn.
[0051] In addition, both the band saw 120 and the drill assembly 150 optionally include pressure sensors to determine the amount of pressure placed upon the casing by the rotating drill bit 151 or the rotating saw blade 121 . Gauges may be provided at the control panel 125 indicating pressures on the drill bit 151 or the rotating saw blade 121 . For example, core heads and saw blades provided by Mirage Tool Co ltd. (U.K.) and core heads from Alf I Larsen (Norway) may be used.
[0052] The clamp assembly 130 also has controls that are located on the control panel 125 . For instance, the clamp assembly 130 includes a panel-mounted control which opens and closes the gate 135 located on the clamp assembly 130 . Optionally, a gauge indicating pressure between the casing 200 ′ and a clamp 140 may be provided and pressure of the clamps 140 . A corresponding sensor is positioned on at least one of the clamp members 140 for sensing pressure of the clamp member 140 against the casing 200 when the gate 135 is closed. [Per: what type of sensor would work? Do you have an example?] Preferably, the sensor is placed on the clamp member 140 on the gate 135 .
[0053] In use, the severing apparatus of the present invention operates as follows:
[0054] First, a casing cutting means (not shown) is run into a wellbore. The cutting means is typically disposed on the end of a run-in string or wireline. The cutting means is placed in the wellbore at a predetermined depth, and then actuated. In this way, a selected length of casing is severed downhole. Thereafter, the severed portion of casing 200 is pulled or “jacked out” of the wellbore and lifted to the rig platform within an elevator.
[0055] A predetermined amount of the severed portion of casing 200 ′ is pulled upwards past the slip 172 located at the level of the platform floor. The casing 200 ′ is held in place by the slip 172 , exposing the upper portion of the casing 200 ′ above the platform floor. Thereafter, a tubular severing apparatus 100 of the present invention is moved towards the casing 200 ′ by the telescopic arm assembly 110 with its extending and retracting sections 112 . As the apparatus 100 reaches a location proximate to the casing 200 ′, the clamp assembly 130 is actuated to open the gate 135 and to receive the casing 200 ′. The gate 135 is then closed around the casing 200 ′, and the clamp assembly 130 is secured to the casing 200 ′ by the clamping members 140 . In this way, the severing apparatus 100 is properly positioned with respect to the casing 200 ′.
[0056] Thereafter, with the outer casing string 200 clamped in the apparatus 100 , the drill assembly 150 is operated. Preferably, remote actuation of the drill assembly 150 is conducted through the control panel 125 . The drill bit 151 disposed on the drill assembly 150 is rotated and advanced towards the casing 200 to form an aperture therein. The aperture is created through at least the front wall of the casing section 200 ′ at an angle substantially perpendicular to the longitudinal axis of the outer casing 200 . A retention mechanism such as a pin 165 is then inserted through the casing 200 ′ to ensure that any inner string of casing 205 is longitudinally fixed with respect to the outer string of casing 200 .
[0057] The next step involves actuation of the band saw 120 . Preferably, actuation of the band saw 120 is performed remotely via the control panel 125 . The blade 121 of the band saw 120 is actuated, and is advanced through the casing 200 ′ at a point above the pin 165 . The retention pin 165 anchors the smaller diameter casing 205 within the larger diameter casing 200 . In this manner, the inner 205 and outer 200 casing strings in the lower section 200 ″ are prevented from separating below the rig floor. The severed portion of the casing section 200 ′ is then lifted away, leaving an upper end of the lower portion of casing 200 ″ remaining within the clamping assembly 130 .
[0058] Once the severed piece of casing 200 ′ has been disposed of, an elevator or other lifting device works with the slips to lift the casing 200 ′ another predetermined distance upwards. The slips 172 are then used to re-grasp the casing 200 ′ for the operation to be repeated. Each time a severing operation is completed, the clamp assembly 130 is de-activated, and the gate 135 is reopened so that the apparatus 100 can move away from the severed piece of casing 200 ′. In addition, it is noted that the pin 165 may be retained in the newly lifted section of casing 200 ′ to be severed. A new pin 165 can then be inserted once a new aperture is formed within the casing 200 ′.
[0059] As demonstrated in the foregoing disclosure, the apparatus 100 of the present invention provides a safe and efficient means for severing casing during a plug and abandonment operation. In one aspect, the apparatus 100 is operated via a remotely located control panel 125 .
[0060] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. | The present invention provides an apparatus and method for severing casing as it is pulled from a wellbore. An apparatus is first provided, comprising a clamping assembly, a drilling assembly and a cutting assembly. In one aspect, the apparatus is disposed at the end of a telescopic arm, with the components being remotely operated by personnel using a control panel. The apparatus can be positioned adjacent casing and clamped thereto. Thereafter, the apparatus can drill a hole completely through the casing for the insertion of a retention pin. The apparatus can then severe the casing into manageable lengths to facilitate disposal, such as during a plugging and abandonment procedure. | 4 |
BACKGROUND OF THE INVENTION
In the past the conventional sled for downhill recreational coasting has been constructed of a steel frame employing a pair of hollow ground steel runners and a wooden deck. While such sleds have enjoyed long standing popularity, they bog down in deep show and are best suited for snow that is packed. It has long been a problem for obtaining a suitable sled for such deep snow operation that is strong, yet light in weight such that it may be operated by children as well as adults.
Various types of sleds employing a main runner as well as outrigger runners have been proposed. Such sleds have generally been provided with raised seats or the like and are unsuitable for the rigors involved in downhill "belly flop" coasting where the rider lays down flat on the sled.
SUMMARY OF THE INVENTION
By means of this invention there has been provided a ski sled that may be used in relatively deep snow in the same manner as a conventional sled having a pair of steel runners and a body supporting deck. The ski sled has a single main runner in the center and a pair of outrigger or side runners to provide stability and turning or precise maneuverability by changing body weight position.
A unique tubular aluminum arch cross frame is employed to anchor the central main ski runner to the outrigger runners. A separate arch cross frame is used for each of the outrigger runners and support a longitudinally running body supporting deck. A longitudinally running bowed or arched strut support also is employed to connect the bowed cross frames above the outrigger runners and support a deck cross-brace at the middle of the deck. By means of the bowed tubular aluminum strut, maximum strength and flexing upon impact may be achieved while maintaining a light weight obtained by the use of wooden skis and deck.
A further feature of the invention employs a pivot connection between the outrigger skis and the arched or bowed cross frame. In this manner coasting upon uneven terrain or the impact and uneveness encountered in the launching operation may be readily accommodated. A height adjustment is also provided for elevation and lowering of the outrigger skis with respect to the main ski permiting adjustment for varying snow conditions.
As a further feature to facilitate body stability and staying on the sled while coasting the body of the sled may be slightly concave or cupped cross-wise of the deck. This provides a trough-like configuration aiding the rider in staying on the sled should it rock from side to side while coasting. In addition, the deck may be provided with a Velcro-like covering and the rider may wear bands or a tight apron of Velcro for literally sticking to the sled.
The sled of this invention is simply constructed of tubular aluminum and wood or like materials to provide a strong, rugged and light weight structure. It is simply employed and may be used in the manner of a conventional sled without the requirement of any special training or skill.
The above features are object of this invention. Further objects will appear in the detailed description which follows and will be otherwise apparent to those skilled in the art.
For the purpose of illustration of this invention a preferred embodiment is shown in the accompanying drawing. It is to be understood that this is for the purpose of example only and that the invention is not limited thereto.
IN THE DRAWING
FIG. 1 is a top plan view of the sled;
FIG. 2 is a view in side elevation taken from the right side of FIG. 1;
FIG. 3 is an enlarged fragmentary view in rear elevation showing the pivotal support for the side runner and height adjustment;
FIG. 4 is a view in side elevation similar to FIG. 3 taken from the right side of FIG. 3;
FIG. 5 is an enlarged view in section taken on the line 5--5 of FIG. 1;
FIG. 6 is a top plan view similar to FIG. 1 showing the sled deck covered with a Velcro-like material; and
FIG. 7 is a top plan view of a body garment having a Velcro-like material for use in the sled operation.
DESCRIPTION OF THE INVENTION
The ski sled of this invention is generally indicated by the reference numeral 10 in FIGS. 1, 2, 5 and 6. It is comprised of, as its main elements, a deck 12, a handle bar 13, a central main ski 14, outrigger or side skis 16 and 18 and a supporting frame 20 for supporting the deck upon the skis.
The frame 20 is comprised as best shown in FIGS. 1, 2 and 5 of bowed or arched tubular cross frames 22 and 24 which connect the main ski 14 to the outrigger skis 16 and 18, respectively. A wooden anchoring block 26 glued or otherwise affixed to the main ski, is provided with openings 28 and 30, anchoring ends of the two cross frames to the center ski or runner by glue or conventional bolts if needed (not shown).
The arched cross frames further support at a top crown portion a wooded cross-brace 32. The brace supports the deck 12 which is comprised of a center slat 34 and side slats 36 and 38 positioned over the crown portion of the arched frames 22 and 24 for optimum stress distribution. The center slat 34 is connected at the front to an upturned portion of the main ski 14 to provide strength to the deck and the main ski. Wedges 40 and 42 are employed to tilt the side slats and provide a trough-like configuration for efficient body retention. Bolts are employed to connect the main ski frames to the brace and the outrigger skis through the wedges, the cross-brace and the crown portion of the tubular arched frames. The frame structure is further provided with a rear arched tubular frame and cross-brace, as shown in FIGS. 1 and 2, which is identical to that described for the front frame and the same reference numerals are applied.
The ends of the arched cross frames 22 and 24 are affixed to the outrigger skis 16 and 18 as best shown in FIGS. 3, 4 and 5. The connection provides for a slight pivot movement of the outrigger skis through an arc as well as height adjustment. The pivotal connection is of a pivot pin 46 connecting a flattened end 48 of each of the arched cross frames to an L-shaped angle iron support 50 anchored to each of the outrigger skis. The end 48 of the arched cross frame is provided with a plurality of openings 52 which are registrable with a plurality of openings 54 in the angle iron support to receive the pivot pin in varying positions of height adjustment simply by resetting the pivot pin as desired.
An outrigger ski tubular strengthening brace 56 for each of the outriggers may also be provided as shown in FIG. 2. This may have a flattened end provided with holes (not shown) and be attached to the base of the angle iron supports 50 previously described. Where desired the strengthening outrigger brace 56 and the front and rear angle iron supports 50 may also be made integral by flattening the ends of the brace 56 and bending them to the angle iron configuration.
A pair of further longitudinal bowed tubular struts 58 is also provided rigidity to the front and rear arched cross frames and support a middle portion of the deck 12. The support 58 is used on both sides of the sled and is best shown in FIGS. 1 and 2 where it is shown fixed at its opposite ends to an upper portion of the front and rear arched cross frames above each of the outrigger skis. A wooden cross-brace 60 is attached to a crown portion of the two struts 58 and extends laterally underneath the middle portion of the deck and is connected by bolts to each of the center and side slats making up the deck.
The unique tubular frame structure is employed to produce a light weight sled where all components of the sled are load bearing to produce structural integrity of the unit. The arched cross frames 22 and 24 resist direct body weight upward and downward loads are carried through the cross frames 22 and 24 to the cross-brace 32 which keeps the cross frames from spreading. Slats 36 and 38 and deck 12 stabilize the front and rear cross frames through a center cross-brace 60 which is attached to struts 58. The struts 58 stabilize the front and rear cross frames from front and rear forces. The struts 58 further transfer about 30-50% of the riders body loads to the front and rear cross frames. These loads are reacted or absorbed by the outrigger skis in tension loads.
FIG. 6 shows the covering of the deck 12 of the sled with a Velcro-like covering 62. An apron 64 has a body portion 66 covered by a mating Velcro-like material and a plurality of tie strings 68 for wrapping the apron to the body. The Velcro-like self-gripping material, which forms no part of this invention, per se, may be as in Velcro U.S. Pat. Nos. 2,717,437; 3,000,384 and 3,009,235. When the user of the sled lies flat upon the deck of the sled he is held snugly thereupon by the well-known mating of the Velcro-like coverings and stability against rolling off the sled is enhanced. Also, body weight shifts on sled may be precisely directed.
USE
The ski sled 10 of this invention is very simply employed. The outrigger skis 16 and 18 are first ajusted to the desired elevation whether this be level with the main ski or elevated thereto. This is accomplished by the adjustment of the pivot pin 46 in the registering holes 52 and 54 of the end of the arched cross-brace and the upstanding portion of the angle iron support 50 on the outrigger skis. Should it be desired to lock the outrigger skis against pivotal movement two pins may be employed instead of one.
The sled is then ready for use. It may be used as any coasting sled on downhill coasting or may be towed by attaching a tow line to the front handle bar 13 or to the two front arched cross frames 22 and 24. In downhill coasting the rider may in the standing position grasp with both hands the front handle bar 13 or use the arched strut 58 as a handle and then hurl himself downhill in the prone position. The concave trough-like body configuration of the deck 12 aids in body stability upon the sled both in the launching, coasting and maneuvering modes.
The outrigger skis 16 and 18 provide for better coasting in relatively deep snow conditions as compared to the conventional sled with a pair of narrow steel runners. The provision for height adjustment accommodates different snow conditions while the pivotal action of the outrigger skis facilitates coasting in terrain that may vary as well as snow conditions and depth of varying parameters.
The tubular arched construction throughout the frame further provides a strong rugged and light weight sled. This aids greatly to withstand the forces and stress placed upon and main and outrigger skis which must withstand the shock provided in the launching operation as well as the coasting mode. A degree of flexibility is also provided which augments the flexing characteristic of the wooden deck and main and outrigger skis.
Where desired the Velcro-like material 62 covering the deck may be employed along with the Velco-like apron 62 of FIGS. 6 and 7. While the trough-like configuration of the deck 12 aids in body stability and retention the use of the Velcro-like material further enhances the ability of the rider to stay on the sled and avoid being thrown.
Various changes and modifications may be made within this invention as will be apparent to those skilled in the art. Such changes and modifications are within the scope and teaching of this invention as defined in the claims appended hereto. | A sled having a ski as a main runner and a pair of side or outrigger skis for stability. An arched tubular frame located fore and aft connects cross-wise the main runner to each of the side runners and supports a wooden deck at the top. A pair of arched struts connect the fore and aft frame. The side runners are provided with a pivot for tilt stability and a height adjustment for varying snow conditions. To maintain the rider on the sled the deck may be provided with a Velcro covering to stick to a Velcro band or apron worn by the rider. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of International Application No. PCT/CN2016/096444, filed on Aug. 23, 2016, which claims the benefit of Chinese Patent Application No. 201520693145.4, filed on Sep. 9, 2015, each incorporated by reference herein in their entirety.
BACKGROUND OF THE INVENTION
Within the field of indoor horticulture, it is commonly known that adjustable light fixtures offer many advantages, such as allowing horticulturists to customize the intensity and geometry of light radiation emitted from a light fixture to meet the needs of plants at different stages of growth, without adjusting the height at which the light fixture is installed, replacing the fixture, changing the lamp used or making other such changes.
Typically, a light fixture is installed above a planting tray of standard dimensions: 4 ft×4 ft, 4 ft×6 ft or 4 ft×8 ft. It is commonly known that plants require different intensities of light for optimal results at different phases of growth, creating the need for a light fixture capable of emitting a light beam of uniform intensity which can be easily adjusted to a plurality of selected geometries, which correspond to both the standard dimensions of commonly used planting trays and selected degrees of intensities commonly required for optimal results at different stages of plant growth.
In the prior art, adjustable light fixtures which comprise at least one arched, concave reflective surface have no end plates along the curved edges of the reflective sheet, thereby failing to reflect light emitted from the central light source toward the sides of the fixture not bounded by the arched sections of the reflective surface. Such arrangements fail to reflect substantial amounts of light radiation into the target area, resulting in a waste of electricity.
Another shortcoming not addressed in the prior art is the inability to adjust the geometry of the light beam emitted by a light fixture in a single step and without the use of additional tools. Previous art requires multiple steps or the use of tools to adjust the geometry of the emitted light beam. Due to the complexity of the adjustments, horticulturists must spend substantial time and exert substantial effort to carry out the adjustments, which in most practical growing situations must be carried out for a large quantity of light fixtures. In addition, the need for the precise use of hand tools requires a sufficiently high level of visibility in the field. This necessitates the installation and operation of auxiliary lighting sources in the work space, which necessarily incurs additional costs.
In the prior art, light fixtures with concave reflective surfaces substantially surrounding the light source on five sides are built with substantially heavy frames or housings to support the light source and the reflective surfaces. The weight of the fixtures increases the difficulty of installation and necessitates that the structure or architecture supporting the fixture is able to support a heavy object. A rigid housing comprising a latitudinal surface above the light source and rigid, longitudinal sides surrounding the light source limits the degree to which reflective surfaces installed within the concave structure can be easily adjusted, and the necessary complexity and heaviness of the fixtures increase manufacturing and shipping costs.
In the prior art, adjusting the concavity of fixtures with arched reflective surfaces requires changing the degree of curvature of the arched surfaces, which may result in sub-optimal geometries of the reflected light beam or sub-optimal uniformity of the radiation intensity of the light beam.
SUMMARY OF THE INVENTION
The present invention seeks to provide an adjustable reflecting device which substantially overcomes or at least ameliorates the disadvantages of the prior art.
Accordingly, it is an object of the invention to provide a light fixture having a concave reflective sheet with movable end plates that maybe adjustably retained to the fixture's minimal frame in different selected positions, whereby the movable end plates retain the reflective sheet in selected degrees of concavity, thereby enabling the light beam, which is created by reflection of light emitted from a light source positioned substantially centrally within the fixture and substantially in parallel to the apex of the concave reflective sheet, to be of adjustable geometry and intensity.
Another object of the invention is to provide a light fixture which can be easily adjusted without the use of tools and in environments with low visibility to emit a light beam that is adjustable between a plurality of selected geometries. In an environment with relatively low visibility, a horticulturist can make the adjustments to the device by listening for a clicking sound or by taking note of physical reverberations when the adjustable retention mechanisms are engaged in different selected positions.
Still another object of the invention is to provide light fixture which can be easily adjusted to emit a light beam that is adjustable between a plurality of selected geometries, which, when the fixture is installed at a height commonly allowed by ceilings or grow-tent hangers of approximately standard height, correspond to the standard dimensions of planting trays used in the indoor horticulture industry, thereby allowing horticulturists to provide uniform light radiation of relatively low intensity to 4 ft×8 ft or 4 ft×6 ft trays of plants during the early and vegetative phases of growth, and then to re-adjust the light beam to a higher intensity of radiation to be projected onto 4 ft×4 ft trays during the plants' flowering phase of growth. These adjustable geometries of the light beam allow horticulturist to re-arrange their plants in grow trays beneath the fixture to minimize the amount of fixtures needed during early and vegetative growth phases and to customize the light beam's radiation intensity to different growing needs, which allows savings in electricity and equipment costs.
Still another object of the invention is to provide a method of constructing a reflective surface for application in an adjustable light fixture from a single substantially rectangular sheet of material which is reflective on at least one side, thereby simplifying manufacturing and installation processes, as well as reducing the amount of material required by eliminating the potential need for overlapping sheets in cases in which more than one sheet are attached together.
Still another object of the invention is to provide a method of constructing a light fixture with reflective surfaces substantially surrounding a light source on five sides in a concave arrangement that does not require a rigid housing or a substantially heavy frame, thereby minimizing manufacturing and shipping costs, while simultaneously optimizing the fixture's reflectivity and range of adjustable positions. The lack of a rigid housing in the present invention allows it to be manufactured using relatively little material and at a correspondingly low total weight, which subsequently allows the fixture to be supported by relatively weak support structures, thereby increasing its versatility for installation in different situations.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be more fully understood from the following description of a preferred but non-limiting embodiment thereof, described in connection with the accompanying drawings, wherein:
FIG. 1 shows a reflector arrangement installed on a light fixture according to an exemplary embodiment;
FIG. 2 is a perspective view of the reflector arrangement of FIG. 1 ;
FIG. 3 is an enlarged perspective view of a reflector unit according to an exemplary embodiment;
FIG. 4 is a perspective view of a pair of wing frame unit according to an exemplary embodiment;
FIG. 5 is a cross-sectional view of a connector rod attached to a reflective sheet wing;
FIG. 6 is a cross-sectional view of a reflective sheet wing having a free edge;
FIG. 7 is a cross-sectional view of a movable end plate adjustably attached to a fixed end plate;
FIG. 8A is a cross-sectional view of a ball catch unit retained in a higher catch position;
FIG. 8B is cross-sectional view of a ball catch unit retained in a middle catch position;
FIG. 8C is cross-sectional view of a ball catch unit retained in a lower catch position;
FIG. 9A is a perspective view of FIG. 1 in use when the reflector arrangement is retained in the higher catch position, as illustrated in FIG. 8A ;
FIG. 9B is a perspective view of FIG. 1 in use when the reflector arrangement is retained in the middle catch position, as illustrated in FIG. 8B ;
FIG. 9C is a perspective view of FIG. 1 in use when the reflector arrangement is retained in the lower catch position, as illustrated in FIG. 8C ;
FIGS. 10A-10C are perspective views of FIG. 1 in use when the adjustable reflector arrangement is retained the catch positions illustrated in FIG. 8A - FIG. 8C ; and
FIGS. 11A-11C are cross sectional views of the concave reflector sheet in use when retained in corresponding catch positions as illustrated in FIG. 8A - FIG. 8C .
DETAILED DESCRIPTION OF THE INVENTION
Exemplary embodiments of a lighting system according to the present invention are presented with those components of primary interest relative to the inventive apparatus and process. For purposes of clarity, many of the mechanical and electrical elements for attaching and assembling the various components of the lighting system are not illustrated in the drawings. A lighting control panel which provides for the electrical control of an illumination bulb used in the present lighting system is not shown in most of the drawings as such bulbs and their operation are well known within the industry. These omitted elements may take on any of a number of known forms which may be readily realized by one of normal skill in the art having knowledge of the information concerning the mode of operation of the system and of the various components and related processes utilized for horticulture lighting systems as provided herein.
As used herein, the term “light fixture” refers to a system capable of creation of a flux of radiation by activation of a lighting bulb. The terms “lighting”, “radiation” and “illumination” all refer to electromagnetic energy having a wavelength in the infrared, visible and ultraviolet range. Lighting bulbs for use in the present invention are those having metal halide, high pressure sodium radiation sources and combinations thereof.
As used in this application, “up”, “down”, “upper”, “lower”, “beneath”, and “above” are intended to facilitate the description of the adjustable reflector assembly. Such terms are merely illustrative of the reflector assembly and do not limit the reflector assembly to any specific orientation.
As used herein the term concave reflector is to have its broadest meaning, including arched sections of any curve that can be desirable as well as any number of straight sections, especially folded sections between the apex of the convex reflector and the light source which prevent radiation from being reflected off the reflector back at the light source and increase the uniformity of the reflected light.
Referring to FIG. 1 to FIG. 3 , the exemplary embodiment of a winged adjustable reflector unit 1 comprises a substantially rectangular back plate 2 . The winged adjustable reflector unit 1 further comprises two lamp socket housings ( 3 . 1 and 3 . 2 ), two lamp sockets ( 4 . 1 and 4 . 2 ), and two fixed end plates ( 6 . 1 and 6 . 2 ) placed on two ends of the back plate 2 . In one embodiment, each fixed end plate may be attached to one end of the black plate 2 . The winged adjustable reflector unit 1 further comprises movable end plates (such as movable end plates 7 . 1 , 7 . 2 , 7 . 3 , and 7 . 4 as shown in FIG. 1 ). FIG. 1 also shows resilient reflective sheet 9 and reflective sheet wings ( 12 . 1 and 12 . 2 ). Each reflective sheet wing ( 12 . 1 and 12 . 2 ) may have two wing edges. For instance, as shown in FIG. 3 , reflective sheet wing 12 . 1 may comprise wing edges 13 . 1 and 13 . 2 . Reflective sheet wing 12 . 2 may comprise wing edges 13 . 3 and 13 . 4 . Each movable end plate ( 7 . 1 , 7 . 2 , 7 . 3 , and 7 . 4 ) may be placed along a wing edge of a corresponding reflective sheet wing ( 12 . 1 or 12 . 2 ). For instance, the movable end plate 7 . 1 may be placed along wing edge 13 . 1 of the reflective sheet wing 12 . 1 . In FIG. 2, 29 refers to an oblong bolt hole.
With references to FIG. 1 and FIG. 4 , the curvature of the reflective sheet wings may be determined by curvature of curved edges of the movable end plates. For instance, the curvature of the reflective sheet wings 12 . 1 may be determined by curvature of curved edges 10 . 1 and 10 . 3 of the movable end plates 7 . 1 and 7 . 4 . As illustrated in FIG. 4 , each movable end plate, such as 7 . 4 , may have a support strip 25 folded at a 90 degree angle toward the corresponding reflective sheet wing 12 . 1 . With references to FIGS. 1-4 and FIGS. 6-7 , the support strip 25 may be welded to the corresponding reflective sheet wings 12 . 1 and 12 . 2 . The support strip 25 may be reinforced by a wing tab 42 protruding from the wing edge of the reflective sheet wing 12 . 1 and positioned to securely interlock with a tab slot 43 , as shown in FIG. 6 .
FIG. 5 is a cross-sectional view of a connector rod 8 attached to a reflective sheet wing 12 . The connector rod 8 may have a securing hole 37 on one end through which a securing means may be installed thus to secure a movable end plate to the fixed end plate. The securing means may be a screw, a bolt or any other things that may be used to secure the movable end plate to the fixed end plate.
FIG. 6 shows that each reflective sheet wing may comprise a free edge. For instance, the reflective sheet wing 12 . 1 may comprise a free edge 11 . 1 . The rigidity of the free edge may be reinforced by a connector rod. For instance, with additional reference to FIG. 2 , a connector rod 8 . 1 may be configured to reinforce the rigidity of the free edge of the reflective sheet wing 12 . 1 and a connector rod 8 . 2 configured to reinforce the rigidity of the free edge of the reflective sheet wing 12 . 2 . Each connector rod ( 8 . 1 and 8 . 2 ) may connect two movable end plates. For instance, with additional references to FIG. 1 and FIG. 4 , the connector rod 8 . 1 may connect two movable end plates 7 . 1 and 7 . 4 .
FIG. 7 is a cross-sectional view of a movable end plate adjustably attached to a fixed end plate by retaining means. Retaining means may attach the movable end plates and the fixed end plates together strongly enough to resist the force of the resilient reflective sheet's natural resilience or the force of gravity acting on the reflective sheet wings. The retaining means may comprise a hinge pin and a hinge pin nut. As shown in FIGS. 6-7 , the hinge pins ( 22 . 1 and 22 . 3 ) and hinge pin nuts ( 24 . 1 and 24 . 3 ) may attach respective movable end plates ( 7 . 3 and 7 . 4 ) to the corresponding fixed end plates 6 . 1 in a loose manner to allow radial rotation around respective hinge pins 22 . 1 and 22 . 3 . 23 refers to a hinge pin hole. The movable end plates may be disengaged and reengaged in a selected position using a relatively small amount of force, such that a person having average strength and skill can easily change the fixture's degree of concavity with little exertion and without the use of any tools. Each reflective sheet wing of the light fixture may also be flexed independently of the other, enabling horticulturists to adapt use to confined spaces, such as installation in close proximity to a wall on one side, wherein it is advantageous to reflect more light away from the wall on one side while covering a relatively large area on the non-walled side.
Fastening mechanism may fasten the movable end plates to the fixed end plate. The fastening mechanism may comprise ball bearing catches and spring-loaded ball bearing unit. As illustrated in FIG. 7 , ball bearing catches 19 . 3 , 20 . 3 , and 21 . 3 are built into one side of the movable end plate. The movable end plates 7 . 3 and 7 . 4 are attached to the corresponding fixed end plate 6 . 1 in an arrangement allowing the movable end plates 7 . 3 and 7 . 4 to slightly radially rotate around the hinge pins 22 . 1 and 22 . 3 , in such a way as to adjustably engage with a respective spring-loaded ball bearing unit 17 . 1 and 17 . 3 installed in the fixed end plates 6 . 1 through the respective ball bearing unit hole 18 . 1 , 18 . 3 , wherein the spring-loaded ball bearing units 17 . 1 and 17 . 3 face toward the corresponding movable end plates 7 . 3 and 7 . 4 .
With additional reference to FIGS. 6-7 , the ball bearing catches 19 . 1 and 19 . 3 , 20 . 1 and 20 . 3 , 21 . 1 and 21 . 3 on the outward facing surfaces of the movable end plates 7 . 3 and 7 . 4 may adjustably engage with the respective spring-loaded ball bearing units 17 . 1 and 17 . 3 , installed on the inward facing surfaces of the corresponding fixed end plates 6 . 1 in a variety of selected positions.
In exemplary embodiments, three selected positions allow the light fixture to be opened to three different degrees of concavity. The geometries of the light beams emitted by these particular configurations roughly correspond to the three standard dimensions of plant trays (4 ft×4 ft, 4 ft×6 ft and 4 ft×8 ft), but the present invention can be easily adapted to include any number of adjustable positions which may be advantageous for growing situations.
Each of the movable end plates 7 . 1 , 7 . 2 , 7 . 3 , and 7 . 4 is adjustably attached to the corresponding fixed end plate 6 . 1 or 6 . 2 at a plurality of selected angles A, B, and C by using adjustable retainable means. As described above, the adjustable retainable means may comprise hinge pins and hinge pin nuts. The selected angles A, B, and C are illustrated in FIG. 8A , FIG. 8B , and FIG. 8C , respectively. By adjusting the installation angles, the degree of concavity of the resilient reflective sheet may be adjusted which may enable the lighting fixture to emit a light beam of selectable geometry. The movable end plates 7 . 1 , 7 . 2 , 7 . 3 , and 7 . 4 may be placed along wing edge of the corresponding reflective sheet wing 12 . 1 or 12 . 2 in such ways that allow varying degrees of flexibility, securing the reflective sheet wing at a fixed angle or fixed degree of curvature for all or part of the wing edge, thereby allowing the curvature of the reflective sheet to be affected to a greater or lesser degree by the extent to which the fixture is flexed.
In use, the lighting fixture is generally suspended by using hanging eye bolts 32 . 1 and 32 . 2 , as illustrated in FIG. 1 , from the ceiling of the grow space or from a hanging bar or other such setup such that the light fixture emits a beam of light down onto the plants positioned below it. The adjustable reflector unit may also comprise adjustable fastening mechanism that adjustably fastens the movable end plates 7 . 1 , 7 . 2 , 7 . 3 , and 7 . 4 to the corresponding fixed end plates 6 . 1 or 6 . 2 .
The adjustable fastening mechanism that adjustably fastens the movable end plates 7 . 1 , 7 . 2 , 7 . 3 , and 7 . 4 to the corresponding fixed end plates 6 . 1 or 6 . 2 may take any form, comprising ball catches, magnetic latches, adjustable latches, roller latches, touch latches, loft latches, bolt and hole mechanisms, hook and eye mechanisms, or any other mechanism that adjustably fastens the movable end plates 7 . 1 , 7 . 2 , 7 . 3 , and 7 . 4 to the back plate 2 or any other fixed component of the lighting fixture. Adjustable fastening mechanisms may be manually adjusted between pre-determined positions by pushing, pulling or physically manipulating the two free edges of the reflective sheet together or apart. In other words, the adjustable fastening mechanisms may be adjusted without use of any tool. In use, the adjustable fastening mechanism is adjusted by pushing the two free edges of the reflective sheet together or apart without the use of any other tool and which makes an easily audible sound and tactile vibration when the fastener is engaged, thereby enabling the user to make adjustments in environments with little visibility.
With references to FIG. 7 and FIG. 8A , the adjustable fastening mechanism may comprise spring-loaded ball bearing unit and ball bearing catch. For instance, engagement of the spring-loaded ball bearing unit 17 . 1 and 17 . 3 with the lower position ball bearing catch 21 . 1 and 21 . 3 adjustably fastens the movable end plate 7 . 3 and 7 . 4 to the corresponding fixed end plate 6 . 1 such that the selected angle A, which is formed between a line from the hinge pin 22 . 1 to 22 . 3 and the corresponding free edge of the reflective sheet wing is relatively acute compared to other selected positions. The configuration corresponds to a relatively closed arrangement of the resilient reflective sheet, as illustrated in FIG. 11A , which causes light emitted from double ended lamp 5 incident on the ridged central section 14 and arched reflective sheet wings to be reflected uniformly across the geometry of a light beam that approximately corresponds to a 4 ft×4 ft plant tray, as can be inferred from FIG. 9A and FIG. 10A .
Similarly, with references to FIG. 7 and FIG. 8B , engagement of the spring-loaded ball bearing unit 17 . 1 and 17 . 3 with the middle position ball bearing catch 19 . 1 and 19 . 3 adjustably fastens the movable end plate 7 . 3 and 7 . 4 to the corresponding fixed end plate 6 . 1 such that the selected angle B, which is formed between a line from the hinge pin 22 . 1 to 22 . 3 and the corresponding free edge of the reflective sheet wing is relatively acute compared to selected angle B. The configuration corresponds to a relatively open arrangement of the resilient reflective sheet, as illustrated in FIG. 11B , which causes light emitted from double ended lamp, not shown in FIG. 11B , incident on the ridged central section 14 and arched reflective sheet wings 12 . 1 and 12 . 2 to be reflected uniformly across the geometry of a light beam that approximately corresponds to a 4 ft×6 ft plant tray, as can be inferred from FIG. 9B and FIG. 10B .
Similarly, with references to FIG. 7 and FIG. 8C , engagement of spring-loaded ball bearing unit 17 . 1 and 17 . 3 with the higher position ball bearing catch 20 . 1 and 20 . 3 results in the most obtuse selected angle C, which corresponds to the most open configuration of the light fixture, as illustrated in FIG. 9C and FIG. 10C .
FIGS. 11A-11C are cross sectional views of the concave reflector sheet in use when retained in corresponding catch positions as illustrated in FIG. 8A , FIG. 8B , and FIG. 8C . The resilient reflective sheet is folded and flexed to create exemplary arrangements of reflective surfaces. The exemplary arrangements may include any combination of flat, ridged and curved sections. In exemplary arrangements, as illustrated in of FIG. 11A to FIG. 11C , the resilient reflective sheet is folded to feature two symmetrical curved reflective sheet wings (not completely shown), which radially rotate around two parallel pivot axes. The pivot axis is defined by the position of corresponding hinge pins, as described above, and which roughly corresponds to hinge folds 16 . 1 and 16 . 2 on the resilient reflective sheet. Additional folds are made parallel to the hinge folds 16 . 1 and 16 . 2 in the central section 14 of the resilient reflective sheet form a central ridge 15 , which prevents light emitted from the double-ended lamp from being reflected directly back at the double-ended lamp 5 , as shown in FIGS. 9A-9C . A number of auxiliary ridges 36 . 1 and 36 . 2 , as shown in FIGS. 11A-11C are on both sides of the central ridge 15 , which serve the purpose of diffusing the light radiation reflected by the fixture in order to emit a light beam of substantially uniform radiation across its geometry. A peak is formed between the central ridge 15 and an auxiliary ridge. For instance, as shown in FIG. 11A , peak 39 . 1 is formed between the central ridge 15 and the auxiliary ridge 36 . 1 . Peak 39 . 2 is formed between the central ridge 15 and the auxiliary ridge 36 . 2 . | An adjustable reflector device for light fixtures is disclosed. The device comprises a reflector sheet made of a resiliently flexible material with at least one reflective surface folded and flexed along two parallel pivot axes into a concave arrangement of one central section and two flexible wings behind a high-intensity discharge lamp, such that the degree of concavity of the reflector can be adjusted to a plurality of predetermined degrees relative to the lamp by flexing or bending the wings radially around the pivot axes without the use of tools, thereby allowing horticulturists in the field to adjust the geometry of the light beam emitted in order to provide plants positioned below the fixture with a uniform pattern of light radiation of different intensities as needed at different stages of plant growth. | 8 |
BACKGROUND OF THE INVENTION
This invention relates to expanded polystyrene foam products or other open-cell foam products which are useful in the preparation of lightweight building materials, such as insulation boards and the like, and more particularly to expanded polystyrene foam products having open cells or spaced beads of polystyrene wherein the material is impregnated with paraffin, candelilla, montan and other types and blends of waxes to increase the product's density and both its compressive and tensile strengths thereby rendering it resilient, waterproof, and weatherproof at relatively low cost.
DESCRIPTION OF THE PRIOR ART
Foamed resins have gained wide acceptance in recent years for the manufacture of lightweight articles; such articles are obtained by foaming the resin or expanding and fusing beads within a mold. These foam articles have little strength and their resistance to abrasion and wear leaves much to be desired. While some attempts have been made to laminate such products such as polyurethane foam to materials having better wear characteristics, these attempts have not always been successful because of the difficulty in recurring good adhesion between a thermoplastic film or sheet and the porous inert underlying polyurethane foam layer.
Low density foam formulations and processing techniques are readily available; however, the physical properties, i.e. tensile strength, tear strength and compression, deflection behavior and water absorption displayed by these lighter foams are unacceptable for some commercial applications and higher density closed-cell extruded foams are too expensive to be economically attractive.
It would be desirable to saturate a low density foam product to increase its density and improve its physical properties so that it can be used, for example, as a building material such as an insulation board.
The prior art discloses the impregnation of various kinds of foam materials with various substances.
The Turkewitsch U.S. Pat. No. 3,503,822 discloses a polyurethane foam which is impregnated with a thermoplastic substance.
U.S. Pat. Nos. 3,876,221; 3,944,204; and 2,955,056 to Chant, Dirks and knox, respectively, disclose various thermosetting resins which may be impregnated into various open-cell foamed structures.
U.S. Pat. No. Re. 21,311 describes a waterproofing technique wherein wax is employed as the impregnant.
None of these patents disclose a composite product formed by the impregnation of a cellular low density product with wax. One such low density product is expanded polystyrene which when pressure impregnated with thermosetting wax forms a resilient, highly wear-resistant, water and weatherproof board that may serve many building needs, such as, for example, an insulating means which may be readily cut to size and nailed in place.
SUMMARY OF THE INVENTION
In accordance with the invention claimed, a new and improved composite product is provided comprising an expanded polystyrene foam impregnated with wax to any desired degree to obtain a useful, water and weatherproof product that is resilient, easy to cut and nail in place when used as a building material. The material can also be used as a floating barrier on water to prevent evaporation loss as well as conserve energy, for example, on swimming pools.
It is, therefore, one object of this invention to provide a new durable, insulated construction material formed from inexpensive readily available material.
Another object of this invention is to provide a composite material formed from wax and expanded polystyrene.
A further object of this invention is to provide a new method of waterproofing and weatherproofing expanded polystyrene so that the material can be used, for example, as a floating water vapor and energy barrier.
A still further object of this invention is to provide new composite products formed by wax impregnating a low density open cellous product of types other than expanded polystyrene. The properties of the composite product can be controlled by adjusting either the amount or type of wax added.
Further objects and advantages of the invention will become apparent as the following description proceeds and the features of novelty which characterize this invention will be pointed out with particularity in the claims annexed to and forming part of this specification.
BRIEF DESCRIPTION OF THE DRAWING
The present invention may be more readily described by reference to the accompanying drawing, in which:
FIG. 1 is a perspective illustration of a sheet of foamed polystyrene or other type of open cellular product being impregnated with a thermosetting wax;
FIG. 2 is a perspective illustration of the pressurizing vessel and heating system to provide liquid wax;
FIG. 3 is a cross-sectional view of the impregnated foamed polystyrene sheet or other type of cellular product of FIG. 1 compressed between a pair of molding plates; and
FIG. 4 is a perspective view of one finished saturated polystyrene sheet or other type of cellular product.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring more particularly to the drawing by characters of reference, FIG. 1 discloses a sheet 10 of a foamed cellular low density product such as, for example, a sheet of polystyrene having either open cells or spaced beads of polystyrene 10'. A supply 11 of non-foaming thermosetting paraffin, candelilla, montan or other type or blend of wax is provided from a source 12. The sheet 10 covered and at least partly impregnated with the liquid wax is either placed in a closed vessel-like apparatus 13 under pressure and impregnated with wax in a known manner, as shown in FIG. 2, or compressed between molding plates 14 and 15, as seen in FIG. 3. The wax is cured or hardened by cooling the sheet while it is under pressure, if so desired, or cured or hardened at atmospheric pressure once it is impregnated to the predetermined amount.
Upon curing or hardening, the sheet retains substantially its original thickness with the void spaces filled with wax. The resulting article may be flat or any other shape depending on the original shape of the initial unsaturated article.
As shown in FIG. 2, the vessel-like apparatus 13 comprises a chamber 16 which may be horizontally positioned for receiving one or more sheets of material to be impregnated. This chamber is openable from at least one side or end such as end 17 for receiving the sheet or sheets of material 10. For example, one or more spaced 4 foot by 8 foot sheets of a given or different thickness may be spacedly arranged in the chamber or a single sheet up to 18 inches in thickness may be suitably impregnated under pressure.
FIG. 2 further illustrates a further chamber 18 which is heated by a suitable burner 19 for melting a suitable wax product placed therein. The wax in its moltened stage under pressure is then conveyed under pressure through pipe lines 20 to chamber 16 containing sheets 10. The liquid wax is returned to chamber 18 by means of pump 21 through pipe line 22.
It should be noted that the wax in the sheet of polystyrene may be substantially uniformly disposed throughout the article. The intensity of saturation and the firmness of the saturated polystyrene depends on the pressure used in the pressurizing vessel or between the mold plates and the amount and type of liquid wax applied and the length of time the foam is left pressurized in the molten wax.
While the thermosetting liquid wax composition may be clear, i.e. unpigmented and essentially clear, color can be added so that the resulting article may be colored, made reflective, etc.
With relatively small cells, the waxed impregnated polystyrene may obtain a marblized like surface appearing uniform between the cell wall elements or beads of the saturated polystyrene thereby rendering thee wax saturated polystyrene easily cut or machined to fit its various uses.
By utilizing the flexible varieties of waxes and colors, the resulting saturated expanded polystyrene sheet can be substituted for various insulating materials since it can be readily cut and nailed in place and it remains a durable, inexpensive, readily available material. The material can be shipped and seamed together by dipping the edge of the board in molten wax just prior to overlapping with an adjacent sheet. It has waterproofing and weatherproofing characteristics which neither product, the wax or the polystyrene alone, provides. Since the wax is within the insulating polystyrene, it is protected from melting and accordingly, can be exposed to the sun and still retain its weatherproofing properties.
Wax increases the weight of the polystyrene without substantially changing its size and reduces wind and breakage possibilities. This added weight is an essential property to reduce wind damage when the material is used as a floating cover.
Although but few embodiments of the present invention have been emphasized and described, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the spirit of the invention or from the scope of the appended claims. | Wax saturated expanded polystyrene or other type of open-cell foamed product and method of manufacture for increasing its surface and/or body compressive and tensile strengths rendering the resulting product effective as a building material. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to very low cost portable compact scanners and printers. More particularly it is directed to a removable ribbon cassette and drive system accessary and method for use with a portable compact scanner copier/printer which facilitates simple ribbon replacement by consumers. In addition, the present invention relates to an improved thermal transfer printing process wherein the separating of the spent thermal transfer ribbon from the receiver sheet is enhanced by an "L" shaped mechanical member pivotally connected to a translatable thermal print head. Yet still, the present invention relates to methods of ribbon conservation.
Historically, copies of original documents have been produced by a xerographic process wherein the original document to be copied is placed on a transparent platen, either by hand or automatically through the use of a document handler, and the original document illuminated by a relatively high intensity light. Image rays reflected from the illuminated document are focused by a suitable optical system onto a previously charged photoconductor, the image light rays functioning to discharge the photoconductor in accordance with the image content of the original to produce an electrostatic latent image of the original on the photoconductor. The electrostatic latent image so produced is thereafter developed by a suitable developer material commonly referred to as toner, and the developed image transferred to a sheet of copy paper brought forward by a suitable feeder. The transferred image is thereafter fixed to the copy paper by fusing to provide a permanent copy while the photoconductor is cleaned of residual developer preparatory to recharging.
More recently, interest has arisen in electronic imaging where, in contrast to the aforedescribed xerographic system, the image of the document original is converted to electrical signals which may be processed, transmitted over long distances, and/or stored, are used to produce one or more copies. In such an electronic imaging system, rather than focusing the light image onto a photoreceptor for purposes of discharging a charged surface prior to xerographic development, the optical system focuses the image rays reflected from the document original onto an image reading array which serves to convert the image rays reflected to electrical signals. These signals are used to create an image by some means such as operating a laser beam to discharge a xerographic photoreceptor, or by operating some direct marking system such as an ink jet or thermal transfer printing system.
It is generally advantageous if the normally separate document reading and copy printing operations could be combined. If some of these reading/writing functions could be combined, system operation and synchronization could be simplified and system cost reduced through the use of fewer parts.
There are systems in the prior art that address the above identified concerns. For example, U.S. Pat. Nos. 4,496,984 and 4,583,126 to Stoffel, disclose an input/output scanner for simultaneously reading a document and writing a copy thereof. The document and copy sheet are fed in back to back relation with respect to a read/write station. A monolithic full width reading array scans each line in two steps, to improve resolution. The writing array of the read/write station consists of rows of ink jet nozzles, of which the number and disposition is in direct correspondence to the sensors of the read bar/array.
U.S. Pat. No. 4,424,524 to Danisle discloses a full width read/write LED array for scanning a document in the read mode or exposing the photoreceptor in the write mode. A Selfoc optical fiber lens array is used for focusing the full width LED array on the document or photoreceptor.
U.S. Pat. No. 4,724,490 to Tanioka teaches an image input device having an original exposing portion, an image sensor portion, and a thermal print head portion formed by heat generating members. The heat generating members are driven by a signal originating in the image sensor portion and are used to effect printing using a thermosensitive copy medium.
A difficulty with these prior art systems combining imaging and printing is the complexity and cost of separate components such as the complex optics, photoreceptor and developer such as in the Daniele system. In others such as the Stoffel system, it is necessary for an operator to manually combine a document and copy sheet into a single unit for manual insertion to machine feed rolls. Such a system also has a significant cost penalty associated with components such as the monolithic full width reading array.
Several patents assigned to the assignee of the instant application suggest a unique compact alternative to the above-described systems. These include U.S. Pat. Nos. 4,920,421, 5,040,074, 5,032,922, 5,153,736, 5,153,738, 5,162,918 and 5,187,588, all of which teachings are incorporated herein by reference.
The copier concepts described immediately above are attempts to reduce cost and complexity of such a copier while at the same time maximizing compactness and portability. Accordingly, all of the systems described therein rely on ink jet or thermal transfer print technology rather than the more bulky impact type printing apparatus.
Printing with ink jets requires specialized nozzles no which ink is supplied under pressure by a pump from a suitable manifold or other type of reservoir. Generally, the print heads of these systems are connected to a flexible umbilical ink supply tube. Of course, this extra hardware adds to the overall cost of the copier and unnecessarily complicates the print mechanism.
Thermal printing, on the other hand, is a non-impact printing process that enables formation of high resolution images. These printing processes are simple, offer low noise levels, and are very reliable over extended usages. Thermal printing processes may be classified into three categories. Direct thermal printing entails the imagewise heating of special papers coated with heat sensitive dyes, such that an image forms in the heated areas. Another method of thermal printing is known as the dye transfer or dye sublimation technique, and operates by heating a transfer element coated with a sublimable dye, which transfer element is not in contact with the receiving sheet. When the transfer element is imagewise heated, the dye sublimates and migrates to the receiver sheet, which possesses a polymeric coating into which the dye diffuses, forming the image. A third method of thermal printing is known as thermal transfer printing. The thermal transfer printing process entails imagewise heating of a transfer element containing ink. The transfer element is in intimate contact with a heater or heating element on one surface and a blank receiving sheen on the other surface. Imagewise heating of the transfer element affects the ink in such a way as to cause it to transfer from the transfer element to the receiving sheet, thereby resulting in image formation. Thermal transfer printing methods generally employ uncoated plain papers, which enables prints with acceptable appearance and excellent archival properties. In addition, the thermal transfer printing method can be employed for color printing applications by using transfer elements of the desired color or color combinations.
Thermal transfer printing processes generally employ a thermal printhead, a transfer element, and a receiver sheet. The side of the transfer element containing the ink is placed in contact with the receiver sheet, and heat originating from the printhead is then applied to the transfer element. Heat conducted through the element increases the temperature of the ink, which can cause it to melt, soften, decrease in viscosity, or otherwise undergo a transition that enables the ink to transfer to the receiver sheet. After the receiver sheet and transfer element are separated, an image remains on the receiver sheet. The operation of separating the transfer element from the receiver sheet, however, is critical in obtaining a crisp and smudge free copy product.
An alternative method of heating the transfer element, known as resistive heating, employs an array of electrodes instead of a thermal printhead to generate a current between the electrodes and a grounded conductive layer in the transfer element. This method is described in the IBM Journal of Research & Development, Vo. 29, No. 5, 1985, the disclosure of which is incorporated herein by reference. Additional information concerning thermal transfer printing processes is disclosed in Thermal Transfer Printing: Technology, Products, Prospects, published by Datek Information Services, P.O. Box 68, Newtonville, Mass., the disclosure of which is also incorporated herein by reference. Resistive heating methods also critically depends on a definite separating of the transfer element from the receiver sheet for obtaining a crisp final copy product.
As pointed out above, the process of stripping the transfer element from receiver sheet is an important consideration in portable thermal printers. However, perhaps equally significant is the tradeoff between i) the number of pages which can be printed before it becomes necessary to replace the thermal transfer element and ii) the bulk or overall physical size of the cassette structure carrying the transfer element on spools therein. This tradeoff is common to both portable thermal printers and copiers of the type described above.
One obvious method of increasing the number of successive documents created is to silly enlarge the thermal transfer element spool capacity within the cassette structure. However, generally, the length of the transfer element ribbon is proportional to the square of its spool diameter. For prior art systems using ribbon cassettes which move with the print head as illustrated in FIG. 1A to quadruple the ribbon capacity requires adding as much as one inch (1") to the ribbon cassette footprint height and one half inch (0.5") to the footprint width such as demonstrated in FIG. 1A. This results in an increase in volume of forty-two percent (42%) in the resultant size target copier/printer apparatus as best shown in FIG. 2B. The cassette according to the present invention allows for growth without impact on the overall size of the target printer/copier apparatus (FIG. 1C).
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved compact copier or printer having thermal transfer printing capabilities with an easily replaceable ribbon supply cartridge.
It is another object of the present invention to provide a drive system adapted for use with the ribbon supply cartridge.
It is still another object of the present invention to provide a method of operating the drive system in conjunction with the replaceable ribbon supply cartridge for efficient use of the thermal ribbon.
Another object of the present invention is to enhance the thermal transfer printing process by providing a mechanical separating member downstream of a moving thermal printing head selectively engaging spent portions of the transfer element for separating the element from the receiver sheet.
Another object of the present invention is to separate the spent thermal transfer medium downstream of the moving thermal printing head on either the advance or return excursion of the head across the copy sheet to be coincident with the printing operation.
Yet another object of the present invention is to provide a combination brake element and drive element for control of dispensing new ribbon and making up of spent ribbon by appropriately applying a resistive force or a driving force to either the supply spool having a quantity of thermal ribbon thereon and a take-up spool connected to the other end of the ribbon.
These and other objects of the present invention are achieved in one embodiment by providing a pivotable stripper bar member on a thermal print head printing on an advance stroke in a portable copier or printer. The stripper bar selectively engages the spent thermal ribbon downstream of the print head for peeling the transfer element from the receiver sheet at a predetermined angle off-normal with respect to the receiver sheet plane at an appropriate time following the application of heat to the transfer element.
In another embodiment, a fixed stripper roller is provided on the thermal print head printing on the return stroke in a portable copier/printer.
The print head is connected to the drive system of the present invention for coordinating the supply of thermal ribbon to the print head with the position of the print head. The drive system also coordinates the supply of ribbon fed to the print head according to the extent of the printed matter on an original document in the portable copier.
The drive system includes a pivotable member for selectively applying an anti-rotational frictional force to a supply spool and a take-up spool in the replaceable ribbon supply cartridge. The pivotable member also selectively applies a spool driving force for taking up slack on either the supply or the take-up spool in the replacement ribbon supply cartridge.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the present invention, reference is made to the accompanying drawings wherein like reference numerals have been used for like or similar parts in several Figures and wherein:
FIGS. 1A, 1B and 1C are illustrations of a prior art ribbon cassette, printer apparatus for use with the cassette of FIG. 1A and a cassette according to the teachings of the invention in a printer apparatus respectively;
FIGS. 2A, 2B, and 2C are isometric views illustrating the general operation of a compact copier of the type the present invention is ideally applied;
FIG. 3 is an isometric view of the compact scanner of FIGS. 2A-2C in partial cutaway with the top cover removed;
FIG. 4 is an enlarged sectional view illustrating the elements of a typical scanning and printing carriage of the type the present invention is ideally applied;
FIG. 5 is a partial cross sectional view of the compact scanner taken along line 5--5 of FIG. 3 with the scanning carriage at home position and with a replaceable ribbon cassette installed;
FIGS. 6A and 6B illustrate the operation of the ribbon cassette of FIG. 5 and a drive system, therefor, respectively as the scanning carriage advances in preparation of a copy operation;
FIGS. 7A and 7B illustrate the operation of the ribbon cassette and drive system respectively as the scanning carriage advances and dispenses new ribbon while printing;
FIGS. 8A and 8B illustrate the operation of the ribbon cassette and drive systems respectively as the scanning carriage partially retracts back toward home position of FIG. 5;
FIGS. 9A and 9B illustrate the operation of the ribbon cassette and drive system respectively as the scanning carriage completes its movement toward home position;
FIGS. 10A-10F schematically illustrate a method of printer ribbon dispensing control corresponding to the printing operation illustrated in FIGS. 6-9;
FIG. 11 is a plan X-ray view of a second preferred embodiment of the ribbon cassette housing disposed in an apparatus printing on the advancing stroke of the print head;
FIG. 12 is a plan X-ray view of a third preferred embodiment of the ribbon cassette housing of FIG. 11 disposed in an apparatus printing on the return stroke of the print head;
FIG. 13 is a perspective view in partial phantom of another preferred embodiment of the ribbon cassette housing for dual large spool capacities; and,
FIG. 14 is a plan view in partial phantom of a drive system for use with the ribbon cassette housing of FIG. 13.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIGS. 2A, 2B, and 2C a general overview of the first preferred embodiment of the present invention used in a compact scanner is provided. The scanner is generally illustrated as comprising a frame assembly 15 which may have a maintenance station 12 at one end and a top cover 11 pivotally mounted to the frame assembly. To make a copy of document 14 the top cover is rotated to the open position as shown in FIG. 2A, a blank copy sheet 13 is inserted at the entrance of the copy sheet transport path and the document 14 is inserted against a registration stop member in the top cover after which the top cover is closed (FIG. 2B), The copying sequence begins by scanning carriage scanning a band of information across the document using a translatable. During the scanning operation, the document and copy paper are both held in a fixed position and the image on the document is digitized by an input digitizing system. In the preferred embodiment, a digital image is essentially simultaneously printed by a printing system on the copy sheet while the corresponding section of the original is being scanned. Subsequently, the document is indexed to the right and the copy sheet is indexed to the left (FIG. 2C) no enable the scanning carriage to scan a second band of information across the document. The distance of the longitudinal indexing of both the document and copy sheet is the width of the band of information across the document.
With additional reference to FIGS. 3 and 4 of the drawings there is shown a combined input scanner and output scanner designated generally by reference number 10. The scanner 10 includes a frame assembly 15 composed of a base unit 18, rails 19 within which a scanning carriage 20 is transported during its scanning path. When not in scanning operation the scanning carriage 20 is parked in the maintenance station 12 (FIG. 2A) to facilitate one or more of the following functions; clean the head, humidify the head; repair the head and change the ribbon cassette. This position will hereinafter be referred to as the home position.
The scanning carriage 20 includes a reading head 17 and a thermal printing head 25 mounted on a shared frame 52. The reading head comprises a contact image sensor, (CIS) 56, including an array of light emitting diodes 21 mounted to frame 57 for illuminating a document 14 adjacent a glass platen 54, an image of which is reflected through a lens 23 such as a Selfoc lens, to an input sensor chip 26 having an array of photosites for activation by the reflected radiation which is converted to electrical signals or pixels which are processed by an application specific integrated circuit (ASIC) 27 and subsequently transmitted to the printing head 25. The printing head is a thermal print head (TPH) 25 printing by heating ink impregnated in a ribbon 58 as described above and best illustrated in FIG. 4. Typically, the thermal print head comprises an array of heater elements or resistors 53, which when actuated, heat, to form pixels by melting a small portion of ink on ribbon 58 and pressing it into plain paper 13, essentially simultaneously in response to the image read by the reading head. During the operation the scanning carriage scans a document which is in an image plane and prints on the copy sheet which is in a parallel printing plane.
It will be understood that while reference has been made to reading heads and printing heads that the present invention encompasses in a generic sense solid state devices with input reading elements and solid state devices with output printing elements. It will also be understood that the number of scanning elements or sensors that comprise the image reading head 17 determine the initial scanning resolution while the number of heating elements 53 that comprise the printing head 25 determine the resolution of the image copy. Generally, However, the number of input scanning elements equals the number of output printing elements. Usually, the sensor chip has 384 photosites at 400 per inch or 16 per millimeter and the thermal print head also has 384 heater elements at 400 per inch or 16 per millimeter.
Both the reading head and the printing head are secured for movement on scanning carriage 20 which may be mounted for unidirectional scanning movement in a scanning path along the length of the frame assembly by means of scan stepper motor 32 through lead screw 31 to move the scanning carriage on the rails 19. The reading and printing heads are separated on the scanning carriage 20 by a gap 22 adapted to loosely receive the ribbon 58 therethrough.
As the motor rotates the lead screw, the grooves 40 in the lead screw engage threads (not shown) on the interior of the scan carriage to translate the read/write carriage along the lead screw. This motion pulls the ribbon 58 off a spool and through the gap 22. The pitch on the lead screw is selected, such that, each pulse or every second, third or fourth pulse, of the stepper motor corresponds to one pixel width or one 1/400th inch of carriage motion. This enables the same clock pulse generator used to drive the stepper motor to be used to trigger the read/write systems on the scanning carriage. Alternatively, a D.C. motor may be used to actuate the lead screw and together with an encoder wheel generate a signal which is used to trigger the read and/or write functions.
Following a scanning run in either direction across the length of the frame assembly (printing on advancing stroke or returning stroke), the document and the copy sheet are each indexed through the scanner in opposite directions a distance equal to the width of the band of information on the document scanned by the reading head which is the same width as the width of the band of information printed on the copy sheet by the thermal printing head. This width can be any width from a minimum of a single pixel line to a maximum of the width of the entire document in practical terms, however, in order to minimize the size and the cost of the read and write components, the width of the band is of the order of a fraction of an inch to several inches wide. The preferred method for achieving this alternating scanning/printing and sheet indexing is illustrated with further reference to FIG. 3 in conjunction with FIGS. 5-10 wherein an indexing means is provided comprising rotatable drive rolls 35a, b, c and d mounted on drive roll shafts 36a and 36b forming feeding nips for a document with document feed idler rolls contained within the top cover 11 of the scanner. The term "synchronously driven" is intended to define only that the shafts 36 are synchronized to each other. The drive rolls 35a, b, c and d also form feeding nips for a copy sheet with the copy sheet idler rolls 46 in the copy sheet transport path.
With the read/write carriage in the home position, the thermal printing head 25, as well as the reading head 17, is exposed for normal maintenance and repairs and also for convenient ribbon replacement. According to the preferred embodiment of the instant invention, the ribbon 58 is housed within a portable consumer replaceable ribbon cassette apparatus attachable to the copier 10 near the maintenance station 12 using any suitable clips, clamps, hooks or the like. As best shown in FIG. 5, the ribbon cassette 60 includes a housing 62 formed of a rigid lightweight, but durable material such as plastic. The housing 62 includes a generally planar surface adapted to receive a pair of ribbon spools thereon. A supply spool 64 is initially loaded with a quantity of ribbon 58 thereon. The take-up spool 66 is initially empty but connected to a first end of the ribbon 58. Each of the spools 64, 66 are freely rotatable within the housing 60 and adapted to engage a cassette drive system to be described in detail below. In the preferred embodiment, each of the spools 64 and 66 include axle portions extending through the housing 60 and connected to circular members outside of the housing.
With continued reference to FIG. 5, the ribbon cassette 60 includes a ribbon presentation element 70 for convenient threading of the ribbon 58 between the thermal printing head 25 and the reading head 17 through the gap This is especially useful during ribbon cassette replacement. The ribbon presentation element 70 includes a first pair of ribbon guides 72 positioned on the cassette housing and engageable with corresponding members (not shown) on the copier 10 to ensure that the ribbon 58 is properly registered in the gap 22 when the cassette 60 is installed with the scanning carriage at the home position. An auxiliary guide roller 74 is positioned on the housing to prevent the ribbon 58 from snagging on or otherwise contacting the interface between the ribbon presentation element and the housing walls.
With continued particular reference to FIG. 5, the scanning carriage 20 of the compact scanner includes a pivotable stripper bar 80 attached to the scanning carriage 20 at a first pivot point 82. The stripper bar 80 includes a first upper extension member 84 connected to a second lower extension member 86. The second lower extension member 86 is joined on its end by a stripper roller 88 which engages the ribbon 58 during the printing operation in a manner to be discussed below. In general, both the first extension member 84 and the second extension member 86 lie in a direction substantially corresponding to the direction of movement of the scanning carriage 20. On the other hand, the first pivot point 82 and the stripper roller 88 extend substantially perpendicular with the direction of movement of the scanning carriage 20 or into the page as viewed in the FIGURE. A general "L" shape is thereby formed. The stripper roller 88 is free to rotate so as not to score, tear or otherwise destroy the ribbon during the printing operation.
With the read/write carriage in the home position illustrated in FIG. 5, the stepper motor 32 rotates the lead screw 31, which translates the carriage 20 in an imaging sweep across the copier frame 15. FIGS. 6A and 6B illustrate the operation of the stripper bar 80 and the drive system 90 at the beginning of the aforementioned imaging sweep. More particularly, and with reference first to FIG. 6A, the scanning carriage 20 is illustrated in a position offset somewhat from the home position illustrated in FIG. 5. As illustrated in FIG. 6A, fresh ribbon 58 is unrolled from the supply spool 64 due to the movement of the scanning carriage. The ribbon 58 is effectively pulled through the gap 22 of the scanning carriage. At the position illustrated in FIG. 6A, the stripper bar 80 engages a boss 28 on the frame assembly of the copier apparatus. The boss 28 is aligned with at least one of the first pair of roller guides 72 of the ribbon cassette 60. As the scanning carriage 20 moves in the scanning direction A, the extension members 84 of the stripper bar 80 engage the boss 28 urging the stripper bar into pivotal motion generally in the direction B. FIG. 7A illustrates the scanning carriage 20 well into the imaging sweep wherein the stripper roller 88, held by the bail second extension member 86, effectively strips or peels the spent ribbon from the thermal printing head 25 during the imaging sweep.
With reference to FIG. 6B, the drive system 90 of the preferred embodiment is illustrated. The drive system includes a supply spool brake member 92 and a take-up spool brake member 96. The supply spool brake member 92 selectively engages a supply spool circular member 94 extending from the ribbon cassette and connected to the supply spool 64 through the housing 62 with a supply spool axle. Similarly, the take-up spool brake member 96 selectively engages a take-up spool circular member 94 which is connected to the take-up spool 66 through a take-up spool axle 93. The supply spool brake member 92 and the take-up spool brake member 96 are connected to a control member 100 which is pivotable about a pivot point 102. A small D.C. or stepper motor 110 is attached to the control member 100 and includes a first drive wheel 112 engaging a raceway 114. The raceway includes a first ramped surface 120 near the supply spool circular member 94 and a second ramped surface 122 adjacent the take-up spool circular member 98. In the preferred embodiment, the raceway 114 is only semi-rigid to permit some flexing thereof in order to accommodate pivotal motion of the control member 100 and drive wheel 112. Materials which exhibit the resilient characteristics similar to piano wire fixed to the housing on both ends work well for the raceway 114. This resilient raceway provides the force to urge the motor shaft in contact with the circular member 94 and also to urge the break member 96 into contact with the circular member 98.
In the position illustrated in FIG. 6B which corresponds to the position of the printing operation illustrated in FIG. 6A, the electric motor 110 is in an OFF or brake state. The shaft of the motor 110 serves as a small drive wheel 112, enlarged in the Figures for ease of reference and discussion, which engages both the first surface 120 and the supply spool circular member 94. In this position, the supply spool 64 is rotatable against the frictional force between the drive wheel 110 and the supply spool circular member 94. On the other hand, the take-up spool circular member 98 is engaged with the take-up spool brake member 96 due to the toggle position of the control member 100 and the urging force provided by the resilient raceway 120. Accordingly, as the scanning carriage 20 advances in the scanning direction A, the ribbon 58 is pulled from the supply spool 64 against the frictional force between the drive wheel 112 and the supply spool circular member 94. The take-up spool is effectively locked due to the engagement of the take-up spool brake member 96 with the take-up spool circular member 98.
FIGS. 7A and 7B illustrate the operation and function of the ribbon cassette 60 and the drive system 90 during the scanning process, As illustrated, the reading head 17 reads information from the document 14 while the thermal printing head 25 simultaneously prints the same information onto the copy sheet 13 as the carriage moves in the scanning direction A in a manner described above. Further, as the scanning carriage progresses, the stripper roller 88 effectively peels away the unused portions of the thermal ribbon 58 downstream of the printing process. The angle between the first extension member 84 and the second extension member 86 as well as the length thereof determine the sheering angle between the thermal ribbon under the print head 25 and the spent ribbon between the print head and the stripper roller. This prevents the thermal ribbon from sticking or otherwise adhering to the copy sheet 13. As shown in the Figures, the supply spool 64 as well as the supply spool circular member 94 rotate while the take-up spool 66 and the take-up circular member 98 are held stationary.
After The original document is scanned and the copy completed, the scanning carriage 20 reverses direction and moves toward either the home position (FIG. 5) or the ready position (FIG. 7A). Before the scanning carriage 20 commences movement in the returning direction C, the electric motor 110 is powered rotating the drive wheel lit in the counter clockwise direction marked in FIG. 8B. The relative coefficient of friction between the first surface 120, the drive wheel 112, and the supply spool circular member 94 are selected such that the supply spool is effectively driven in the rotational clockwise direction illustrated in FIG. 8A. In addition, the take-up spool brake member 96 is positively inserted into engagement with the take-up spool circular member 98 to effectively hold fixed the take-up spool 66. Accordingly, while the scanning head traverses in the reversing direction C, portions of the ribbon 58 extending from the cassette 60 are rewound onto the supply spool 64. However, at a predetermined position along the excursion of the scanning carriage 20, the electric motor 110 is energized in an opposite direction to rotate the drive wheel 112 clockwise as illustrated in FIG. 9B. The reversing rotation of the drive wheel 112 causes the control member 100 to toggle about the pivot 102 to the position illustrated in FIG. 9B. In this position, the supply spool brake member 92 engages the supply spool circular member 94 to effectively hold fixed the supply spool 64 preventing its rotation. Conversely, the take-up spool 66 is urged into counterclockwise rotation as illustrated in FIG. 9A through the interaction of the drive wheel 112 with the take-up spool circular member 98. As illustrated in FIGS. 9A and 9B, the spent ribbon extending from the cassette 60 is wound onto the take-up spool 66 for the remainder of the movement of the scanning carriage 20 and the reversing direction C.
With reference now to FIGS. 10A-F, a method for effective ribbon conservation and utilization according to the present invention will be described in detail using simplified representations of the scanner, ribbon cassette and brake members. Although the method described finds particular application in apparatus which print on the advancing stroke, only simple modification is required in the method steps for adaptation to apparatus which print on the print head return stroke.
FIG. 10A illustrates the thermal printing head 25 at the extreme end of travel in the scanning direction A after completing a copy onto a copy sheet 13 according to the procedures described above. As illustrated in FIG. 10A, the copy sheet 13 has a width w. The length of ribbon 58 extending from the supply spool 64 to the thermal printing head 25 is unused. However, a portion of the ribbon 58 extending between the take-up spool 66 and a thermal printing head 25 is used. The used portion is hereinafter schematically illustrated using a series of "x" s. The distance between the leading edge (printing head at ready position, FIG. 7A) of the copy sheet 13 and the home position (printing head at the maintenance stations FIG. 5) is schematically represented as the distance d. As indicated above, during the scanning/printing operation, the supply spool 64 is permitted to rotate as illustrated in FIG. 10A while the take-up spool 66 is held fixed using the take-up spool brake member 96.
With reference now to FIG. 10B, the supply spool 64 is urged to rotational movement through the interaction of the motor 110 and the drive wheel 112 on the supply wheel circular member 94 such as described above in connection with FIGS. 8A and 8B. The take-up spool 66 is held fixed by the take-up spool brake member 96. During a first portion of the movement of the scanning carriage in the reversing direction C, a portion of the ribbon 58 is rewound onto the supply spool 64. Also, as schematically represented in FIG. 10B, a used portion of the ribbon 58 is rewound into the region between the thermal printing head 25 and the supply spool 64. Rewinding in this manner is continued until the thermal printing head 25 reaches a position illustrated in FIG. 10C.
FIG. 10C illustrates the thermal printing head at a position midpoint between the extreme edges of the copy sheet 13. That is, the thermal printing head 25 translates in the reversing direction C, a distance w/2. At this position, the motor 112 is reversed in a manner described above FIG. 9B) This effectively clamps the supply spool 64 using the supply spool brake member 92 and engaging the supply spool circular member 94. The clockwise rotation of the drive wheel 112 urges the take-up spool into rotational movement to wind that portion of the ribbon 52 between the thermal printing head 25 and the take-up spool thereon. This operation continues until the thermal printing head reaches the ready position illustrated in FIG. 10D.
As indicated above, FIG. 10D schematically illustrates the thermal printing head 25 in the ready position wherein only new portions of ribbon 58 exist between the thermal printing head 2B and the supply spool 64. All of the spent ribbon is positioned between the thermal printing head 25 and the take-up spool 66. The ready position is also illustrated in FIG. 5. In this position, both the document 14 and the copy sheet 13 are advanced the width of the scanning band described above. There is no need for the thermal printing head to retract any further along the reversing direction C. On the contrary, once the copy sheet 13 and the document 14 are advanced, the predetermined scanned width amount, the thermal printing head moves once again in the scanning direction A illustrated in FIGS. 10A, 6A and 7A. Thus, the steps illustrated in the sequence from FIG. 10A through 10D are repeated until the entire document is scanned and the copy sheet is completed.
After the last image band is scanned and printed onto the copy sheet, the thermal printing head 25 is returned to the home position illustrated in FIG. 5 and 10F. In this special case of movement in the reversing direction C, the thermal printing head and drive system function according to the sequence illustrated in FIGS. 10A, 10B, 10E and 10F. More particularly, the supply spool 64 is urged into rotational movement as illustrated in FIG. 10B until such time as the thermal printing head reaches a position such as illustrated in FIG. 10E. In this position, the amount of spent ribbon between the thermal printing head 25 and the supply spool 64 is given as a=(w/2-d) the amount of spent ribbon between the thermal printing head 25 and the take-up spool 66 is given as b=(w/2+d).
After the thermal printing head 25 reaches the position illustrated in FIG. 10E, the motor 110 is reversed in a manner described above to toggle the control member 100 about the pivot 102 urging the take-up spool into take-up rotation and simultaneously clamping the supply spool 64. When the thermal printing head 25 reaches the home position illustrated in FIG. 10F, the amount of spent ribbon extending between the thermal printing head 25 and the supply spool 64 is d. The amount of spent ribbon between the thermal printing head 25 and the take-up spool 66 is w. In this manner, no ribbon is wasted between separate copy sheets. More particularly, for the next copy sheet, the thermal printing head advances in the scanning direction A unrolling a length d of spent ribbon 58 from the supply spool 64 until the thermal printing head 25 reaches the ready position illustrated in FIGS. 7A and 10D. At the ready position, only fresh ribbon 58 exists between the thermal printing head 25 and the supply spool 64.
The above scheme is easily modifiable to adjust the point of motor reversal to save ribbon on the latter portion of scans where there is no image on the document 14. The extra portion of unused new ribbon is recognized by the scanning head 17 during the scanning operation and the moment of motor reversal is thereby adjusted on the fly. This ensures than the leading edge, or beginning end, of unused ribbon registers with the thermal printing head 25 on the paper edge at the ready position (FIGS. 7A and 10D). A simple adjustment is similarly possible for those portions of the printing operation when the printing head moves to the home position (FIGS. 5 and 10F). Lastly, for multi-strike ribbon applications of this ribbon conservation method, the motor reversal is adjustable over the range of returning motion C in order that a portion of the used ribbon is rewound onto the supply spool 64.
This process is readily adaptable in color printing applications to ensure the proper registration of sequentially presented colored ribbon segments such as cyan, magenta, yellow and black. The color embodiment of the instant invention contemplates the use of a sensor for detecting the spaces between color segments of the ribbon and appropriately controls the rewind sequencing of the take-up and supply spools. This is performed in a manner such that the appropriate spool is rewound to suitably present colored ribbon segments for sequentially repeated scans over the same segment of the receiver sheet. One method is to detect the transparent area of the ribbon between the color portion using the sensor, then overprinting a single strip by each color (e.g. four scans) in turn before the paper sheet is advanced to print the next strip using four scans.
With reference now to FIG. 11, the ribbon cassette according to the present invention is illustrated in an alternative preferred embodiment as a housing containing two spools which are offset from the scanning direction of the print head or "stepped" instead of being disposed on line therewith as illustrated in FIG. 5. For ease of illustration and comprehension of this alternative, like components are identified by like numerals with a primed suffix (') and new components are identified by new numerals.
As indicated above, the preferred environment or application for the instant invention is in a portable copier apparatus. However, the present invention finds application as well in portable printer devices which essentially comprise the same overall hardware of the copier described above but for the absence of the reading head and imaging portions of the copier. Rather, portable printing apparatus merely receive signals from an associated computer device or the like for converting those signals into readable information on a printed page. Accordingly, as illustrated in FIG. 11, the alternative ribbon cassette 60' engages only the thermal printing head 25' without the need for threading through the gap 22 (FIG. 5) associated with copiers using a reading head 17 preceding the thermal printing head 25' for forming copies on the advancing stroke of the scanning carriage 20.
Since no reading head 17 is necessary in a printer application, the stripper bar 80' is pivotally attached directly to the thermal printing head 25'. As in the first preferred embodiment described above, the stripper bar 80' includes downwardly extending extension member 86' which lies in a plane parallel with the page as viewed in the Figure and a stripper roller 88' which lies in a plane perpendicular to or "into" the page of the Figure. Overall, the stripper bar 80' operates substantially as described above for peeling the ribbon 58' from the copy sheet 13' downstream of the printing operation on the advancing stroke of the thermal printing head 25' in a direction Y.
The supply spool 64' and take-up spool 66' are arranged in a manner such that their respective flanges for supporting the ribbon 58' overlap or slidably engage so as to conserve space within the ribbon cassette 60'. Each of the supply and take-up spools rotate about points P1 and P2, respectively. The points P1 and P2 define a line n which is skewed or obtuse with respect to the direction of thermal print head movement Y.
With reference next to FIG. 12, the ribbon cassette 60' of FIG. 11 is illustrated in a printer apparatus which operates to print on the return stroke of the print head instead of the advancing stroke. For ease of illustration and comprehension of this alternative, like components are identified by like numerals with a double primed suffix (") and new components are identified by new numerals.
In the printer apparatus illustrated in this Figure, the thermal printing head 25'" creates readable images on the copy sheet 13" while on the returning stroke which is in the direction Z in the Figure. The stripper bar 80" is attached to the print head and in this case is essentially a stripper roller 88" which lies in a plane perpendicular to or "into" the page of the Figure. Thus, the stripper roller 88" peels the ribbon 58" from the copy sheet 13" downstream of the print operation which is in the direction Z.
Turning now to FIGS. 13 and 14, an alternative embodiment of the ribbon cassette is illustrated as comprising two side by side spools instead of the spool arrangement illustrated in FIGS. 5, 11 and 12. For ease of illustration and comprehension once again, like components are identified by like numerals with a triple primed suffix ('") and new components are identified by new numerals.
The general arrangement of the supply spool 64'" and the take-up spool 66'" is best illustrated in FIG. 13. As can be seen in that Figure, each of the spools are co-axial in this preferred alternative embodiment. However, they need not be coaxially but only offset from one another in a direction F perpendicular to the plane of the page of that Figure which is perpendicular to the axis of the return stroke Z of the thermal printing head 25'". As illustrated in FIG. 13, the thermal printing head 25'" is generally aligned with the supply spool 64'" such that the ribbon 58'" peels directly therefrom and across the thermal printing head 25'" and stripper roller 88'". The take-up spool 66'", however, is offset from both the thermal printing head 25'" and the supply spool 64'" in order to make the most efficient use of the cross sectional footprint size of the cassette 60'" while maintaining maximum ribbon length.
A diverter roller mechanism 130 includes a first and second set of rollers 132, 134 respectively for laterally shifting the ribbon 58'" from the plane of the supply spool 64'" to that of the take-up spool 66'". The first diverter roller 112 shifts the ribbon slightly while the second diverter roller 114 further shifts the ribbon 58'" towards the direction F where it is readily squarely received onto the take-up spool 66'". Although this Figure illustrates only one divertes roller mechanism 118, a pair may be used in instances where three spaced apart parallel planes are defined by the supply spool 64'", the thermal printing head 25'" and the take-up spool 64'". In that case, a first diverter roller mechanism (not shown) Shifts the ribbon from the plane of the supply spool 64'" to that of the thermal printing head 25'" The second diverter roller mechanism 110 further shifts the ribbon from the plane of the thermal printing head 25'" into that of the take-up spool 66'" for ready threading thereon.
With reference now to FIG. 14, the drive system 90'" of the second preferred ribbon cassette embodiment is illustrated. The drive system includes a supply spool brake member 92'" and a take-up spool brake member 96'". A set of gears 140, 142 and 144 couple the ribbon supply spool to the ribbon take-up spool. The supply spool brake member 92'" selectively engages a supply spool circular member 94'" extending from the ribbon cassette and connected to the supply spool 64'" through the housing 62'" with a supply spool axle. Similarly, the take-up spool brake member 96'" selectively engages a take-up spool circular member 94'" which is connected to the take-up spool 66'" through a take-up spool axle 93'". The supply spool brake member 92'" and the take-up spool brake member 96'" are connected to a control member 100'" which is pivotable about a pivot point 102'". A small D.C. or stepper motor 110'" is attached to the control member 100'" and includes a first drive wheel 112'" engaging a raceway 114'". The raceway includes a first ramped surface 120'" near the supply spool circular member 94'" and a second ramped surface 122'" adjacent the take-up spool circular member 98'". In the preferred embodiment, the raceway 114'" is only semi-rigid to permit some flexing thereof in order to accommodate pivotal motion of the control member 100'" and drive wheel 112'". Materials which exhibit the resilient characteristics similar to piano wire fixed to the housing on both ends work well for the raceway 114'".
In the position illustrated in FIG. 14 which corresponds to the position of the printing operation, the electric motor 110'" is in an OFF or brake state. The drive wheel 110'" is engaged with both the first surface 120'" and the supply spool circular member 94'". In this position, the supply spool 64'" is rotatable against the frictional force between the drive wheel 110'" and the supply spool circular member 94'". On the other hand, the take-up spool circular member 98'" is engaged with the take-up spool brake member 96'" due to the toggle position of the control member 100'". Accordingly, as the scanning carriage 20'" advances in the scanning direction A, the ribbon 58'" is pulled from the supply spool 64'" against the frictional force between the drive wheel 112'" and the supply spool circular member 94'" The take-up spool is effectively locked due to the engagement of the take-up spool brake member 96'" with the take-up spool circular member 98'".
While the invention has been described with reference to specific embodiments thereof, it would be apparent to those skilled in the art that many alternatives, modifications and variations may be made. For example, while the invention has been illustrated with respect to having a scanner having a both a reading head and a thermal printing head, it would be understood that it has application to stand alone scanners and printers including impact type stand along printers. Accordingly, it is intended to embrace all such alternatives and modifications as may fall in the spirit of the appended claims. | A ribbon cartridge and drive system for use in printers, typewriters, copiers or the like in which a supply spool and a take-up spool are enclosed in a housing with each spool extending from the housing for selective alternate engagement with a drive member connected to a brake member, both being coordinated with the movement of a printing head. A stripper bar peels the ribbon from a copy sheet downstream of printing head movement. The drive system cooperates with the printing head whereby a method of ribbon conservation is realized. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
The present application claims priority to and is a divisional of parent application Ser. No. 10/028,084 filed Dec. 21, 2001, now U.S. Pat. No. 6,754,104 and which parent application is a continuation-in-part and claims priority to each of the following applications, all of which were filed Jun. 22, 2000 and are hereby incorporated by reference as if fully set forth herein:
Ser. No. 09/603,101 entitled “A CMOS-PROCESS COMPATIBLE, TUNABLE NDR (NEGATIVE DIFFERENTIAL RESISTANCE) DEVICE AND METHOD OF OPERATING SAME”; now U.S. Pat. No. 6,512,274; and
Ser. No. 09/603,102 entitled“CHARGE TRAPPING DEVICE AND METHOD FOR IMPLEMENTING A TRANSISTOR HAVING A NEGATIVE DIFFERENTIAL RESISTANCE MODE”; now U.S. Pat. No. 6,479,862; and
Ser. No. 09/602,658 entitled “CMOS COMPATIBLE PROCESS FOR MAKING A TUNABLE NEGATIVE DIFFERENTIAL RESISTANCE (NDR) DEVICE” now U.S. Pat. No. 6,596,617
The present application is also related to the following applications, all of which were filed simultaneously with the above parent application and which are hereby incorporated by reference as if fully set forth herein:
An application Ser. No. 10/029,077 entitled “MEMORY CELL UTILIZING NEGATIVE DIFFERENTIAL RESISTANCE FIELD-EFFECT TRANSISTORS”; now U.S. Pat. No. 6,724,655;
An application Ser. No. 10/028,394 entitled “DUAL MODE FET & LOGIC CIRCUIT HAVING NEGATIVE DIFFERENTIAL RESISTANCE MODE”; now U.S. Pat. No. 6,518,589;
An application Ser. No. 10/028,089 entitled “CHARGE PUMP FOR NEGATIVE DIFFERENTIAL RESISTANCE TRANSISTOR” now U.S. Pat. No. 6,594,193;
An application Ser. no. 10/028,085 entitled “IMPROVED NEGATIVE DIFFERENTIAL RESISTANCE FIELD EFFECT TRANSISTOR (NDR-FET) & CIRCUITS USING THE SAME”; now U.S. Pat. No. 6,559,470.
FIELD OF THE INVENTION
This invention provides a semiconductor device, having a variety of applications such as a bistable latch or a logic circuit, in which one or more insulated-gate field-effect transistor (IGFET) elements and one or more negative differential resistance (NDR) field-effect transistor elements are combined and formed on a common substrate. The present invention is applicable to a wide range of semiconductor integrated circuits, particularly for high-density memory and logic applications.
BACKGROUND OF THE INVENTION
Devices that exhibit a negative differential resistance (NDR) characteristic, such that two stable voltage states exist for a given current level have long been sought after in the history of semiconductor devices. A new type of CMOS compatible, NDR capable FET is described in the aforementioned applications to King et al. referenced above. The advantages of such device are well set out in such materials, and are not repeated here.
NDR devices and their applications are further discussed in a number of references, including the following that are hereby incorporated by reference and identified by bracketed numbers [ ]where appropriate below:
[1] P. Mazumder, S. Kulkarni, M. Bhattacharya, J. P. Sun and G. I. Haddad, “Digital Circuit Applications of Resonant Tunneling Devices,” Proceedings of the IEEE , Vol. 86, No. 4, pp. 664–686,1998.
[2] W. Takao, U.S. Pat. No. 5,773,996, “Multiple-valued logic circuit” (issued Jun. 30, 1998)
[3] Y. Nakasha and Y. Watanabe, U.S. Pat. No. 5,390,145, “Resonance tunnel diode memory” (issued Feb. 14, 1995)
[4] J. P. A. Van Der Wagt, “Tunneling-Based SRAM,” Proceedings of the IEEE , Vol. 87, No. 4, pp. 571–595, 1999.
[5] R. H. Mathews, J. P. Sage, T. C. L. G. Sollner, S. D. Calawa, C.-L. Chen, L. J. Mahoney, P. A. Maki and K. M Molvar, “A New RTD-FET Logic Family,” Proceedings of the IEEE , Vol. 87, No. 4, pp. 596–605, 1999.
[6] H. J. De Los Santos, U.S. Pat. No. 5,883,549, “Bipolar junction transistor (BJT)-resonant tunneling diode (RTD) oscillator circuit and method (issued Mar. 16, 1999)
[7] S. L. Rommel, T. E. Dillon, M. W. Dashiell, H. Feng, J. Kolodzey, P. R. Berger, P. E. Thompson, K. D. Hobart, R. Lake, A. C. Seabaugh, G. I(limeck and D. K. Blanks, “Room temperature operation of epitaxially grown Si/Si 0.5 Ge 0.5 /Si resonant interband tunneling diodes,” Applied Physics Letters , Vol. 73, No. 15, pp. 2191–2193, 1998.
[8] S. J. Koester, K. Ismail, K. Y. Lee and J. O. Chu, “Negative differential conductance in lateral double-barrier transistors fabricated in strained Si quantum wells,” Applied Physics Letters , Vol. 70, No. 18, pp. 2422–2424, 1997.
[9] G. I. Haddad, U. K. Reddy, J. P. Sun and R. K. Mains, “The bound-state resonant tunneling transistor (BSRTf): Fabrication, d.c. I–V characteristics, and high-frequency properties,” Superlattices and Microstructures , Vol. 7, No. 4, p. 369, 1990.
[10] Kulkanni et. al., U.S. Pat. No. 5,903,170, “Digital Logic Design Using Negative Differential Resistance Diodes and Field-Effect Transistors (issued May 11, 1999).
A wide range of circuit applications for NDR devices are proposed in the above references, including multiple-valued logic circuits [ 1 , 2 ], static memory (SRMM) cells [ 3 , 4 ], latches [ 5 ], and oscillators [ 6 ]. To date, technological obstacles have hindered the widespread use of NDR devices in conventional silicon-based integrated circuits (ICs). The most significant obstacle to large-scale commercialization has been the technological challenge of integrating high-performance NDR devices into a conventional IC fabrication process. The majority of NDR-based circuits require the use of transistors, so the monolithic integration of NDR devices with predominant complementary metal-oxide-semiconductor (CMOS) transistors is the ultimate goal for boosting circuit functionality and/or speed. Clearly, the development of a CMOS-compatible NDR device technology would constitute a break-through advancement in silicon-based IC technology. The integration of NDR devices with CMOS devices would provide a number of benefits including at least the following for logic and memory circuits:
1) reduced circuit complexity for implementing a given function; 2) lower-power operation; and 3) higher-speed operation.
Significant manufacturing cost savings could be achieved concomitantly, because more chips could be fabricated on a single silicon wafer without a significant increase in wafer-processing cost.
A tremendous amount of effort has been expended over the past several decades to research and develop silicon-based NDR devices in order to achieve compatibility with mainstream CMOS technology, because of the promise such devices hold for increasing IC performance and functionality. Efforts thus far have yielded NDR devices that require either prohibitively expensive process technology or extremely low operating temperatures which are impractical for high-volume applications. One such example in the prior art requires deposition of alternating layers of silicon and silicon-germanium alloy materials using molecular beam epitaxy (MBE) to achieve monolayer precision to fabricate the NDR device [ 7 ]. MBE is an expensive process which cannot be practically employed for high-volume production of semiconductor devices. Another example in the prior art requires the operation of a device at extremely low temperatures (1.4K) in order to achieve significant NDR characteristics [ 8 ]. This is impractical to implement for high-volume consumer electronics applications.
Three (or more) terminal devices are preferred as switching devices, because they allow for the conductivity between two terminals to be controlled by a voltage or current applied to a third terminal, an attractive feature for circuit design as it allows an extra degree of freedom and control in circuit designs. Three-terminal quantum devices which exhibit NDR characteristics such as the resonant tunneling transistor (RTT) [ 9 ] have been demonstrated; the performance of these devices has also been limited due to difficulties in fabrication, however. Some bipolar devices (such as SCRs) also can exhibit an NDR effect, but this is limited to embodiments where the effect is achieved with two different current levels. In other words, the current-vs.-voltage (I–V) curve of this type of device is not as useful because it does not provide two stable voltage states for a given current.
Accordingly, there exists a significant need for the monolithic integration of three-terminal NDR devices with conventional field-effect transistors by means of a single fabrication process flow.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide a semiconductor device having a variety of applications such as bistable latch or logic circuits through the combination of one or more insulated-gate field-effect transistor (GFET) elements and one or mote negative differential resistance field-effect transistor NDR-FEI) elements.
A second object of the present invention is to provide a practical method of manufacturing a semiconductor device utilizing a single fabrication process flow, so that an IGFET and an NDR-FET can be formed on a common substrate.
For achieving the first object, the invention provides a semiconductor device comprising an IGFET including a gate and source/drain electrodes, and an NDR-FET including gate and source/drain electrodes, wherein the IGFET and NDR-FET elements are formed on a common substrate, and one of the gate or source/drain electrodes of the IGFET element is electrically connected with one of the source/drain electrodes of the NDR-FET. Thusly, various types of circuits having a variety of functions can be attained through the combination of an IGFET and an NDR-FET.
In one aspect of this invention, the NDR-FET can utilize silicon as the semiconductor material. Thus, the NDR-FET and the IGFET can be fabricated on a common silicon substrate and hence a semiconductor device incorporating one or more NDR elements and one or more conventional field-effect transistor elements can be practically realized.
In another aspect of this invention, the IGFET can be an n-channel enhancement-mode transistor, with the gate electrode and the drain electrode of the IGFET semiconductor element short-circuited and connected to a power-supply terminal, the source electrode of the IGFET electrically connected together with the drain electrode of the NDR-FET to a control terminal, the source of the NDR-FET connected to a grounded or negatively biased terminal, and the gate electrode of the NDR-FET biased at a constant voltage. Thus, among plural intersections between the current-vs.-voltage (I–V) characteristic of the NDR-FET and the I–V characteristic of the IGFET semiconductor element, an intersection at which the gradients (obtained as a change in current in accordance with a change of the control terminal voltage) of the characteristics have different signs (positive, negative, or zero) is a stable operating point of the semiconductor device. Therefore, the semiconductor device can function as a bistable memory cell.
In another aspect of this invention, the IGFET can be an n-channel enhancement-mode transistor, with the source electrode connected to a grounded or negatively-biased terminal, the gate electrode and the drain electrode of the IGFET semiconductor element short-circuited and electrically connected together with the source of the NDR-FET to a control terminal, the drain electrode of the NDR-FET connected to a power-supply terminal, and the gate electrode of the NDR-FET biased at a constant voltage. Thus, among plural intersections between the I–V characteristic of the NDR-FET and the I–V characteristic of the IGFET semiconductor element, an intersection at which the gradients (obtained as a change in current in accordance with a change of the control terminal voltage) of the characteristics have different signs (positive, negative, or zero) is a stable operating point of the semiconductor device. Therefore, the semiconductor device can function as a bistable memory cell.
In another aspect of this invention, the IGFET can be an n-channel depletion-mode transistor, with the gate electrode and the source electrode of the IGFET semiconductor element short-circuited and the drain electrode connected to a power-supply terminal, the source electrode of the IGFET electrically connected together with the drain electrode of the NDR-FET to a control terminal, the source of the NDR-FET connected to a grounded or negatively biased terminal, and the gate electrode of the NDR-FET biased at a constant voltage. Thus, among plural intersections between the I–V characteristic of the NDR-FET and the I–V characteristic of the IGFET semiconductor element, an intersection at which the gradients (obtained as a change in current in accordance with a change of the control terminal voltage) of the characteristics have different signs (positive, negative, or zero) is a stable operating point of the semiconductor device. Therefore, the semiconductor device can function as a bistable memory cell.
In another aspect of this invention, the IGFET can be an n-channel depletion-mode transistor, with the gate electrode and the source electrode of the IGFET semiconductor element short-circuited and connected to a grounded or negatively-biased terminal, the drain electrode of the IGFET electrically connected together with the source of the NDR-FET to a control terminal, the drain electrode of the NDR-FET connected to a power-supply terminal, and the gate electrode of the NDR-FET biased at a constant voltage. Thus, among plural intersections between the I–V characteristic of the NDR-FET and the I–V characteristic of the IGFET semiconductor element, an intersection at which the gradients (obtained as a change in current in accordance with a change of the control terminal voltage) of the characteristics have different signs (positive, negative, or zero) is a stable operating point of the semiconductor device. Therefore, the semiconductor device can function as a bistable memory cell.
In another aspect of this invention, the IGFET can be an n-channel enhancement-mode transistor, with one of the source/drain electrodes of the IGFET semiconductor element connected to the source electrode of a first NDR-FET and also to the drain electrode of a second NDR-FET, the gate electrode of the IGFET connected to a first control terminal, the other one of the source/drain electrodes of the IGFET connected to a second control terminal, the drain electrode of the first NDR-FET connected to a power-supply terminal, the source electrode of the second NDR-FET connected to a grounded or negatively-biased terminal, and the gate electrodes of the NDR-FETs each biased at a constant voltage. Thus, among plural intersections between the I–V characteristic of the first NDR-FET and the I–V characteristic of the second NDR-FET, an intersection at which the gradients (obtained as a change in current in accordance with a change of the control terminal voltage) of the characteristics have different signs (positive, negative, or zero) is a stable operating point of the semiconductor device. Therefore, the semiconductor device can function as a bistable memory cell, with access to the data storage node provided via the IGFET.
For achieving the second object, the invention provides a method of manufacturing a semiconductor device including an IGFET semiconductor element having a gate electrode, a gate insulating film and a channel region and source/drain regions of semiconductor, and a NDR-FET having a gate electrode, a gate insulating film and a channel region and source/drain regions of semiconductor, wherein the IGFET and NDR-FET elements are formed on a common substrate, and at least one of the gate or source/drain electrodes of the IGFET element is electrically connected to one of the source/drain electrodes of the NDR-FET.
The method comprises the following steps: simultaneously forming electrically isolated “active” regions for the IGFET and NDR-FET elements in the surface of a semiconductor substrate; sequentially and separately adjusting the NDR-FET and IGFET channel dopant concentrations in the surface regions of the semiconductor substrate; forming the gate insulating films for the NDR-FET and IGFET elements by thermal oxidation and/or thin-film deposition; selectively forming charge traps in the gate insulating film or at the interface between the gate insulating film and the semiconductor channel of the NDR-FET element either by ion implantation and/or diffusion of an appropriate species or by depositing a charge-trapping layer either before or after part or all of the NDR-FET gate insulating film has been formed; forming contact holes in the source or drain region of the IGFET if needed; blanket depositing a gate-electrode material on the gate insulating films of the IGFET and the NDR-FET elements; simultaneously completing the fabrication of the IGFET and NDR-FET elements using conventional IC fabrication process steps to pattern the gate electrodes, dope the gate electrodes and form the source and drain electrodes, deposit passivation layer(s), and form interconnects.
In one aspect, the IGFET and NDR-FET may be fabricated side-by-side in the same active region, or “well.”
In another aspect, the semiconductor substrate is monocrystaliine silicon.
In another aspect, the semiconductor substrate is a silicon-on-insulator (monocrystalline silicon layer on top of an electrically insulating SiO 2 layer on top of a silicon wafer) substrate.
In another aspect, the channel dopant concentration in the NDR-FET may be substantially different from the channel dopant concentration in the IGFET.
In another aspect, a portion or all of the gate insulating film for the NDR-FET may be formed before the gate insulating film for the IGFET is formed.
In another aspect, the semiconductor substrate may contain one or more layers of silicon-germanium in either or both of the IGFET and NDR-FET active regions.
In another aspect, the thickness of the gate insulating film in the NDR-FET may be substantially different from the thickness of the gate insulating film in the IGFET.
In another aspect, formation of charge traps in the gate insulating film of the NDR-FET is facilitated by incorporating boron, which may be achieved by thermal oxidation of a boron-doped channel and/or thermal diffusion of boron from the channel into the gate insulating film.
In another aspect, charge traps are formed in the gate insulating film of the NDR-FET by depositing a layer of material, such as silicon or silicon-rich oxide, after a portion of the gate insulating film has been formed, and before the remaining portion of the gate insulating film is formed. The deposited layer may be continuous, in the form of a thin film, or it may be discontinuous, in the form of islands.
In another aspect, charge traps are formed in the gate insulating film of the NDR-FET by depositing a layer of material which contains a high density of charge traps, such as silicon-rich oxide, silicon oxynitride, silicon nitride, or high-permittivity dielectric, before the remaining portion of the gate insulating film is formed.
In another aspect, charge traps are formed in the gate insulating film of the NDR-FET by implantation of arsenic, phosphorus, fluorine, silicon, germanium, nitrogen, or metallic atoms.
In another aspect, a polycrystalline silicon (poly-Si) or polycrystalline silicon-germanium (poly-SiGe) film can be deposited as the gate-electrode material.
In another aspect, a metal or conductive metal-nitride or conductive metal-oxide or metal-silicide film can be deposited as the gate-electrode material.
In this manner, a semiconductor device comprising one or more IGFET elements and one or more NDR-FET elements can be manufactured on a common substrate utilizing a fabrication sequence consisting of conventional process steps. Accordingly, the manufacture of the semiconductor device can be eased and the manufacturing cost can be relatively low.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a circuit diagram of a bistable memory cell consisting of the combination of one enhancement-mode IGFET pull-up element and one NDR-FET pull-down element;
FIG. 2 is a plot of the current-vs.-voltage characteristic of the bistable memory cell of FIG. 1 ;
FIG. 3 is a circuit diagram of a bistable memory cell consisting of the combination of one NDR-FET pull-up element and one enhancement-mode IGFET pull-down element;
FIG. 4 is a plot of the current-vs.-voltage characteristic of the bistable memory cell of FIG. 3 ;
FIG. 5 is a circuit diagram of a bistable memory cell consisting of the combination of one depletion-mode IGFET pull-up element and one NDR-FET pull-down element;
FIG. 6 is a plot of the current-vs.-voltage characteristic of the bistable memory cell of FIG. 5 ;
FIG. 7 is a circuit diagram of a bistable memory cell consisting of the combination of one NDR-FET pull-up element and one depletion-mode IGFET pull-down element;
FIG. 8 is a plot of the current-vs.-voltage characteristic of the bistable memory cell of FIG. 7 ;
FIG. 9 is a circuit diagram of a static random access memory (SRAM) cell consisting of the combination of two NDR-FET elements which form a bistable latch and one enhancement-mode IGFET access element;
FIG. 10 is a plot of the current-vs.-voltage characteristic of the bistable latch formed by the combination of two NDR-FETs as shown in FIG. 9 ;
FIG. 11 is a schematic cross-sectional view of a starting substrate used to manufacture a semiconductor device comprising one or more IGFET elements and one or mote NDR-FET elements;
FIG. 12 is a schematic cross-sectional view showing the step of forming electrically isolated active areas in the surface region of the substrate;
FIG. 13 is a schematic cross-sectional view showing the step of forming an initial insulating layer on the surface of the substrate in the active areas;
FIG. 14 a is a schematic cross-sectional view showing the step of selectively introducing impurities into the surface of the substrate in the active area where the NDR-FET will reside;
FIG. 14 b is a schematic cross-sectional view showing the step of selectively removing the initial insulating layer from the active area where the IGFET will reside;
FIG. 15 a is a schematic cross-sectional view showing the step of selectively introducing impurities into the initial insulating layer in the active area where the NDR-FET will reside;
FIG. 15 b is a schematic cross-sectional view showing the step of selectively removing the initial insulating layer from the active area where the IGFET will reside;
FIG. 16 is a schematic cross-sectional view showing the step of forming an additional insulating layer on the surface of the substrate in the active regions;
FIG. 17 is a schematic cross-sectional view showing the step of depositing a gate film;
FIG. 18 is a schematic cross-sectional view showing the step of patterning the gate film into gate electrodes;
FIG. 19 is a schematic cross-sectional view showing the step of forming the source and drain electrodes for the NDR-FET and IGFET devices;
FIG. 20 is a schematic cross-sectional view showing the step of depositing an electrically insulating interlayer film, forming contact holes in the interlayer film, and depositing a metal layer and patterning the metal layer to form interconnections to the NDR-FET and IGFET devices.
DETAILED DESCRIPTION OF THE INVENTION
A semiconductor device according to a first embodiment of the invention will now be described with reference to FIGS. 1 and 2 . FIG. 1 is a circuit diagram of a bistable memory cell 100 consisting of one enhancement-mode IGFET “pull-up” element 110 and one NDR-FET “pull-down” element 120 , and FIG. 2 is a current-vs.-voltage plot illustrating the operational characteristics of the bistable memory cell of FIG. 1 .
As is shown in FIG. 1 , a positive voltage V cc is supplied to a drain electrode and gate electrode of IGFET 110 , and a source electrode of IGFET 110 is connected together with a drain electrode of NDR-FET 120 to a common control terminal at potential V control , and a source electrode of NDR-FET 120 is connected to a ground terminal. With its drain electrode and gate electrode biased at the same potential, IGFET 110 operates in a saturation mode. A current flowing in IGFET 110 , I IGFET , is directly dependent on a voltage difference between its drain electrode potential and its source electrode potential, V cc −V control , and increases as V cc −V control increases, i.e. as V control decreases below V cc . A positive voltage V bias is supplied to the gate electrode of NDR-FET 120 , such that a current flowing in NDR-FET 120 , I NDR-FET , will exceed that of IGFET 110 over a range of values for V control I NDR-FET is dependent on a difference between its drain electrode potential and its source electrode potential, V control , at first increasing rapidly as V control increases (i.e., operating as a conventional FET), reaching a peak value when V control is equal to a critical voltage V NDR , and rapidly decreasing to nearly zero as V control increases beyond the critical voltage V NDR (i.e., operating as an NDR FET).
Now the operation of memory circuit 100 of FIG. 1 will be described. FIG. 2 shows a current-vs.-voltage (I–V) characteristic curve I GFET of IGFET 110 obtained by changing a control voltage V control applied to a control terminal in a range between 0 and V cc , superimposed with the I–V characteristic curve I NDR-FET of NDR-FET 120 . A stable operating point of circuit 100 occurs at a point where I–V characteristic curve I IGFET of IGFET 110 crosses an I–V characteristic curve I NDRFET of NDR-FET 120 and additionally the characteristic curves I IGFET and I NDRFET have different gradient signs (positive, negative, or zero). (A crossing point where both characteristic curves I IGFET and I NDRFET have positive or negative gradient is not a stable operating point.) Therefore it is understood that circuit 100 is stable when a potential V control at a control terminal is one of two values V low and V cc as shown in FIG. 2 . Accordingly, circuit 100 can be used as a bistable memory cell by applying a potential of one of the two values V low and V cc to control terminal as a write voltage. If the value of V control falls slightly below that of a stable operating point, the IGFET current I IGFET becomes higher than the NDR-FET current I NDR-FET , causing the value of V control to be increased toward V cc , to restore it to that of the stable operating point. Thus IGFET 110 serves as a “pull-up” device. If the value of V control increases slightly above that of a stable operating point, the NDR-FET current I NDR-FET becomes higher than the IGFET current I IGFET , causing the value of V control to be decreased toward 0 V (ground potential), to restore it to that of the stable operating point. Thus NDR-FET 120 serves as a “pull-down” device.
In this manner, a bistable memory cell can be obtained when an NDR-FET and an IGFET are formed on the same semiconductor substrate. Data can be written or read from such cell 100 in any conventional fashion known to those in the art.
NDR FET 120 and IGFET 110 can thus share a number of common structural features, including isolation regions, source/drain regions, gate insulating layers, gate electrode layers, contact layers, etc., and be manufactured according to a common set of processing operations. This latter feature ensures that the present invention is easily integrable into contemporary conventional wafer manufacturing facilities.
For the discusson below, except where otherwise noted, like numbered structures referenced in the text and in the drawings are intended to correspond to the same structures as previously discussed in connection with FIGS. 1 and 2 .
A semiconductor circuit according a second embodiment of the invention will now be described with reference to FIGS. 3 and 4 . FIG. 3 is a circuit diagram of a bistable memory cell 100 consisting of one NDR-FET “pull-up” element 120 and one enhancement-mode IGFET “pull-down” element 110 , and FIG. 4 is a current-vs.-voltage plot illustrating the operational characteristics of the bistable memory cell of FIG. 3 .
As is shown in FIG. 3 , a positive voltage V cc is supplied to the drain electrode of NDR-FET 120 , the source electrode of NDR-FET 120 is connected together with the drain electrode of IGFET 110 and the gate electrode of IGFET 110 to a common control terminal at potential V control , and the source electrode of IGFET 110 is connected to a ground terminal. With its drain electrode and gate electrode biased at the same potential, IGFET 110 again operates in the saturation mode. The current flowing in IGFET 110 , I IGFET , is directly dependent on the difference between its drain electrode potential and its source electrode potential, V control , and increases as V control increases. A positive voltage V bias is supplied to the gate electrode of NDR-FET 120 , such that the current flowing in the NDR-FET, I NDR-FET , will exceed that of IGFET 110 over a range of values for V control . I NDR-FET is dependent on the difference between its drain electrode potential and its source electrode potential, V cc −V control , at first increasing rapidly as V cc −V control increases, reaching a peak value when V cc −V control is equal to a critical voltage V NDR , and rapidly decreasing to nearly zero as V cc −V control increases beyond the critical voltage V NDR .
Now the operation of circuit 100 of FIG. 3 will be described. FIG. 4 shows the current-vs.-voltage (I–V) characteristic curve I IGFET of IGFET 110 obtained by changing the control voltage V control applied to the control terminal in a range between 0 and V cc , superimposed with the I–V characteristic curve I NDR-FET of the NDR-FET. As before, a stable operating point of the circuit is a point where the I–V characteristic curve I IGFET of IGFET 110 crosses the I–V characteristic curve I NDRFET of NDR-FET 120 and additionally the characteristic curves I IGFET and I NDRFET have different gradient signs (positive, negative, or zero). (A crossing point where both of the characteristic curves I IGFET and I NDRFET have positive or negative gradient is not a stable operating point.) Therefore it is understood that the circuit is stable when the potential V control at the control terminal is one of two values 0 and V high as shown in FIG. 4 . Accordingly, circuit 100 also can be used as a bistable memory cell by applying a potential of one of the two values 0 and V high to the control terminal as a write voltage. If the value of V control falls slightly below that of a stable operating point, the NDR-FET current I NDR-FET becomes higher than the IGFET current I IGFET , causing the value of V control to be increased toward V cc , to restore it to that of the stable operating point. Thus in this embodiment NDR-FET 120 serves as a “pull-up” device. If the value of V control increases slightly above that of a stable operating point, IGFET current I IGFET becomes higher than the NDR-FET current I NDR-FET , causing the value of V control to be decreased toward 0 V (ground potential), to restore it to that of the stable operating point. Thus IGFET 110 serves as a “pull-down” device in this embodiment. In this manner, a bistable memory cell can be obtained when an NDR-FET and an IGFET are formed on the same semiconductor substrate.
A semiconductor device according a third embodiment of the invention will now be described with reference to FIGS. 5 and 6 . FIG. 5 is a circuit diagram of a bistable memory cell 100 consisting of one depletion-mode IGFET “pull-up” element 115 and one NDR-FET “pull-down” element 120 , and FIG. 6 is a current-vs.-voltage plot illustrating the operational characteristics of the bistable memory cell of FIG. 5 .
As is shown in FIG. 5 , a positive voltage V cc is supplied to the drain electrode of IGFET 115 , the gate electrode of IGFET 115 is connected together with the source electrode of IGFET 115 and the drain electrode of NDR-FET 120 to a common control terminal at potential V control , and the source electrode of NDR-FET 120 is connected to a ground terminal. The current flowing in the IGFET, I IGFET , is directly dependent on the difference between its drain electrode potential and its source electrode potential, V cc −V control ) and increases as V cc −V control increases, i.e. as V control decreases below V cc . I GFET increases relatively slowly as V cc −V control increases above a saturation voltage V Dsat . A positive voltage V bias is supplied to the gate electrode of NDR-FET 120 , such that the current flowing in the NDR-FET, I NDR-FET , will exceed that of IGFET 115 over a range of values for V control . I NDR-FET is dependent on the difference between its drain electrode potential and its source electrode potential, V control , at first increasing rapidly as V control increases, reaching a peak value when V control is equal to a critical voltage V NDR , and rapidly decreasing to nearly zero as V control increases beyond the critical voltage V NDR .
Now the operation of the circuit of FIG. 5 will be described. FIG. 6 shows the current-vs.-voltage (I–V) characteristic curve I IGFET of IGFET 115 obtained by changing the control voltage V control applied to the control terminal in a range between 0 and V cc , superimposed with the I–V characteristic curve I NDR-FET of NDR-FET 120 . A stable operating point of circuit 100 is a point where the I–V characteristic curve I IGFET of the IGFET crosses the I–V characteristic curve I NDRFET of the NDR-FET and additionally the characteristic curves I IGFET and I NDRFET have different gradient signs (positive, negative, or zero). (A crossing point where both of the characteristic curves I IGFET and I NDRFET have positive or negative gradient is not a stable operating point.) Therefore it is understood that the circuit is stable when the potential V control at the control terminal is one of two values V low and V cc as shown in FIG. 6 .
Accordingly, circuit 100 can be used as a bistable memory cell by applying a potential of one of the two values V low and V cc to the control terminal as a write voltage. If the value of V control falls slightly below that of a stable operating point, the IGFET current I IGFET becomes higher than the NDR-FET current I NDR-FET , causing the value of V control to be increased toward V cc , to restore it to that of the stable operating point. Thus IGFET 115 serves as a “pull-up” device. If the value of V control increases slightly above that of a stable operating point, the NDR-FET current I NDR-FET becomes higher than the IGFET current I IGEFT , causing the value of V control to be decreased toward 0 V (ground potential), to restore it to that of the stable operating point. Thus NDR-FET 120 serves as a “pull-down” device. In this manner, a bistable memory cell can be obtained when an NDR-FET and an IGFET are formed on the same semiconductor substrate.
A semiconductor device according a fourth embodiment of the invention will now be described with reference to FIGS. 7 and 8 . FIG. 7 is a circuit diagram of a bistable memory cell 100 consisting of one NDR-FET “pull-up” element 120 and one depletion-mode IGFET “pull-down” element 115 , and FIG. 8 is a current-vs.-voltage plot illustrating the operational characteristics of the bistable memory cell 100 of FIG. 7 .
As is shown in FIG. 7 , a positive voltage V cc is supplied to the drain electrode of NDR-FET 120 , the source electrode of NDR-FET 120 is connected together with the drain electrode of IGFET 115 to a common control terminal at potential V control , and the gate electrode of IGFET 115 is connected together with the source electrode of IGFET 115 to a ground terminal. The current flowing in the IGFET, I IGFET is directly dependent on the difference between its drain electrode potential and its source electrode potential, V control , and increases as V control increases. I GFET increases relatively slowly as V control increases above a saturation voltage V Dsat . A positive voltage V bias is supplied to the gate electrode of NDR-FET 120 , such that the current flowing in the NDR-FET, I NDR-FFT , will exceed that of IGFET 115 over a range of values for V control . I NDR-FET is dependent on the difference between its drain electrode potential and its source electrode potential V cc −V control , at first increasing rapidly as V cc −V control increases, reaching a peak value when V cc −V control is equal to a critical voltage V NDR , and rapidly decreasing to nearly zero as V cc −V control increases beyond the critical voltage V NDR .
Now the operation of the circuit of FIG. 7 will be described. FIG. 8 shows the current-vs.-voltage (I–V) characteristic curve I IGFET of IGFET 115 obtained by changing the control voltage V control applied to the control terminal in a range between 0 and V cc , superimposed with the I–V characteristic curve I NDR-FET of the NDR-FET. A stable operating point of the circuit is a point where the I–V characteristic curve I IGFET of IGFET 115 crosses the I–V characteristic curve I NDRFET of NDR-FET 120 and additionally the characteristic curves I IGFET and I NDRFET have different gradient signs (positive, negative, or zero). (A crossing point where both of the characteristic curves I IGFET and I NDRFET have positive or negative gradient is not a stable operating point.) Therefore it is understood that circuit 100 is stable when the potential V control at the control terminal is one of two values 0 and V high , as shown in FIG. 8 . Accordingly, circuit 100 can be used as a bistable memory cell by applying a potential of one of the two values 0 and V high to the control terminal as a write voltage. If the value of V control falls slightly below that of a stable operating point, the NDR-FET current I NDR-FET becomes higher than the IGFET current I IGFET , causing the value of V control to be increased toward V cc , to restore it to that of the stable operating point. Thus NDR-FET 120 serves as a “pull-up” device. If the value of V control increases slightly above that of a stable operating point, the IGFET current I IGFET becomes higher than the NDR-FET current I NDR-FET , causing the value of V control to be decreased toward 0 V (ground potential), to restore it to that of the stable operating point. Thus IGFET 115 serves as a “pul-down” device. In this manner, a bistable memory cell 100 can be obtained when an NDR-FET and an IGFET are formed on the same semiconductor substrate.
A semiconductor device according a fifth embodiment of the invention will now be described with reference to FIGS. 9 and 10 . FIG. 9 is a circuit diagram of a static memory (SRAM) cell 150 consisting of two NDR-FET elements which form a bistable latch 140 and one enhancement-mode IGFET access element, and FIG. 10 is a current-vs.-voltage plot illustrating the operational characteristics of the static memory cell of FIG. 9 .
As is shown in FIG. 9 , an IGFET 118 is configured as a transfer gate, allowing a data node at potential V data to be connected to a storage node at potential V store under the control of an access signal V access . One of the source/drain electrodes of IGFET 118 is connected to the storage node, the other source/drain electrode of IGFET 118 is connected to the data node, and the gate electrode of IGFET 118 is connected to an access signal terminal (read or write). The source electrode of a first NDR-FET 120 is connected to a ground terminal, the gate electrode of the first NDR-FET 120 is supplied with a first bias voltage V bias1 , the drain electrode of the first NDR-FET 120 is connected together with the source electrode of a second NDR-FET 130 to the storage node, the gate electrode of the second NDR-FET 130 is supplied with a second bias voltage V bias2 and the drain electrode of the second NDR-FET 130 is supplied with a positive voltage V cc . The current flowing in the first NDR-FET, I NDR1 , is dependent on the difference between its drain electrode potential and its source electrode potential, V store , at first increasing rapidly as V store increases, reaching a peak value when V store is equal to a critical voltage V NDR1 , and rapidly decreasing to nearly zero as V store increases beyond the critical voltage V NDR1 . The bias voltage V bias1 is sufficiently high so as to ensure that the first NDR-FET is turned on for values of V store ranging from 0 V (ground potential) to V NDR1 . The current flowing in the second NDR-FET, I NDR2 , is dependent on the difference between its drain electrode potential and its source electrode potential, V cc −V store , at first increasing rapidly as V cc −V store increases, reaching a peak value when V cc –V store is equal to a critical voltage V NDR2 , and rapidly decreasing to nearly zero as V cc –V store increases beyond the critical voltage V NDR2 . The bias voltage V bias2 is sufficiently high so as to ensure that the second NDR-FET is turned on for values of V cc –V store ranging from 0 V (ground potential) to V NDR2 .
Now the operation of the bistable latch 140 in the SRAM cell 150 of FIG. 9 will be described. FIG. 10 shows the current-vs.-voltage (I–V) characteristic curve I NDR1 of the first NDR-FET 120 obtained by changing the storage node voltage V store in a range between 0 and V cc , superimposed with the I–V characteristic curve I NDR2 of the second NDR-FET 130 . A stable operating point of circuit 150 is a point where the I–V characteristic curve I NDR1 of the first NDR-FET 120 crosses the I–V characteristic curve I NDR2 of the second NDR-FET 130 and additionally the characteristic curves I NDR1 and I NDR2 have different gradient signs (positive, negative, or zero). (A crossing point where both of the characteristic curves I NDR1 and I NDR2 have positive or negative gradient is not a stable operating point.) Therefore it is understood that circuit 150 is stable when the potential V store at the storage node is one of two values 0 and V cc as shown in FIG. 10 . Accordingly, circuit 150 can be used as a bistable memory cell by applying a potential of one of the two values 0 and V high to the control terminal as a write voltage. If the value of V store increases slightly above that of a stable operating point, current I NDR1 flowing in the first NDR-FET 120 becomes higher than the current I NDR2 flowing in the second NDR-FET 130 , causing the value of V store to be decreased toward 0 V (ground potential), to restore it to that of the stable operating point. Thus first NDR-FET 120 serves as a “pull-down” device. If the value of V store falls slightly below that of a stable operating point, the current I NDR2 flowing in the second NDR-FET 130 becomes higher than the current I NDR1 flowing in the first NDR-FET 120 , causing the value of V store to be increased toward V cc , to restore it to that of the stable operating point. Thus second NDR-FET 130 serves as a “pull-up” device. IGFET 118 is controlled by the access signal as follows: when the access signal potential is sufficiently high, IGFET 118 is turned on, connecting the data node to the storage node to allow data transfer (reading data from the storage node, or writing data to the storage node); when the access signal potential is low, IGFET 118 is turned off, so that the storage node is electrically isolated from the data node. In this manner, a bistable latch 140 is realized with two series-connected NDR-FET elements, and a static memory cell 150 is obtained when two NDR-FETs and an IGFET are formed on the same semiconductor substrate.
It will be understood by those skilled in the art that the particular implementation of circuit 100 (i.e., in one of the forms noted above or some apparent variation) will likely vary from application to application. Moreover, it is likely that such circuit will be combined with other well-known circuit elements (including sense amplifiers, buffers, decoders, etc.) for purposes of creating larger memory cell arrays. Furthermore, it is expected that IGFETs and NDR FETs will be combined by skilled artisans to effectuate a number of different memory and logic circuits not shown explicitly herein, and the present invention is by no means limited to the specific examples depicted. For example, multi-valued memory cells can be synthesized through well-known techniques by using appropriate combinations of IGFETS and NDR FETs having different NDR onset behavior.
A preferred fabrication process flow for manufacturing a semiconductor device comprising one or more NDR-FETs and one or more IGFETs will now be described with reference to FIGS. 11 through 20 , which are schematic cross-sectional views at various steps in the process flow.
First, as is shown in FIG. 11 , a preferred substrate 1000 consisting substantially of silicon (Si) is prepared. Because the NDR-FET and IGFET are n-channel devices, the portions of the substrate in which the NDR-FET(s) and IGFET(s) are to be formed are preferably p-type. P-type wells can be formed in the surface (within the top 1000 nm) of the substrate by ion implantation and/or diffusion, either before or after the definition of “active” areas, in any number of known techniques known to those skilled in the art. It should be noted that substrate 1000 could also be silicon-on-insulator (SOI), and may eventually contain one or more additional layers of silicon-germanium alloy material (not shown).
Next, as is shown in FIG. 12 , electrically isolated “active” areas 1015 in a surface of substrate 1000 are formed by any of several well-established techniques, including preferably by local oxidation of silicon (LOCOS) and/or shallow trench isolation (STI). The thickness of an isolation oxide layer 1010 typically falls in a range from 100 nm to 700 nm, while a depth of shallow trench isolation structures typically falls in the range from 100 nm to 1000 nm. It should be noted that the precise details of these areas are not critical to the operation of the present invention, but a significant advantage of course lies in the fact that such structures (however formed) can be share by both conventional active devices as well as the NDR devices in accordance with the present teachings.
Afterwards, ion implantation of dopants into the surface of substrate 1000 is preferably performed (either selectively with a mask or non-selectively) for the purpose of adjusting the threshold voltages of the NDR-FET(s) and IGFET(s) to their desired values. It is possible, of course, that different threshold voltages may be needed, so that additional masking and implanting operations may be needed for separate adjustments to such devices. However, as before, the details of such threshold adjust is not critical to the operation of the present invention, but yet in many instances both time and cost savings can be achieved by sharing such operational step between both conventional active devices as well as the NDR devices.
Next, as is shown in FIG. 13 , a first electrically insulating layer 1020 is preferably formed on the surface of substrate 1000 in active areas 1015 by one of several well-known techniques, including thermal oxidation of silicon, physical vapor deposition and chemical vapor deposition. This electrically insulating layer 1020 can consist entirely or in part of SiO 2 , SiO x N y , Si 3 N 4 , or a high-permittivity dielectric material such as metal oxide or metal silicate or their laminates. As with the other processing steps noted above, an advantage of the present invention lies in the fact that this layer can be shared later by both conventional and NDR FET devices.
If electrically insulating layer 1020 does not contain a sufficiently high density of charge traps as formed, then it is preferable to introduce charge traps at or near the silicon substrate interface. This can be accomplished by one of several known approaches, including ion implantation and/or diffusion of an appropriate species. If electrically insulating layer 1020 is very thin (e.g. less than 1.5 nm) charge traps can be formed by deposition of an additional continuous or discontinuous layer of charge-trapping material such as SiO x N y , Si 3 N 4 , Si, Ge or metal.
Two representative examples of techniques to form charge traps neat the silicon substrate interface are illustrated in FIGS. 14 and 15 . Other approaches will be apparent to those skilled in the art, and the present invention is by no means limited to such examples.
In a first approach shown in FIG. 14 a , impurity atoms are selectively implanted into a surface of substrate 1000 in the areas where NDR-FETs are to be formed to form a charge trapping region 1030 near the silicon substrate interface. These impurity atoms may be dopants such as boron, indium, arsenic and phosphorus, or fluorine, chlorine, or germanium. Electrically insulating layer 1020 may then be selectively removed from the areas where IGFETs are to be formed, as is shown in FIG. 14 b , if it is undesirable to have it remain in those areas. Thus, in this instance, this particular operation (creation of charge trapping layer 1030 ) is performed uniquely for the NDR FETs, but not for the conventional FETs.
In a second approach shown in FIG. 15 a , impurity atoms can be selectively implanted directly into electrically insulating layer 1020 in the areas where NDR-FETs are to be formed to form a charge trapping region within such insulating layer. These impurity atoms may be dopants such as boron, indium, arsenic and phosphorus, or fluorine, chlorine, or germanium. Again, as before, electrically insulating layer 1020 may then be selectively removed from the areas where IGFETs are to be formed, as is shown in FIG. 15 b , if it is undesirable to have it remain in those areas.
If electrically insulating layer 1020 is selectively removed from the areas where IGFETs are to be formed, then a high-quality gate insulating film 1040 is then preferably formed next on the surface of substrate 1000 in active areas 1015 , as is shown in FIG. 16 to form a gate insulation layer for such IGFETs. Gate insulating film 1040 can be formed by one of several techniques, including thermal oxidation, physical vapor deposition and chemical vapor deposition. If the formation process for gate insulation layer 1040 uses sufficiently high temperatures, impurities present in the surface of substrate 1000 (as in FIG. 14 ) can be incorporated by diffusion into electrically insulating film 1020 / 1040 to form charge traps in such insulating film near the substrate interface (for illustrative purposes, films 1020 and 1040 are shown as a single composite gate film in FIG. 16 ). Gate insulating film 1040 can consist entirely or in part of SiO 2 , SiO x N y , Si 3 N 4 , or a high-permittivity dielectric material such as metal oxide or metal silicate or their laminates.
In this manner, charge traps are selectively formed in a gate insulating film 1040 in the NDR-FET areas, either by ion implantation and/or diffusion of an appropriate species or by depositing a charge-trapping layer, either before or after part or all of the NDR-FET gate insulating film 1040 has been formed. Again, in the above process steps, features and structures of the NDR FETs are manufactured at the same time and common processing steps as those used for IGFETs in the integrated circuit.
If a “buried contact” between the gate electrode and source or drain region of the IGFET (or NDR FET) is required, then contact hole(s) are formed in gate insulating film 140 using standard lithography and etching processes. As before, such contacts can also be created at the same time for both types of FETs.
Next as shown in FIG. 17 , a gate electrode film/layer 150 is deposited onto substrate 100 , on top of gate insulating film 14 and patterned using standard lithography and etching processes to form gate electrodes ( FIG. 18 ). The gate electrode material 150 may be polycrystallite silicon (poly-Si) or a silicon-germanium alloy (poly-SiGe), or it may be a metal or conductive metal nitride or conductive metal oxide. An advantage of the present invention, again, is apparent because the gates of both NDR FETs and conventional FETs can be made of the same material, and at the same time.
If gate electrode material 150 is poly-Si or poly-SiGe, it may doped in-situ during the deposition process or it may be doped ex-situ by ion implantation and/or diffusion, to achieve low resistivity and a proper work function value. Gate electrode 1060 may consist of a multi-layered stack, with a lowest layer providing a desired gate work function and overlying layer(s) providing sufficient thickness and conductivity. After gate patterning, a thermal anneal may be performed in an oxidizing ambient (e.g. O 2 or H 2 O) to anneal out any damage to gate insulating film 1050 at the edges of gate electrodes 1060 . If boron is to be incorporated into electrically insulating film 1040 in the NDR-FET areas of substrate 1000 , it can enhance the formation of water-related traps in the electrically insulating film during an anneal in a steam (H 2 O) ambient.
As shown in FIG. 19 , source and drain contact regions (electrodes) are then formed by ion implantation of n-type dopants such as arsenic and phosphorus and subsequent thermal annealing to remove damage and to activate the dopants. In this particular implementation, gate electrodes 1060 are sufficiently thick to prevent implanted ions from entering the surface of substrate 1000 underneath the gate electrodes. If boron is incorporated into electrically insulating film 1040 in the NDR-FET areas, it can enhance the formation of water-related traps in the electrically insulating film during an anneal in a steam (H 2 O) ambient
In order to achieve good short-channel IGFET performance Low leakage current when the transistor is turned off, shallow source/drain extension regions (not shown) may be formed first by ion implantation or diffusion in the IGFET areas, either before or after deep source and drain regions. In this case, the deep source and drain regions are offset from the edges of the gate electrode by spacers formed along the sidewalls of the gate electrodes. The sidewall spacers are formed by conformal deposition and anisotropic etching of a spacer film. (The thickness of this spacer film determines the width of the sidewall spacers and hence the offset from the gate electrode.)
If the shallow source/drain extension regions are to be formed after the deep source and drain regions, then disposable sidewall spacers (e.g. composed of germanium or silicon-germanium, which can be removed selectively with respect to Si, SiO 2 , SiO x N y , Si 3 N 4 , metal, metal nitrides and metal oxides) must be used. The dopant concentration in the shallow source/drain extension regions may be lower than the dopant concentration in the deep source and drain regions, to reduce hot-carrier effects which can cause reliability problems. Shallow source/drain extension regions may be formed in the NDR-FET areas simultaneously with the shallow source/drain extension regions in the IGFET areas. The dopant concentration and junction depth of the shallow source/drain extensions for the NDR-FET can be made to be different from those for the NDR-FET, if necessary, by selective (masked) ion implantation.
As shown in FIG. 20 , device fabrication is completed by deposition of an electrically insulating interlayer film 1080 , formation of contact holes 1085 , filling of contact holes with metal plugs 1090 , deposition and patterning of a metal layer to form interconnections, and a low temperature (350° C.–450° C.) anneal in a hydrogen-containing ambient (forming gas). Multiple layers of metal wiring, if necessary, may be formed by deposition and patterning of alternate layers of insulating material and metal.
In this manner, a semiconductor device comprising one or more IGFET elements and one or more NDR-FET elements can be manufactured on a common substrate utilizing a fabrication sequence utilizing conventional processing techniques. For example, an NDR FET and a conventional IGFET share a number of common layers in their respective areas including: a common substrate 1000 ; gate film 1040 and 1040 ′; gate electrode 1060 and 1060 ′; interlayer insulation layer 1080 and 1080 ′; metal plugs/layer 1090 and 1090 ′. Furthermore, they also share certain isolation areas 1010 , and have source/drain regions 1070 and 1070 ′ formed at the same time with common implantation/anneal steps. In some cases, there can be direct sharing of such regions of course, so that the drain of an NDR FET can correspond to a drain/source of an IGFET, or vice versa. It will be understood that other processing steps and/or layers may be performed in addition to those shown above, and these examples are provided merely to illustrate the teachings of the present inventions. For example, additional interconnect and/or insulation layers are typically used in ICs and can also be shared.
While this invention has been described with reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. It will be clearly understood by those skilled in the art that foregoing description is merely by way of example and is not a limitation on the scope of the invention, which may be utilized in many types of integrated circuits made with conventional processing technologies. Various modifications and combinations of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to the description. Such modifications and combinations, of course, may use other features that are already known in lieu of or in addition to what is disclosed herein. It is therefore intended that the appended claims encompass any such modifications or embodiments. While such claims have been formulated based on the particular embodiments described herein, it should be apparent the scope of the disclosure herein also applies to any novel and non-obvious feature (or combination thereof) disclosed explicitly or implicitly to one of skill in the art, regardless of whether such relates to the claims as provided below, and whether or not it solves and/or mitigates all of the same technical problems described above. Finally, the applicants further reserve the right to pursue new and/or additional claims directed to any such novel and non-obvious features during the prosecution of the present application (and/or any related applications). | A semiconductor device is disclosed that includes integrated insulated-gate field-effect transistor (IGFET) elements and one or more negative differential resistance (NDR) field-effect transistor elements, combined and formed on a common substrate. Thus, a variety of circuits, including logic and memory are implemented with a combination of conventional and NDR capable FETs. Because both types of elements share a number of common features, they can be fabricated with common processing operations to achieve better integration in a manufacturing facility. | 7 |
FIELD OF THE INVENTION
This invention relates to a valve for pressure difference relief between a liquid container and the ambient atmosphere.
An important field of use of such relief valves is for the oil tanks of oil cargo vessels, and in the following explanation and description this field of use will be taken as point of departure, but it will be understood that the same principles will be equally applicable to other fields of use, e.g. for stationary storage tanks or for rolling transportation tanks for liquid petroleum products or chemicals.
PRIOR ART
There are two categories of pressure difference relief valves, viz. pressure relief valves (venting valves) and vacuum relief valves. Examples of these are disclosed in U.S. Pat. No 5,060,688.
A pressure relief valve is opened against a built-in closing force by the pressure of the gas above the liquid level in the tank when this pressure rises to a value above that of the ambient atmosphere beyond a pre-determined value, referred to as the opening pressure. It is closed when the gas pressure drops below the opening pressure.
When oil is loaded into the tank at a certain volumetric rate, gas must escape through the pressure relief valve at the same volumetric rate. The valve is designed for a maximum permissible loading rate, at which the pressure drop across the valve assumes a maximum permissible value, which is chosen well below a prescribed safety limit to obtain ample safety against rupture, or even explosion, of the tank.
At the maximum permissible loading rate the valve assumes a fully open position defined by stop means. At a lower loading rate the valve assumes an intermediate position between the closed position and the fully open position.
The operation of a vacuum relief valve is exactly similar to that described, when considering the situation of unloading the tank, and substituting "relative vacuum" for "pressure above that of the ambient atmosphere", and substituting "collapse" for "explosion".
Whenever a relief valve of either category is in an intermediate position, its flow-control element is sensitive to fluctuations of the rate of gas flow caused e.g. by turbulence or non-uniform distribution of the flow. The resulting vibratory movement of the flow control element will act back on the rate of flow, and thereby a reciprocal-amplifying effect may be initiated which may cause the valve to vacillate forth and back between the fully open and the closed position. Thereby the valve may be subjected to a series of heavy clashes of metal against metal, which is in itself undesirable for mechanical reasons and besides may produce a heavy noise, which may even be amplified by the tank wall as a reverberator.
SUMMARY OF THE INVENTION
It is an object of the invention to remedy this drawback without in any way jeopardizing the regular operation and the safety functions of the valve.
Briefly speaking, the salient feature of the invention is the provision of springs which are symmetrically clamped against a slidably mounted stem of the valve from opposite sides thereof in such a manner as to create an accurately controlled frictional resistance to slidable movement of the stem, thereby eliminating or reducing any tendency to vacillation.
More precisely, the invention, for which protection is sought, consists in the combinations of features set forth in the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a vertical section through a pressure relief valve and a vacuum relief valve built together and each constituting an embodiment of the invention.
FIG. 2 is a perspective view on a larger scale of a frictional device, with which each of the relief valves of FIG. 1 is constructed.
FIG. 3 is a horizontal section through the frictional device of FIG. 2, taken along either of the lines III--III in FIG. 1.
FIG. 4 is a corresponding horizontal section through a slightly modified embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Apart from the frictional device to be described further below with reference to FIGS. 2-4, the pressure relief valve of FIG. 1 is identical to that disclosed in U.S. Pat. No. 5,060,688.
1 is a vertically oriented valve housing, which at its lower end has a flange 2 which is bolted to a flange 3 of a tubular socket 4 constructed at its lower end with a flange 5 that can be bolted to a pressure relief outlet of an oil tank or to the upper end of a pressure relief pipe connected to one or more tank compartments. In the embodiment shown, the socket 4 has a lateral opening 6 to which a vacuum relief valve 7 is connected, which will be described further below.
At its lower end, the valve housing has a cylindrical wall portion 8 which in a direction upwards is followed by a diverging wall portion 9 and thereafter a converging wall portion 10 which at the top of the valve housing is terminated by a blow off opening 11.
In the blow-off opening there is mounted a mouth ring 12 at the inner side of which a conical valve seat 13 is formed. In the blow-off opening 11 there is arranged a drop-shaped body 14 on the underside of which a conical valve surface 15 is formed which in the closed condition of the valve sealingly engages the valve seat 13.
For improving the tightness, an annular elastic gasket 16 may be arranged on the inner side of the mouth ring 12, said gasket having a lip 17 engaging the underside of the drop-shaped body 14.
A stem 18 is connected to the drop-shaped body and extends down through the housing where it is guided by an upper stem guide 19 in the valve housing and a lower stem guide 20 in the socket 4. The stem 18 carries a lifting disc 21 which is located in the interior of the cylindrical wall portion 8 and has a slightly smaller diameter than the latter so that a free passage slot 22 is formed around the lifting disc. Under the lower end of the stem 18 there is mounted a rocking lever 24 for use in check-lift of the valve.
A compressional spring 23 is interposed between the upper stem guide 19 and the lifting disc 21. Thus, the structure, referred to herein as the flow-off controlling member, comprising the drop-shaped body 14, the stem 18 and the lifting disc 21 is subjected to a downwardly directed closing force equal to the compressional force of the spring 23+the total weight of all parts of the structure. If these are so constructed that their own weight provides a suitable closing force, the spring 23 may be omitted.
If a pressure in excess of that of the atmosphere comes up in the tank, then, owing to the leakage through the slot 22, this pressure will propagate to the space above the lifting disc 21, and this will therefore be subjected to the same pressure from above and from below. A lifting force is therefore produced solely by the action of the excess pressure on the underside of the drop-shaped body. This lifting force is equal to the excess pressure multiplied by the cross-sectional area of the blow-off opening inside the valve seat.
When the lifting force exceeds the previously mentioned closing force, the valve is opened. This takes place at a predetermined value of the tank pressure, the opening pressure, which is pre-set by dimensioning the weight of the drop-shaped body 14, the stem 18 and the lifting disc 21, which may be supplemented by an additional weight load and/or a compressional spring 23. When the blow-off commences at the opening of the valve, the pressure on the upper side of the lifting disc drops, and the net value of the lifting force becomes equal to the tank pressure multiplied by the area of the lifting disc. Since this is larger than the area of the blow-off opening, the lifting force is augmented, and thereby the lifting speed and hence the blow-off quantity per time unit are increased.
When the valve is further lifted, the lifting disc 21 arrives into the area of the diverging wall portion 9, whereby the blow-off quantity is further increased.
The upward movement of the flow-off controlling member 14, 18, 21 is limited by stop noses 25 extending inwards from the wall of the valve housing 1 into the path of movement of the lifting disc 21. When the lifting disc 21 strikes these noses 25, the valve is in a fully open position. The valve is so dimensioned that this position is reached, when the volumetric rate of the gas flow-off rises to a value corresponding to the maximum permissible loading rate. For further details of the construction, dimensioning and operation of the pressure relief valve, reference is made to U.S. Pat. No. 5,060,688.
When the tank is loaded at a volumetric rate less than the maximum permissible value, the valve will assume an intermediate position between the closed position and the fully open position, and for the reasons previously explained vacillation between these positions may occur resulting in alternate clashes of the valve surface 15 of the drop-shaped body against the valve seat 13, and of the lifting disc 21 against the noses 25. The risk of vacillation particularly exists where the valve is connected to one or more tanks through pipes or conduits of considerable length and/or having bends or angles or other irregularities.
To eliminate or reduce the risk of vacillation, the valve is constructed with a frictional device 26 to be described further below with reference to FIGS. 2-4.
The vacuum relief valve 7 is of a conventional construction and corresponds to that illustrated in FIG. 1 of U.S. Pat. No. 5,060,688, but not described in detail in the specification of the patent.
The vacuum relief valve 7 has a valve housing 51 which at its left end is constructed with a connecting portion 52 connected to the socket 4.
The valve housing 51 has a bottom opening in which is mounted a valve seat 53 carrying a valve stem guide 54. The valve seat 53 is engaged by a valve body 55, which by means of a stem 56 is guided in the stem guide 54. The valve housing 51 is closed at its top by means of a cover 57.
At its bottom, the vacuum valve is in well-known manner constructed with a net ring 58 carrying a double flame arresting net 59, and with a shield 60 having a hub 61 accomodating a check-lifting button 62.
The valve body 55 is urged towards the valve seat by a built-in closing force which in the embodiment illustrated is constituted by the gravity of the valve body. In the vacuum condition of the tank, the closing force is counted-acted by a lifting force which is equal to the free are of the underside of the valve body 55 multiplied by the pressure difference between the underside and the upper side of the valve body, i.e. between the ambient pressure and the pressure in the valve housing, and thereby in the tank with which the vacuum valve is connected. If a vacuum comes up in the tank, the valve body will be lifted when the lifting force exceeds the closing force, and thereby air will flow from the surroundings via the valve opening and the interior of the valve housing to the tank. When the pressure in the tank thereby rises to a value equal to the ambient pressure less the pressure drop across the valve, the lifting force will be equal to the closing force, and the valve is again closed.
The upward movement of the valve body is limited by the engagement of an upward projection 63 on the valve body 55 with a downward projection 64 on the cover 57, thereby defining a fully open position of the valve. The valve is so dimensioned that this position is reached when the volumetric rate of the air inflow rises to a value corresponding to the maximum permissible unloading rate.
When the tank is unloaded at a volumetric rate less than the maximum permissible value, the valve will assume an intermediate position between the closed position and the fully open position, and for the reasons previously explained vacillation between these positions may occur resulting in alternate clashes between the valve body 55 against the valve seat 53, and of the projections 63 and 64 against each other. As will be seen the situation is exactly the same as for the pressure relief valve, and the remedy proposed according to the invention is again the provision of a frictional device 26, which will now be described with reference to FIGS. 2-4.
In these figures, 101 is a stem representing the stem 18 of the pressure relief valve 1 or the stem 56 of the vacuum relief valve of FIG. 1 102 is a bushing forming a stem guide, which slidably supports the stem 101 and thus represents the stem guide 19 of the pressure relief valve 1 or the stem guide 54 of the vacuum relief valve 7.
At its upper end the stem guide carries two traverses 103 and 104 which extend perpendicularly to a diametrical plane of the stem 101 on opposite sides of the stem. The traverses 103 and 104 may be separate elements attached to the upper end of the stem guide 102 by any suitable means, but preferably the stem guide and the traverses are made in one piece, e.g. from a unitary workpiece which comprises a cylindrical portion and a block of rectangular cross-section and is shaped into the required configuration and to accurate measures by machine tool operations.
The traverses 103 and 104 serve as spring holders for two spring wires 105 and 106, which are mounted in holes 103a, 103b and 104a, 104b of the traverses 103 and 104, respectively. The distance between the holes 103a, 103b/104a, 104b of each traverse is slightly smaller than the diameter of the stem 101, so that the spring wires will be bent in a shallow arc and will thereby be urged against diametrically opposite areas of the cylindrical surface of the stem 101 so as to create a frictional force opposing sliding movement of the stem.
In the embodiment of FIG. 3, the wires 105 and 106 are rigidly clamped or otherwise fastened in the holes 103a and 103b, but freely slidable in the holes 104a and 104b, so that they will never be subjected to axial stresses, but only to a bending stress which is determined exclusively by the geometrical configuration of the system. In the embodiment of FIG. 4, the same effect is obtained by mounting the spring wires 105,106 freely slidably in the holes of both traverses 103,104 and bending up their ends at a right angle to form stops 105a, 105b and 106a, 106b preventing the wires from sliding out of engagement with the holes of the traverses.
In FIG. 3, the dimensions of the various parts of the arrangement are designated as follows:
D=diameter of stem,
L=distance between inner sides of traverses,
B=distance between spring mounting positions of each traverse,
d=diameter of spring,
Δ=deflection of spring.
It will be seen that ##EQU1## Thus, the deflection Δ, and hence the spring force, can be calculated determinately from the dimensions D, B and d, and by suitably selecting these dimensions it will therefore be possible to obtain a spring force creating a frictional resistance which is substantially smaller than both the built-in closing force and the net opening force occurring at a maximum permissible pressure difference between the interior of the valve housing and the ambient atmosphere. Such a frictional resistance can never prevent opening or closing of the valve in response to the pressure difference between the interior of the valve housing and the ambient atmosphere--which might have disastrous results--and it has been found that even a frictional resistance amounting to a small fraction only of the forces mentioned will normally suffice for preventing vacillation as a consequence of irregularities of the flow of gas or air through the valve.
It is desirable that the frictional force should remain as nearly as possible constant at ambient temperature variations within a relatively large interval, say from -50° C. to +50° C.
From equation I it will be seen that the spring deflection, and hence the frictional force primarily depends on D-B. By making the stem and the spring holders from materials having substantially the same coefficient of thermal expansion, certainty is therefore obtained that the variation of the spring deflection at ambient temperature variations within the contemplated interval of 100° C. will be limited to a small percentage, viz. the same percentage as that of the thermal expansion or contraction of the stem and the spring holders.
Advantageously, the stem and the spring holders can be made from the same material. Preferred construction materials for these elements are stainless steel or bronze alloys. The same applies to the stem guide, which, as previously mentioned, may suitably be integral with the spring holders. The spring elements are preferably made from stainless steel.
Since the absolute value of the spring deflection is approximately proportional to D-B, the variations of this absolute value within the contemplated temperature interval can be kept at a minimum by making D-B as small as possible, i.e. by so selecting the geometrical configuration of the frictional device that the distance between the mounting positions of one spring element and the other in each traverse is slightly smaller than the diameter of the stem.
At a given deflection of a given spring, the spring force will be the greater, the smaller the free length of the springs. To obtain the required spring force at a small value of the deflection it is therefore recommendable to make the distance L between the inner sides of the traverses as small as possible, i.e. by so arranging the traverses that their inner sides are located immediately adjacent to, but not in contact with the surface of the stem.
In a numerical example, the dimensions indicated in FIG. 3 are as follows:
D=20.0 mm
L=20.5 mm
B=19.0 mm
d=1.0 mm
hence
Δ=1.0 mm.
It has been found in practice that satisfactory results can be obtained if the distance L between the inner sides of the traverses is so selected as to leave a clearance of a few tenths of a millimeter between each traverse and the stem, and the spring bending elasticity and the spring deflection at 20° C., as determined by equation I, are so selected that the frictional resistance created by the springs is less than 25% of both the built-in closing force and the net opening force occurring at a maximum permissible pressure difference between the interior of the valve housing and the ambient atmosphere, and more than 5%, preferably 10-15%, of the lower one of these limits, which is normally the built-in closing force.
It is a further advantage of the arrangement described that the frictional device as a whole forms a very compact structure and therefore interferes as little as possible with the flow or gas or air through the valve housing.
In the preferred embodiment, where the traverses are integral with the stem guide, the still further advantage is obtained that the frictional device forms a self-contained unit that can be mounted in an existing pressure difference relief valve.
Moreover, since the frictional device is held in correct position relative to the stem by the stem itself, the frictional force is immune to any deformations or dimensional changes to which other parts of the valve may be subjected, and can therefore never rise to a value jeopardizing the regular operation and the safety functions of the valve.
It will be understood that the spring wires described can be replaced by leaf springs mounted in slots of the traverses without in any way changing the principles of operation.
The frictional device according to the invention can also be used for flow control systems other than pressure difference relief valves or for operative systems in general, where similar problems are encountered in connection with a slidably mounted stem. | A pressure difference relief valve, viz. a pressure relief valve or a vacuum relief valve, for a liquid container has a valve body which opens or closes a valve opening of a valve housing in response to the pressure difference between the interior of the valve housing and the ambient atmosphere. The valve body is connected to a slidably mounted stem. The valve is constructed with spring elements which are clamped against the stem from opposite sides thereof at a controlled force to create a frictional resistance to sliding movement of the stem. Hereby any tendency of the valve to vacillate between the closed position and a fully open position under the influence of fluctuations of the gas or air flow, e.g. caused by turbulence, is eliminated or reduced. | 5 |
This application is a continuation of application Ser. No. 549,447, filed Nov. 4, 1983, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to a lift car support and in particular to a manner of mounting a lift car in a supporting frame to permit a limited degree of horizontal movement of the lift car relative to the frame.
In the case of high speed lifts or elevators in particular, it has been recognised that slight mis-alignment of the guide rails in the lift shaft, or movement of the building due to wind loads or other causes, may induce transverse vibrations in a lift car during operation. The lift car is suspended within or from a framework to which the lift hoisting mechanism is attached, and the lift car can move transversely due to various applied forces. This transverse movement or vibration can cause some degree of discomfort or uneasiness to the occupiers of the lift car.
Australian Patent Specification No. 464,496 discloses the proposal of a freely moving lift car mounted either like a pendulum or freely on ball bearings retained in bolsters, means being provided for cushioning the lift car against the frame and preventing over-movement.
A further development in the art was proposed by the present applicants and is described in Australian Patent Specification No. 43223/80 in which there is disclosed a lift car suspension which in the preferred embodiment is known as "a Ball's point suspension".
However it is still considered desirable to provide alternative methods of mounting the lift car in the support frame which can be readily constructed into lift cars either as original equipment or as a modification to be fitted subsequently. Furthermore, it is desirable that any such design achieve compactness and easy access for servicing.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a support structure for a lift car which will go at least part of the way toward meeting the foregoing desiderata in a simple yet effective manner, or which will at least provide the public with a useful choice.
Accordingly the invention consists in a support structure for a lift car, comprising a frame adapted to be connected to a lift hoisting mechanism to support the lift car, first and second pairs of parallel rails arranged substantially horizontally in a parallelogram configuration between the lift car and the frame, and first and second sets of followers arranged to roll or slide on said first and second pairs of rails respectively, said lift car being supported from said frame by way of said rails and followers in a manner such that one pair of rails is supported from the other pair of rails by way of at least one said set of followers and can traverse along the line of the other pair of rails allowing the lift car to move in any horizontal direction relative to the frame.
In the preferred form of the invention the frame incorporates portions located beneath the lift car, and the rails and followers are located beneath the lift car between the lift car floor and the frame.
It is preferred that the first pair of rails is substantially at right angles to the second pair of rails so that the parallelogram configuration becomes a square or rectangle.
In one particular embodiment of the invention the first pair of rails is mounted on the frame, the second pair of rails is mounted on the lift car, and the sets of followers are mounted back-to-back in four bogies, each bogie incorporating one of the first set of followers and one of the second set of followers.
In an alternative embodiment of the invention the first pair of rails is mounted on the frame, the second pair of rails is mounted on the first set of followers, and the lift car is mounted on the second set of followers.
In one form of the invention the followers are provided with wheels which roll on the rails and in a further form of the invention the followers may be linear bearings such as recirculating ball bearings which slide on appropriately profiled rails.
The invention also envisages the provision of positive centralising means adapted to centralise the lift car to a datum position relative to the frame when the lift is stationary at any particular floor of the building for loading or unloading.
In the preferred form of the invention the centralising means comprise a toggle brace arrangement mounted on the frame wherein the central knuckle of the toggle is movable transversely by a linear actuator causing the outer ends of the toggle to move toward and away from one another, to and from retracted and extended positions, and wherein the outer ends of the toggle mechanism are provided with V-shaped notches arranged to engage rotatable wheels protruding downwardly from the lift car when the toggle is in the extending position.
DESCRIPTION OF THE DRAWINGS
Notwithstanding any other forms that may fall within its scope, one preferred form of the invention will now be described by way of example only with reference to the accompanying drawings, in which:
FIG. 1 is a diagrammatic part sectional front elevation of a lift car and support structure according to a first embodiment of the invention;
FIG. 2 is a corresponding side elevation of the embodiment shown in FIG. 1;
FIG. 3 is an enlarged sectional partial front elevation corresponding to FIG. 2, the section being taken along the line III--III of FIG. 4;
FIG. 4 is a half cross-sectional enlarged side elevation of one side of the lift car support, taken along the line IV--IV of FIGS. 3 and 5;
FIG. 5 is a plan view taken partially in cross-section along the line V--V of FIG. 4;
FIG. 6 is an enlarged perspective view of a linear bearing unit which is an alternative to the unit used in the first embodiment of the invention;
FIG. 7 is a diagrammatic part sectional front elevation similar to FIG. 1 but showing a second embodiment of the invention;
FIG. 8 is a side elevation of the construction shown in FIG. 7;
FIG. 9 is perspective view of one of the bogies used in the second embodiment of the invention;
FIG. 10 is a plan view of a centralising device used in a lift car according to the invention, in the extended position; and
FIG. 11 is a similar view to FIG. 10 in the retracted position.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In the preferred form of the invention a lift car 1 is supported in a cage 2 which is typically connected to a lift hoisting mechannism by a cable 3. The cage is guided by guide rails at either side of the lift shaft (not shown) for vertical movement of the cage and hence the lift car within the lift shaft. The lift cage incorporates a lower support frame 4 which may be an integral part of the cage 2 as shown in FIGS. 1, 2, 7 and 8, or alternatively may be an additional portion which is bolted on to an existing lift cage to modify a lift which is already in service. The lower frame 4 is supported by the upright members 5 of the lift cage and also by diagonal braces 6.
The lift car is supported in the cage by a support structure comprising the frame 4, a first pair of rails 7, a second pair of rails 8, a first set of followers 9 arranged to roll or slide on the first pair of rails, and a second set of followers 10 arranged to roll or slide on the second pair of rails.
The first pair of rails are parallel to one another and similarly the second pair of rails are also parallel to one another and all of the rails are arranged substantially horizontally in a parallelogram configuration between the lift car 1 and the frame 4. In the preferred form of the invention the first pair of rails is at right angles to the second pair of rails so that the parallelogram comprises a rectangle or square.
In a first embodiment of the invention as shown in FIGS. 1 to 6, the first pair of rails 7 are mounted on the frame 4, for example by way of mounting trunions 11. The first set of followers 9 are free to slide or roll on the rails 7 and in turn are provided with mounting brackets 12 arranged to support the second pair of rails 8. The floor 13 of the lift car 1 is in turn supported on the second set of followers 10 by way of suitable support brackets 14.
The rails and followers may take any suitable form but in the embodiment shown in FIGS. 1 to 6 the rails are circular in section and the followers comprise linear bearings and preferably recirculating ball bearings.
Because the lift car is free to move in one horizontal direction by movement of the followers 10 on the rails 8 and in a different horizontal direction by movement of the followers 9 on the rails 7, it will be apparent that the lift car is free to move in any horizontal direction by compound movement of the respective sets of followers on their respective pairs of rails.
The followers and rails are provided with biasing means arranged to bias the position of the lift car to a central datum position, and in the preferred form of the invention the biasing means comprise helical compression springs 15 acting between one side of the followers and a suitable abutment in the form of a collar 16 on the rails. The characteristics of the springs 15 are chosen so that there is a relatively small biasing force toward the datum position at small displacements immediately adjacent the datum position, and so as to give a very low natural transverse vibration frequency in the order of 1 Hz of the lift car relative to the frame or cage.
As may be most clearly seen in FIG 3, the frame 4 may be provided as a separate component provided with upper mounting flanges 17 which enable the frame and the support structure mounted on the frame to be bolted or otherwise secured to the undersides of existing lift cages.
Although the invention has thus far been described with reference to a support structure wherein the first pair of rails are mounted on the frame and the second pair of rails are mounted for transverse movement on the first pair of rails, it will be apparent that this configuration may be totally inverted or that the second pair of rails may be mounted directly to the underside of the lift car. A further embodiment of the invention incorporating this latter configuration will now be described with reference to FIGS. 7 to 9. Like numerals are used to describe like components where these components are common to the embodiment shown in FIGS. 1 to 6.
In the preferred form of the invention as shown in FIGS. 7 to 9, the first pair of rails are mounted on the frame 4 and the second pair of rails on the underside of the lift car floor 13. The sets of followers are mounted back-to-back in a plurality of bogies 18 (as typically shown in FIG. 9), each bogie incorporating one of said first set of followers and one of said second set of followers. Four such bogies are provided located at the corners of the rectangle defined by the rails, and the followers incorporate wheels or rollers 19 having peripheries shaped to engage and follow the rails which are provided with corresponding profiles. For example in the configuration shown diagrammatically in FIG. 9, the wheels have plain flat peripheries and the rails, typically shown in cross-section at 20, are provided with rectangular section grooves 21 in which the wheels 19 run. It is preferred that the wheels are provided in tandem pairs with the pair of wheels 22 in the first set of followers being positioned to support the bogie 18 on the first pair of rails and the pair of wheels 23 in the second set of followers being positioned to support the second set of rails, and hence the floor of the lift car, on the bogies. In the form of bogie diagrammatically shown in FIG. 9, the first set of wheels are supported on cross arms 24 and the second set of wheels on cross arms 25, vertically spaced above and positioned at right angles to the cross arms 24 by a central column 26.
Although the invention has thus far been described with the lift car being supported by its floor 13 from a lower frame 4, it will be apparent that the entire support structure could be located above the lift car which is suspended from its roof.
It is desirable to provide limit stops to restrain the amplitude of movement of the lift car in any one direction which is typically no greater than 10 mm from a central datum. The limit stops may conveniently be provided in the form of brackets 27 on the lift cage 2 which support circular resilient collars 28. The lift car 1 is provided with pins 29 extending upwardly from the lift car within the collars 28 and provided with a radial clearance therebetween to allow the desired amplitude of motion of the lift car relative to the cage 2.
It is also desirable that the support mechanism be provided with a positive centralising device to centralise the position of the lift car to its datum positions when the lift car is stopped at a particular floor of a building for the entry or exit or passengers. Such a centralising device will now be described with reference to FIGS. 10 and 11 of the accompanying drawings.
The centralising device comprises a horizontal track 30 on which is slidably mounted a pair of trucks 31 which may typically be supported and guided for linear motion on the track by way of guide rollers 32. The trucks are provided with upwardly extending abutments 33 each having a V-shaped cross-section with the included angle of the V facing outwardly as shown in the drawings, conveniently formed from lengths of angle iron.
The motion of the trucks toward and away from one another is controlled by a toggle brace mechanism 34 having toggle arms 35 pivotally mounted to the trucks at their outer ends by way of vertical pivot pins 36 and pivotally connected to a central knuckle 37. The central knuckle of toggle is movable transversely by a linear actuator 38 causing the outer ends of the toggle and the abutments 33 to move toward and away from one another, to and from retracted and extended positions. The linear actuator 38 could conveniently comprise a worm and rack mechanism driven by an electric motor 39 but may be of any other known alternative such as a hydraulic piston and cylinder assembly.
The centralising device described above is mounted on the frame 4 so that the abutments 33 protrude upwardly to a position adjacent the underside of the lift cage floor 13. The underside of the lift cage floor is provided with two downwardly extending axles (not shown) on which are rotatably mounted wheels adapted to nestle in said V-shaped abutments when the abutments are in the extended position as shown in FIG. 10. The wheels are preferably ball races mounted on the downwardly extending vertical axles.
When the lift is moving between floors the centralising device is moved to the retracted position as shown in FIG. 11 so that the abutments 33 are clear of the ball races enabling the lift car to move transversely as previously described. Once the lift car reaches a floor and the doors are about to be opened, the linear actuator is actuated to move the toggle brace into the extended position as shown in FIG. 10, causing the ball races to roll on the arms of the angle iron abutments until they nestle in a predetermined centralised position within the V of each abutment.
In this manner a lift car support structure is provided which enables transverse vibrations in a horizontal plane to be absorbed by movement of the lift cage without transmitting that movement to the lift car and disturbing the occupants thereof. | A support structure for a lift car or elevator comprising two pairs of parallel rails and followers arranged in a horizontal parallelogram array between the lift car and support frame, such that compound movement of the followers on their respective rails allows the lift car to move in any horizontal direction to absorb transverse vibration due to misalignment of the vertical guide rails in the lift shaft. Also described are biassing devices arranged to lightly bias the lift car to a centralized horizontal position, and centralizing devices arranged to positively centralize the lift car for entry and egress at each floor. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation of PCT application No. PCT/EP2013/071471, entitled “DEVICE AND METHOD FOR PRODUCING STRUCTURED PLASTIC YARNS, PLASTIC YARN AND SPIRAL FABRIC MADE FROM PLASTIC YARN”, filed Oct. 15, 2013, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention is directed to a device for producing plastic spirals, a method for producing plastic spirals using such a device, a plastic spiral thus produced, and a spiral fabric consisting of such plastic spirals.
[0004] 2. Description of the Related Art
[0005] Textile clothing is found in a multitude of positions in machines for the production of fibrous web material, for example in paper or cardboard machines. In the forming section, the clothing facilitates sheet formation and dewatering; in the press section, absorption of water pressed from the fibrous web; in transfer positions, transfer into the next machine section; and in all sections it supports the fibrous web material.
[0006] In the dryer section of a fibrous web machine, clothing—normally referred to as dryer fabric—in addition to supporting the fibrous web, serves to increase the drying efficiency and the energy efficiency of the dryer section. The dryer fabrics must be thin and, at the same time, dimensionally stable with low stretch, must not mark the fibrous material, not carry along air, provide optimal moisture removal, must have optimal sheet release characteristics, and ensure a uniform drying profile across the width of the fibrous web material.
[0007] In particular, the last two characteristics are very strongly associated with the surface structure of the yarns forming the dryer fabric, whereas the characteristics of not marking the material and the high dimensional stability are also determinable through the cross sectional shape of the yarns.
[0008] Among other arrangements, today's dryer fabrics consist of spiral structures wherein plastic spirals are formed from plastic yarns which are deposited overlapping adjacent next to one another in such a way that the individual spirals can be connected with pintle wires. The yarns used for this type of spiral fabric structures are either round or are already provided with a cross sectional shape that deviates from the round shape which can be, for example, flat-oval or approximately rectangular.
[0009] A device to produce spirals from plastic yarns is known from WO09/130036 A1, comprising a winding device for the yarns which includes a guide rotatable around its axis, and having a forming body onto which the spirals are deposited by means of the winding device and from which they can be pulled. For the cross section of the respective yarn, a forming device that is rotatable with the winding device is assigned to the winding device. Accordingly, the produced spirals have a cross sectional shape that is determinable and can be adjusted to the aforementioned desirable characteristics of a dryer fabric.
[0010] A disadvantage with the produced plastic spirals is that although a change in the cross-sectional shape of the wire is achieved, its surface, in particular on a microscopic scale, is not altered. This results in the dryer fabrics becoming dirty quickly and, as a result, cannot fulfill their tasks. Deteriorations are noted in sheet release, in the drying efficiency due to poorer moisture removal, and variable moisture cross profiles in the fibrous web material.
[0011] What is needed in the art is a device and a method by which the yarns provided for the production of plastic spirals can be produced in a way that overcomes some of the known disadvantages of the prior art.
SUMMARY OF THE INVENTION
[0012] The invention provides a device and method by which the yarns provided for the production of plastic spirals can be influenced during the manufacturing process not only in their cross sectional shape, but also in their surface structure. An accordingly formed and structured yarn and a spiral fabric can produced from the yarn. The plastic spirals that can be formed and structured in one simultaneous process step. This can occur by accordingly shaped rolls mounted in a roller bearing assembly that, in addition to a suitable shape for cross section deformation of the previously extruded yarns, have a surface design which embosses a structure into the yarn surface.
[0013] The rolls can have a shape which differs, at least in regions, from a cylindrical shape and/or have a surface structure so that the surface design of the yarn can be discretionary in order to obtain the desired characteristics profile.
[0014] In one embodiment, a shell surface of the rolls—at least in regions—has the shape of single, dual or multiple hyperboloid of revolution, of cones or tapers. This provides an easily realizable engineering adaptation of existing devices for the production of plastic spirals for spiral fabrics.
[0015] The surface structures of the rolls can be in the form of strips, ribs, grooves, or wavy lines.
[0016] The strips, ribs, grooves or wavy lines can assume random positions between axially parallel to an axis of the rolls and parallel to a circumferential direction of the rolls.
[0017] According to another embodiment of the invention, it may be provided that the surface structures are designed in the form of protrusions of various shapes, or recesses of various shapes.
[0018] The surface structures may be distributed evenly or unequally over the surface of the rolls.
[0019] According to another embodiment of the invention the surface structures may be designed as a macro-structure and/or a micro-structure. The macro-structure can have a size range of 0.9 mm to 0.9 μm. The micro-structure can have a size range of 0.9 μm to 0.01 μm.
[0020] The depth of the surface structures can be 0.01 μm to 0.3 mm, such as 0.01 mm to 0.2 mm.
[0021] The distance between two adjacent surface structures may be 0.1 μm to 0.9 mm, or 0.01 mm to 0.6 mm.
[0022] The roughness in the region of the surface structure can be less than 0.3.
[0023] A method for the production of plastic spirals by winding plastic yarn into individual spirals that are inserted into each other, overlapping in cross direction on a work surface and are merged with pintle wires into flat structure can provide that, after being wound, the spirals are deposited next to one another on the work surface and are engaged with each other on this work surface through a joining device and are respectively connected with one another by the pintle wires. The spirals are thereby produced by the at least one winding device and after thermal forming are placed—due to a movement of the joining device —besides a guide rail on the work surface. The respectively subsequent spirals are placed on the work surface between the guide rail and the spirals previously placed on the work surface due to the movement of their winding device and the joining device which is located downstream from it. The at least one previously placed spiral is moved in a transverse direction on the work surface through movement of the joining device by a measure of the overlap, and the respectively last placed spirals are respectively connected with each other by at least one inserted pintle wire, and the yarn is formed in a roller bearing assembly. The roller bearing assembly is designed with at least two rolls with a roll nip between them through which the yarn is guided and a change of the outside shape and/or surface of the yarn occurs.
[0024] The change in the shape of the yarn can occur through an appropriate shape of the rolls mounted in the roller bearing assembly.
[0025] The change to the surface of the yarn can occur through embossing of a surface structure that is provided on at least one of the rolls, at least partially, into the yarn.
[0026] A plastic spiral for the use in dryer fabrics in the dryer section of a machine for the production of a fibrous web such as a paper or cardboard web can be produced according to the aforementioned method. The yarn forming the plastic spiral has a cross sectional shape deviating from a round shape and/or the yarn forming the plastic spiral has at least partial surface structuring.
[0027] The surface structuring can be in the form of strips, ribs, grooves, wavy lines, protrusions of various shapes and/or recesses of various shapes.
[0028] According to one embodiment of the invention, the strips, ribs, grooves or wavy lines can assume random positions between parallel to a direction of extension of the yarn and parallel to a circumferential direction of the yarn.
[0029] The surface structures may be distributed evenly or unequally over the surface of the yarn.
[0030] One embodiment of the invention provides that the surface structuring is done at least partially on one outside and/or on one inside of the plastic spiral after laying the yarn into the spiral shape.
[0031] The surface of the plastic spiral can have a roughness of less than 0.3.
[0032] A spiral fabric for use in a machine for the production of a fibrous web such as a paper or cardboard web, comprises a plurality of plastic spirals that are connected with one another by pintle wires. The plastic spirals are provided at least partially with a surface structuring which positively influences dirt resistance and sheet release characteristics of the spiral fabric, thus providing constant quality of the produced fibrous web.
[0033] According to another embodiment of the invention, plastic spirals having different surface structures can be combined in unequal or equal sequences, whereby the sheet release characteristics can be significantly improved.
[0034] The spiral fabrics according to the invention can be used in a multitude of locations in the paper machine, such as forming fabric or dryer fabric, but also as the base structure for a press felt.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:
[0036] FIG. 1 is a sectional view of a device for the production of plastic spirals according to the prior art;
[0037] FIG. 2A is a schematic view of an embodiment of a roller bearing assembly according to the present invention that can be used in the device shown in FIG. 1 ;
[0038] FIG. 2B is a schematic view of another embodiment of a roller bearing assembly according to the present invention that can be used in the device shown in FIG. 1 ;
[0039] FIG. 3A is a schematic view of a plastic spiral with a surface structure that can be produced using the devices shown in FIGS. 1-2 ;
[0040] FIG. 3B is a schematic view of another plastic spiral with a surface structure that can be produced using the devices shown in FIGS. 1-2 ;
[0041] FIG. 3C is a schematic view of yet another plastic spiral with a surface structure that can be produced using the devices shown in FIGS. 1-2 ; and
[0042] FIG. 4 is a schematic lateral view of an individual loop of a plastic spiral with embossed surface structures that can be produced according to the present invention.
[0043] Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate embodiments of the invention and such exemplifications are not to be construed as limiting the scope of the invention in any manner.
DETAILED DESCRIPTION OF THE INVENTION
[0044] Referring now to the drawings, FIG. 1 shows a strongly schematized sectional view of a device 1 for producing plastic spirals for production of paper machine clothing, in particular spiral fabrics for use in the dryer section of a paper or cardboard machine according to the current state of the art.
[0045] Such devices 1 are known so a detailed description of device 1 is omitted. The device is described only in regard to its invention-relevant components, in order to simplify understanding of the present invention.
[0046] Device 1 include a housing 2 where a roller bearing assembly 3 is disposed. The roller bearing assembly includes a first roll 4 and a second roll 5 between which a roll nip 6 is formed. In roll nip 6 , an already deformed yarn 7 can be seen that has been transformed into a longitudinal oval cross sectional shape from an original approximately round cross sectional shape in which it, for example, exits an extruder that is not illustrated.
[0047] First roll 4 is mounted adjustably in an adjustment device 8 , while second roll 5 is mounted stationary in housing 2 . The adjustment of the position and the drive of first roll 4 are possible via a drive 9 which is arranged suitably in housing 2 .
[0048] Rolls 4 and 5 that are mounted in roller bearing assembly 3 are smooth and cylindrical according to the current state of the art. Deformation of yarn 7 therefore occurs only by moving first roll 4 closer to second roll 5 by reducing roll nip 6 and a corresponding displacement of the still deformable plastic material of yarn 7 toward the outside.
[0049] The produced yarn 7 with altered cross section therefore has an altered cross section, but a smooth surface. Accordingly, the previously discussed properties of yarn 7 , or respectively of the dryer fabric produced from yarn 7 , are not satisfactory in regard to sheet release and dirt resistance.
[0050] Remedial action can be provided by modification of rolls 4 and 5 that are mounted in roller bearing assembly 3 . Such modified rolls 24 and 25 are illustrated in FIGS. 2A and 2B according to the present invention. In order to maintain clarity, only rolls 24 and 25 respectively are shown in FIGS. 2A and 2B , as well as yarn 7 .
[0051] In FIG. 2A , a combination is shown of a first roll 24 which has a double hyperbolic rotational shape with a second roll 25 which is cylindrical and which is provided with a surface structure 10 .
[0052] First roll 24 imparts a macroscopic structure to yarn 7 which, in this case, can produce a groove 11 in the longitudinal direction of the yarn, whereas second roll 25 provides yarn 7 with surface structuring 12 which is imparted into the material of yarn 7 by pressing into surface structure 10 of roll 5 .
[0053] Consequently, a yarn 7 is obtained which, on one top side and one bottom side can have differently designed surface shapes and structures. Depending on the orientation of yarn 7 in the subsequent plastic spiral, groove 11 can point inward or outward, and embossed surface structure 12 can point inward or outward.
[0054] FIG. 4 shows an example of a single loop of a plastic spiral in whose upper region only a surface structuring 12 is visible, whereas yarn 7 may, for example, be provided with groove 11 on the outside (not visible in FIG. 4 ).
[0055] In FIG. 2B , an additional embodiment of a roller bearing assembly 3 according to the present invention is shown, where both rolls 24 and 25 have a double hyperbolic rotational shape and accordingly impart a shape with grooves 11 onto the top and bottom side of yarn 7 .
[0056] First roll 24 moreover has a surface structure 10 which is shark skin like. This produces a corresponding surface structuring 12 on yarn 7 which provides excellent characteristics in regard to dirt and water resistance, as well as to flow properties of air and water. Such effects (for example the so-called Lotus-effect) are known from nature and are used in many ways technologically.
[0057] There are hardly any limits in regard to the shape of rolls 24 and 25 and to the arrangements of their surface structures 10 . Any combination of single, double or multiple hyperboloids of revolution, as well as combinations of conical, cylindrical or optional other geometrical shapes are possible.
[0058] Surface structures 10 can be in the form of strips, ribs, grooves or wavy lines and can assume positions parallel, tilted or diagonal relative to the roll axis, as far as to the circumferential direction of the rolls. Protrusions in any discretionary shape or recesses in any discretionary shape, even or uneven, can be distributed at least over regions over the surface of rolls 24 , 25 . Several surface structures 10 may also be combined on one of the rolls 24 , 25 . Moreover, it is possible to combine, for example, the rotational hyperbolic shape with a surface structure 10 .
[0059] Dimensioning of surface structures 10 can thereby be divided into a macro- and a micro-structuring which can be used individually or in combination with each other. The macrostructure may have a size range of 0.9 μm to 0.9 mm, whereas the microstructure can have a size range of 0.01 μm to 0.9 μm.
[0060] The depth of surface structures 10 can be 0.01 μm to 0.3 mm or 0.01 mm to 0.2 mm. A distance between two adjacent surface structures 10 can be 0.1 μm to 0.9 mm or 0.01 mm to 0.6 mm.
[0061] The roughness in the region of surface structures 10 can be less than 0.3 so that the surface roughness of yarns 7 is also less than 0.3.
[0062] Suitable limiting elements (not illustrated) in roll nip 6 can limit the width of squeezed yarn 7 and produce an almost rectangular cross sectional shape. By structuring these limiting elements, the sides of yarn 7 can also undergo targeted structuring.
[0063] FIGS. 3A , 3 B and 3 C illustrate examples of several plastic spirals 13 which together form a dryer fabric 14 . Plastic spirals 13 are held together in a generally known manner by pintle wires 15 .
[0064] As shown in FIG. 3A , the plastic spirals 13 can each be provided with an embossed groove 11 , as well as an overlaid surface structuring 12 .
[0065] As shown in FIG. 3B , the plastic spirals 13 can all be provided with a diagonally progressing groove-type surface structuring 12 .
[0066] As shown in FIG. 3C , a combination of two differently arranged plastic spirals 13 can be arranged always alternating. Spiral fabrics of this type can be produced in one work cycle wherein several spiral producing units are operated with different embossing units.
[0067] As already mentioned, FIG. 4 illustrates a single loop of a plastic spiral 13 which can be used in a dryer fabric 14 for a paper or cardboard machine which is provided in the upper region on its inside and in the lower region on its outside with a surface structuring 12 , as previously described. The diverse arrangement of surface structuring 12 may have a variety of consequences in regard to the performance of plastic spiral 13 or, respectively, subsequently in the dryer fabric. An improved dirt resistance on the inside of plastic spiral 13 results in greater uniform drying efficiency, since the open volume of the dryer fabric still remains intact even after prolonged use. Exterior surface structures 12 can improve the sheet release characteristics, in particular if differently structured plastic spirals 13 alternate with each other, as illustrated in FIG. 3C .
[0068] Different structuring can be provided on the outside and on the inside of plastic spiral 13 , thereby being able to achieve different characteristics. Transverse structuring of the inside simplifies insertion of pintle wires 15 , whereas with other suitable structuring the fixation of filler wires can be favored. At the same time, a modification can be provided on the outside that is different from the structuring on the inside, for example, with the objective to influence the sheet release characteristics or to reduce the contamination susceptibility.
[0069] Utilization of described plastic spirals 13 is possible in almost any paper machine clothing, such as dryer fabrics and former fabrics. Use as base structure for press felts is also conceivable and possible.
[0070] While this invention has been described with respect to at least one embodiment, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims. | A device for producing plastic spirals for use in a machine for producing a fibrous web includes at least two rolls between which an adjustable roll nip is formed. The rolls have a shape which differs in at least one region from a cylinder shape and/or have a surface structure in at least one region on the surface thereof. | 8 |
RELATED APPLICATION
This application claims priority to U.S. Provisional Patent Application Ser. No. 60/430,434 filed Dec. 3, 2002, and titled “Distributed Digital Antenna System,” which is commonly assigned and incorporated by reference herein.
TECHNICAL FIELD
The present invention relates generally to communications and particularly to communications through a distributed antenna system.
BACKGROUND
Various types of wireless communication systems have become prevalent around the world. For example, cellular communication systems cover most major metropolitan areas as well as major highways through remote areas. Cellular systems permit individuals with cellular handsets to communicate with base stations that are connected to the public switched telephone network (PSTN) or some other communication network.
As with any communication system, cellular systems can leave coverage “holes” where the signal from the base stations cannot reach. The holes can be in tunnels, valleys, city streets between tall buildings, or any other location where a radio frequency (RF) signal is blocked.
Placing additional base stations where these coverage holes are located is not always an option. Base stations tend to be very expensive due not only to the cost of the equipment but also because of land acquisition costs. Additionally, large base station antennas may not fit within an area either physically or aesthetically.
One solution to hole coverage is to use smaller remote antennas where coverage is needed but a base station is not warranted or desired. One problem with remote antennas, however, is that coaxial cable cannot be run long distances due to attenuation. Remote antennas are difficult to install along a highway or through a tunnel due to this attenuation problem. Using repeaters may not be an option since this only adds to the expense and complexity of the system. There is a resulting need in the art for a distributed antenna system that does not suffer from attenuation problems.
SUMMARY OF THE INVENTION
The embodiments of the present invention encompass a distributed digital antenna system that has a host unit for converting radio frequency signals to digital optical signals and digital optical signals to radio frequency signals. The digital optical signals are transmitted over an optical medium to a plurality of remote units that are daisy-chained along the optical medium. Each remote unit transmits an analog representation of the digital optical signals from the host unit and receives radio frequency signals that are converted by the remote unit to digital optical signals for use by the host unit.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a block diagram of one embodiment of a distributed digital antenna system of the present invention.
FIG. 2 shows a block diagram of another embodiment of a distributed digital antenna system of the present invention.
FIG. 3 shows a block diagram of one embodiment of a remote unit in accordance with the system of FIG. 1 .
FIG. 4 shows a block diagram of one embodiment of a remote unit in accordance with the system of FIG. 2 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The embodiments of the present invention provide a digital distributed antenna system that enables a communication system to fill coverage holes without the expense of additional base stations. This is accomplished by distributing a fiber optic cable through the area in which coverage is desired and tapping into the fiber at desired antenna locations.
The embodiments of the present invention refer to fiber optics as a means of communication between remote units and the host unit. However, any optical medium, such as a laser through the air, can be substituted for the optical fiber.
FIG. 1 illustrates a block diagram of one embodiment of a distributed digital antenna system of the present invention. The system has a base station ( 100 ) that communicates over an RF link using an antenna ( 110 ). The base station communicates over the RF link using any appropriate air interface standard. For example, the air interface standard comprises one of Advanced Mobile Phone System (AMPS), code division multiple access (CDMA), time division multiple access (TDMA), or Global System for Mobile communications (GSM) or any other appropriate air interface standard.
The RF link is made up of a forward link over which the base station ( 100 ) transmits to a subscriber unit wireless terminal ( 150 ). The subscriber unit ( 150 ) transmits back to the base station ( 100 ) over a reverse link. The subscriber unit ( 150 ) is either a mobile station or a fixed station such as in a wireless local loop system.
The base station ( 100 ) has the transmitters and receivers that enable the subscriber unit ( 150 ) to communicate with the public switched telephone network (PSTN) ( 130 ). In one embodiment, the base station also links the subscriber unit ( 150 ) to other subscriber units that are communicating with other base stations. In one embodiment, the base station ( 100 ) is connected to the PSTN through a mobile switching center that handles the switching of calls with multiple base stations.
A host unit ( 101 ) is connected to the base station ( 100 ) through an RF link ( 115 ). In one embodiment, this link ( 115 ) is a coaxial cable. Other embodiments use other types of connections such as an air interface or an optical fiber carrying digital RF signals. U.S. patent application Ser. No. 09/619,431, assigned to ADC Telecommunications, Inc. and incorporated herein by reference, discusses digital RF signals.
The host unit ( 101 ) is responsible for converting the RF signal from the base station ( 100 ) to an optical signal for transmission over an optical medium. The host unit ( 101 ) also converts a received optical signal to an RF signal for transmission to the base station ( 100 ). In other embodiments, the host unit ( 101 ) performs additional functions.
One or more remote units ( 105 - 108 ) are connected to the host unit ( 101 ) through an optical medium, such as fiber optic lines ( 120 and 125 ), in a daisy-chain arrangement. The remote units ( 105 - 108 ) are placed in locations that require additional signal coverage due to a lack of coverage by the base station ( 100 ). The remote units ( 105 - 108 ) communicate with subscriber units in a particular remote unit's coverage area over an RF link provided by the remote unit antennas ( 135 - 138 ).
For purposes of illustration, four remote units ( 105 - 108 ) are shown. However, alternate embodiments use other quantities of remote units. If only a small geographic area requires coverage, as few as one remote unit ( 105 ) is used. If a highway in a remote area requires additional coverage, more than four remote units are typically used.
The embodiment of FIG. 1 uses a separate fiber optic line for each direction of communication. Each fiber carries a different wavelength. For example, the fiber optic line ( 120 ) from the host unit ( 101 ) to the remote units ( 105 - 108 ) carries a wavelength of λ 1 . The fiber optic line ( 125 ) from the remote units ( 105 - 108 ) to the host unit ( 101 ) carries a wavelength of λ 2 . In alternate embodiments, each fiber carries the same wavelength.
The fiber optic line ( 120 ) from the host unit ( 101 ) to the remote units ( 105 - 108 ) carries the digital optical signal for transmission by the ( 105 - 108 ). The fiber optic line ( 125 ) from the remote units ( 105 - 108 ) carries a digital optical signal comprising the sum of the received signals from each of the remote units ( 105 - 108 ). The generation of this summation signal from the remote units is discussed subsequently.
FIG. 2 illustrates a block diagram of another embodiment of a distributed digital antenna system of the present invention. This system is similar to the embodiment of FIG. 1 except that the remote units ( 205 - 208 ) are connected to the host unit ( 201 ) over a single optical medium ( 220 ).
The system of FIG. 2 has a base station ( 200 ) that communicates over an RF link using an antenna ( 210 ). The base station can communicate over the RF link using any air interface standard. For example, the air interface standard may be code division multiple access (CDMA), time division multiple access (TDMA), or Global System for Mobile communications (GSM).
The RF link is made up of a forward link over which the base station ( 200 ) transmits to a subscriber unit ( 250 ). The subscriber unit ( 250 ) transmits back to the base station ( 200 ) over a reverse link. The subscriber unit ( 250 ) may be a mobile station or a fixed station such as in a wireless local loop system.
The base station ( 200 ) has the transmitters and receivers that enable the subscriber unit ( 250 ) to communicate with the public switched telephone network (PSTN) ( 230 ). The base station may also link the subscriber unit ( 250 ) to other subscriber units that are communicating with other base stations. In one embodiment, the base station ( 200 ) is connected to the PSTN through a mobile switching center that handles the switching of calls with multiple base stations.
A host unit ( 201 ) is connected to the base station ( 200 ) through an RF link ( 215 ). In one embodiment, this link ( 215 ) is a coaxial cable. Other embodiments use other types of connections such as an air interface or an optical fiber carrying digital RF signals.
The host unit ( 201 ) is responsible for converting the RF signal from the base station ( 200 ) to a digital optical signal for transmission over an optical medium. The host unit ( 201 ) also converts a received optical signal to an RF signal for transmission to the base station ( 200 ). In other embodiments, the host unit ( 201 ) performs additional functions.
One or more remote units ( 205 - 208 ) are connected to the host unit ( 201 ) through an optical medium, such as a fiber optic line ( 220 ), that is connected in a daisy-chain arrangement. The remote units ( 205 - 208 ) are placed in locations that require additional signal coverage due to a lack of coverage by the base station ( 200 ).
For purposes of illustration, four remote units ( 205 - 208 ) are shown. However, alternate embodiments use other quantities of remote units.
The embodiment of FIG. 2 uses a single fiber optic line ( 220 ) for communication both to and from the remote units ( 205 - 208 ). This is accomplished by the single fiber ( 220 ) carrying multiple wavelengths. For example, the fiber optic line ( 220 ) uses a wavelength of λ 1 for the digital signal from the host unit to the remote units ( 205 - 208 ). The fiber optic line ( 220 ) also carries a digital summation signal with a wavelength of λ 2 . This digital summation signal is the sum of the received signals from the remote units ( 205 - 208 ). The generation of this summation signal from the remote units is discussed subsequently.
FIG. 3 illustrates a block diagram of one embodiment of a remote unit ( 105 ) of FIG. 1 . Each of the remote units ( 105 - 108 ) of the embodiment of FIG. 1 are substantially identical in functional composition.
The remote unit ( 105 ) transmits and receives RF signals over the antenna ( 135 ). Both the receive and transmit circuitry is connected to the antenna ( 135 ) through a diplexer ( 301 ).
Alternate embodiments use other quantities of antennas. For example, one embodiment uses three antennas to cover three different sectors of an area.
An analog signal that is received on the antenna ( 135 ) is split off by the diplexer ( 301 ) to an analog-to-digital converter ( 305 ). The analog-to-digital converter ( 305 ) digitizes the received analog signal by periodically sampling the signal. The sampling generates a digital representation of the received analog signal.
The digitized received signal is input to a summer ( 315 ) to be added to the digitized signals from the preceding remote units in the daisy-chain. The input of the summer ( 315 ), therefore, is coupled to an output of a previous remote unit. The output of the summer ( 315 ) is a summation signal that is coupled to either the input of a subsequent remote unit or to the host unit. The host unit thus receives a summation signal that represents the sum of all the signals received by the remote units ( 105 - 108 ) of the system.
A digital signal from the host unit is coupled to a digital-to-analog converter ( 310 ). The digital-to-analog converter ( 310 ) takes the digital representation of an analog signal and converts it to the analog signal for transmission by the antenna ( 135 ).
Optical-to-Electrical converters ( 320 - 323 ) are located at the optical ports ( 330 and 335 ) of the remote unit ( 105 ). Each optical port ( 330 and 335 ) has an input and an output that are each coupled to an Optical-to-Electrical converter ( 320 - 323 ).
Since the remote unit ( 105 ) operates with electrical signals that are represented by the optical signals coming in through the optical ports ( 330 and 335 ), the Optical-to-Electrical converters ( 320 - 323 ) are responsible for converting the optical signals to electrical signals for processing by the remote unit ( 105 ). The Optical-to-Electrical converters ( 320 - 323 ) are also responsible for converting received electrical signals from electrical to an optical representation for transmission over the optical fiber.
FIG. 4 illustrates a block diagram of one embodiment of a remote unit ( 205 ) of FIG. 2 . Each of the remote units ( 205 - 208 ) of the embodiment of FIG. 1 is substantially identical in functional composition.
The remote unit ( 205 ) transmits and receives RF signals over the antenna ( 435 ). Both the receive and transmit circuitry are connected to the antenna ( 435 ) through a diplexer ( 401 ).
Alternate embodiments use other quantities of antennas. For example, one embodiment uses three antennas to cover three sectors of an area.
An analog signal that is received on the antenna ( 435 ) is split off by the diplexer ( 401 ) to an analog-to-digital converter ( 405 ). The analog-to-digital converter ( 405 ) digitizes the received analog signal by periodically sampling the signal. The sampling generates a digital representation of the received analog signal.
The digitized received signal is input to a summer ( 415 ) to be added to the digitized signals from the preceding remote units in the daisy-chain. The host unit thus receives a summation signal that represents the sum of all the signals received by the remote units ( 205 - 208 ) of the system.
A digital signal from the host unit is coupled to a digital-to-analog converter ( 410 ). The digital-to-analog converter ( 410 ) takes the digital representation of an analog signal and converts it to the analog signal for transmission by the antenna ( 435 ).
Optical-to-Electrical converters ( 420 - 423 ) are located at the optical ports ( 440 and 445 ) of the remote unit ( 205 ). Each optical port ( 440 and 445 ) has an input and an output that are each coupled to an Optical-to-Electrical converter ( 420 - 423 ).
Since the remote unit ( 205 ) operates with electrical signals that are represented by the optical signals coming in through the optical ports ( 440 and 445 ), the Optical-to-Electrical converters ( 420 - 423 ) are responsible for converting the optical signals to electrical signals for processing by the remote unit ( 205 ). The Optical-to-Electrical converters ( 420 - 423 ) are also responsible for converting received electrical signals from electrical to an optical representation for transmission over the optical fiber.
A wavelength division multiplexer (WDM) ( 430 and 431 ) is located at each optical port ( 440 and 445 ). The WDMs ( 430 and 431 ) perform the optical processing necessary to combine several optical signals having several wavelengths. The WDMs ( 430 and 431 ) also perform the optical demultiplexing necessary to split the multiple wavelengths of a single fiber to their own signal paths.
In summary, the distributed digital antenna system provides multiple daisy-chained antennas on a single medium such as optical fiber. The fiber can be tapped anywhere along its length multiple times to provide economical radio coverage in areas where a base station would be cost prohibitive.
Numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. | An optical medium, such as fiber, is tapped to provide an antenna port wherever radio service coverage is desired. Each antenna port is a bi-directional remote unit that receives a digital optical signal from a host unit and transforms the signal to a radio frequency signal for transmission by the remote unit. The remote unit receives radio frequency signals that are converted to digital signals and summed with signals from other remote units and converted to an optical signal for transmission to the host unit. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method of, and an apparatus for, sewing a slide fastener to a pair of fabric pieces, such as, for example, of a curtain, a tent or a lady's dress. It relates to the field of copending application for U.S. patent, Ser. No. 535,729 filed Sept. 26, 1983, now U.S. Pat. No. 4,497,270, dated Feb. 5, 1985.
2. Description of the Prior Art
As shown in FIGS. 1 and 2 of the accompanying drawings, a concealed slide fastener 1 comprises a pair of fastener stringers 4, 4, each stringer including a stringer tape 2 having an inner longitudinal edge folded on itself supporting a row of coupling elements 3 attached to the tape edge. The opposed rows of coupling elements 3, 3 are brought into and out of intermeshing engagement by a slider 5 which is slidably mounted on the rows of coupling elements 3, 3. The slider 5 has a slider body disposed on the coupling-element side of the concealed slide fastener 1 and a pull tab 6 pivotally connected to the slider body and projecting therefrom through the seam-like junction between the folded edges of the opposed stringer tapes 2,2.
Conventionally, for attaching the concealed slide fastener 1 to a pair of fabric pieces 7,7 (FIG. 3), on a sewing machine, the slider 5 is moved on the rows of coupling elements 3, 3 to a bottom end stop (not shown) to uncouple the opposed stringers 4,4 except at their bottom end portions. The uncoupled stringers 4, 4 are simultaneously sewn to the respective fabric pieces 7, 7 with sewn stitches 12, 12 along a pair of folding lines of the respective stringer tapes 2,2 as shown in FIG. 3. At that time, the folded tape edge of each stringer 4 is unfolded until the coupling elements 3 are erected with their head portions 10 directed downwardly, and the coupling elements 3 and the element-supporting tape edge of each stringer 4 are slidably received in a respective one of a pair of parallel downwardly opening grooves 8,8 in a presser foot 9 of the sewing machine. A pair of parallel sewing needles 11,11 are reciprocable through a pair of vertical holes in the presser foot 9. Also, during this sewing, the two stringers 4, 4 are superimposed over the respective fabric pieces 7,7 in such a manner that initially-outer (as seen in FIGS. 1 and 2) longitudinal edges of the opposed stringer tapes 2,2 are directed inwardly, i.e. toward each other.
This sewing operation is continued until the sewing stiches 12, 12 reach a position immediately short of the slider 5 disposed adjacent to the bottom end stop (not shown) of the slide fastener 1. As a result, the two stringers 4, 4 have been sewn to the respective fabric pieces 7,7 leaving the lower end portions of the stringers 4, 4 not sewn and hence floating from the fabric pieces 7,7.
As shown in FIGS. 4, 5 and 6, the sewn fabric pieces 7,7 are folded back on themselves about the sewn stiches 12, 12 as the two stringers 4,4 are progressively coupled together by moving the slider 5 from the bottom end stop (not shown) to a pair of top end stops (not shown) to close the concealed slide fastener 1. At that time, in order for their correct coupling, the two stringers 4, 4 need to assume proper twisted positions that are in mirror symmetry (FIG. 5).
Practically, however, because the lower end portion of the sewn slide fastener 1 is not sewn and hence floating from the fabric pieces 7,7, the opposed stringers 4,4 would tend to assume an improper twisted position that is not in mirror symmetry (FIG. 7), thus causing portions of the fabric pieces 7,7 to bulge inwardly between the two stringers 4,4 (FIG. 8). The bulged portions of the fabric pieces 7,7, can be caught by the slider 5 during the coupling of the two stringers 4,4; in such occurrence, the coupling of the two stringers 4,4 must be restarted after removing the caught fabric pieces 7,7 from the slider 5, which is laborious, time-consuming, and annoying.
Accordingly, this conventional method causes problems in the case where a plurality of the concealed slide fasteners 1 are successively sewn to successive pairs of the fabric pieces 7,7 and in which the sewn concealed slide fasteners 1 are temporarily stacked and are then supplied one after another to a finishing station where the opposed stringers 4,4 of each concealed slide fastener 1 are coupled by moving the slider 5.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method and apparatus for sewing a slide fastener to a pair of fabric pieces, in which a pair of opposed fastener stringers with the fabric pieces sewn thereto can be coupled together smoothly and quickly without occurrence of any objectionable inward bulge of the fabric pieces between the opposed stringers.
Another object of the present invention is to provide a method and apparatus for sewing a plurality of slide fasteners one after another to successive pairs of fabric pieces, in which a pair of opposed fastener stringers of the individual slide fastener with the fabric pieces sewn thereto can be coupled together smoothly and quickly without occurrence of any objectionable inward bulge of the fabric pieces between the opposed stringers.
Other objects, features and additional advantages of the present invention will become manifest to those versed in the art upon making reference to the detailed description and the accompanying drawings in which a preferred embodiment incorporating the principles of the present invention is shown by way of illustrative example.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary perspective view of a concealed slide fastener;
FIG. 2 is a transverse cross-sectional view taken along line II--II of FIG. 1;
FIG. 3 is a transverse cross-sectional view of a pair of uncoupled and unfolded fastener stringers, illustrating the manner in which the two stringers are sewn to a pair of fabric pieces, respectively, on a sewing machine;
FIG. 4 is a transverse cross-sectional view of the opposed stringers sewn to the respective fabric pieces and coupled together by a slider;
FIG. 5 is a fragmentary perspective view of the concealed slide fastener sewn to the fabric pieces, with the opposed stringers uncoupled;
FIG. 6 is a fragmentary perspective view of the sewn slide fastener of FIG. 5, closed by the slider;
FIGS. 7 and 8 are views similar to FIGS. 5 and 6, respectively, illustrating the prior problem;
FIG. 9 is a fragmentary perspective view of a sewing apparatus embodying the present invention;
FIG. 10 is another perspective view, with parts omitted, of the apparatus shown in FIG. 9.
FIG. 11 is a side elevational view, with parts omitted of the apparatus, showing a slider-moving unit in detail;
FIG. 12 is a fragmentary side elevational view, on a reduced scale, of FIG. 11;
FIG. 13 is a view similar to FIG. 12, illustrating the operations of a gripping mechanism and a stacker;
FIG. 14 is an enlarged perspective view, with parts omitted, of the slider-moving unit;
FIGS. 15 to 17 are side elevational views of FIGS. 14, illustrating the operation of the slider-moving unit;
FIGS. 18A and 18B are cross-sectional views illustrating the operation of a brake;
FIGS. 19A to 19F are plan views of a concealed slide fastener, each illustrating successive steps of the present sewing method relative thereto;
FIGS. 20A to 20G are side elevational views corresponding to FIGS. 19A to 19F, illustrating the sequence of steps of operation of the apparatus;
FIG. 21 is a fragmentary plan view of a concealed slide fastener sewn to the fabric pieces, with the opposed stringers uncoupled;
FIG. 22 is a perspective view of FIG. 21;
FIG. 23 is a fragmentary plan view of the concealed slide fastener of FIG. 21, showing the slide fastener fully closed;
FIGS. 24A-24D are plan views of a non-concealed, or exposed, slide fastener illustrating successive steps of the present sewing method.
FIG. 25 is a cross-sectional view taken along the line XXV--XXV of FIG. 24.
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 9 through 13 show an apparatus for sewing a concealed slide fastener 1 to a pair of fabric pieces 7,7.
As shown in FIG. 9, the apparatus generally comprises a table 13, a sewing machine 15 mounted centrally on the table 13 and defining a sewing station 14, a fabric guide 16 supported on the table 13 upstream of the sewing station 14, a slide-fastener guide 17 supported on the table 13 and disposed above the fabric guide 16, a gripper mechanism 18 mounted on the table downstream of the sewing station 14 for horizontal linear movement, a stacker 19 disposed beneath the gripper mechanism 18, a sewn-product guide 20 disposed downstream of the sewing station 14 for vertical movement, and a slider-moving unit 21 (FIGS. 10 and 11) disposed beneath the sewn-product guide 20 for horizontal linear movement.
The sewing machine 15 may be a conventional type on the market. It includes a presser foot 9, a pair of feed dogs (not shown), and a pair of sewing needles 11,11. As shown in FIG. 3, the presser foot 9 has in its bottom surface a pair of parallel grooves 8, 8, each receptive of an inner longitudinal edge of the respective stringer tape 2 together with a row of coupling elements 3 attached thereto. Upon depression of a start button (not shown), the presser foot 9 is lowered and then the sewing of the concealed slide fastener 1 and the fabric pieces 7,7 in "lock stitch" takes place. This lock-stich sewing is followed by back-tucking, cutting the sewing threads and raising of the presser foot in this order. The details of the sewing machine 15 itself are not pertinent here and its detailed description is omitted for clarity. As better shown in FIGS. 9 AND 10, the fabric guide 16 includes a pair of transparent horizontal guide plates 22, 22 spaced from the upper surfaces of the table 13 by a gap substantially equal to the thickness of the individual fabric piece 7, and a pair of guide rods 23, 23 mounted on the front or upstream side of the table 13. The pair of convergent guide rods 23, 23 lie in a horizontal plane substantially coplanar to the upper surface of the table 13. As the pair of fabric pieces 7, 7 are supplied to the sewing station 14, each fabric piece 7 is supported on the respective guide rod 23 and is then introduced into the gap between the corresponding guide plate 22 and the table 13.
As shown in FIGS. 9, 10, 12 and 13, the slide-fastener guide 17 includes an elongated flanged guiding plate 24 sloping downwardly toward the sewing station 14 and an elongated flanged auxiliary guiding plate 28 disposed upstream of the guiding plate 24 and sloping upwardly toward the guide plate 24, for guiding the substantially uncoupled stringers 4, 4 over the two guiding plates 24,28.
As shown in FIG. 10, the slide-fastener guide 17 also includes a pair of spaced track bodies 25,25 mounted on the guiding plate 24 at one end thereof adjacent to the sewing station 14 for guiding the respective coupling element rows 3,3 in such a manner that each coupling element row 3 assumes an erected position. A slider detector 26 is mounted on the guiding plate 24 and is pivotable vertically between the two track bodies 25,25 when the slider 5 on the concealed slide fastener 1 passes through the space between the two track bodies 25,25. The detector 26 is associated with a microswitch 27 which is operative, in response to the pivotal movement of the detector 26, to terminate the advance of the slide fastener 1.
The purposes of the gripper mechanism 18 are to keep the tension of both the slide fastener 1 and the fabric pieces 7,7 to a constant degree during the sewing, thus not only causing a uniform rate of sewing but making the sewn stiches 12, 12 aligned with the respective folding lines of the opposed stringers 4,4. The gripper mechanism 18 also serves to quickly discharge the sewn product, i.e., the slide fastener 1 with the fabric pieces sewn thereto.
As shown in FIGS. 9, 11, 12 and 13, the gripper mechanism 18 includes a pair of laterally spaced grippers 29,29, each gripper 29 being composed of an upper grip member 33 and a lower grip member 30. The lower grip member 30 is secured to a horizontal connector 31 in the form of a rod and is disposed slightly above the upper surface of the table 13. The upper grip member 33 is pivotally connected to the connector 31 near the downstream end of the lower grip grip member 30 by a pin 32. The upper grip member 33 is also connected to an air cylinder 36 via a link 34 which is connected to a piston rod 35 of the air cylinder 36. Two such air cylinders 36 are pivotally mounted on the connector 31 remotely from the grippers 29,29. Upon energization or de-energization of the two air cylinders 36,36, each piston rod 35 projects or is retracted to close or open its respective gripper 29.
Fixed to the downstream side of the sewing machine 15 is a holder 37 from which a guide rail 38 extends horizontally in the direction of discharging the sewn product. A free end of the guide rail 38 is fixed to a bracket 40 supported by a hanger rod 39. A slider 41 is slidably mounted on the guide rail 38. As better shown in FIGS. 12 and 13, an endless belt 44 is wound about a pair of pulleys 42,43 rotatably mounted on the holder 37 and the bracket 40, respectively, the endless belt 44 being fixed to the slide 41. The pulley 42 is connected to a servo motor (not shown) which drives the slide 41 selectively forwardly (downstream) and backwardly (upstream) and which changes the rate of movement of the slide 41 depending on the load. The downstream end of the connector 31 of the gripper mechanism 18 is integrally connected to a transverse shaft 45 rotatably supported by the slide 41.
The backward or upstream movement of the slide 41 is limited by a stop (not shown) projecting therefrom and engageable with the holder 37; thus the backward movement of the two grippers 29, 29 terminates in a retracted position close to the sewing station 14. At that time, the approach of the slide 14 is detected by a proximity switch (not shown) which issues a signal to reduce the rate of rotation of the non-illustrated servo motor, and the arrival of the slide 41 is detected by a limit switch (not shown) which has an actuator engageable with the non-illustrated stop and which is responsible to this engagement to issue a signal to terminate the rotation of the non-illustrated servo motor. The forward or downstream movement of the slide 41 is limited by a contact member 48 extending therefrom and engageable with an actuator of a microswitch 47 which is adjustably mounted on a support rod 46 extending between the holder 37 and the bracket 40 in parallel relationship to the guide rail 38.
Upon its actuation, the microswitch 47 produces a signal to stop the rotation of the servo motor, thus terminating the forward movement of the slide 41. As a result, the forward movement of the two grippers 29, 29 terminates in an advanced position, which is adjustable by changing the position of the microswitch 47 on the support rod 46.
The transverse shaft 45 is operatively connected to a drive, such as a motor or an air cylinder, for turning the transverse shaft 45 through a predetermined angle about its axis. In response to clockwise turning of the transverse shaft 45, the connector 31 of the gripper mechanism 18 is angularly movable about the transverse shaft 45 in the direction of an arrow b from the position (horizontal), of FIG. 12 to the position (vertical in this embodiment) of FIG. 13. This arrangement is particularly useful when a relatively long sewn product 49 is to be discharged without elongating the guide rail 38.
As shown in FIGS. 9, 10, 12 and 13, the stacker 19 is disposed beneath the gripper mechanism 18 for receiving the successive sewn products 49 (released from the gripping mechanism 18 as described below) one over another and for discharging a stack of the sewn products 49 out of the apparatus when the stack reaches a predetermined amount.
The stacker 19 includes a generally T-shaped hanger having a horizontal pipe 50 connected to an upper end of an arm 51 pivotally mounted on a base beneath the table 13. An air cylinder 52 is pivotally supported by the base, and a piston rod 53 of the air cylinder 52 is pivotally connected to the arm 51 at a midportion thereof. In timed relation to the forward movement of the two grippers 29, 29, the piston rod 53 of the air cylinder 52 projects to cause the stacker 19 to pivotally move in the direction of an arrow d in FIG. 13 from a retracted position (solid lines) to an advanced position (dash-and-dot lines) where the sewn product 49 released from the grippers 29, 29 is received on the transverse pipe 50. Thereafter, when the piston rod 53 of the air cylinder 52 is retracted, the stacker 19 is returned in the direction of an arrow e in FIG. 13 to its original or retracted position, with the sewn product 49 hanging on the transverse pipe 50.
As shown in FIGS. 10 and 11, the finished-product guide 20 is disposed downstream of the sewing station 14 and is vertically movable in the direction of arrows f and g by means of an air cylinder 54 supported by the holder 37. The finished-product guide 20, as shown in FIGS. 18A and 18B, has a downwardly opening guide channel 55. When the sewn product 49 is pulled forwardly by the gripper mechanism 18, the sewn-product guide 20 is lowered from the dash-and-dot-line position to the solid-line position in FIG. 18A and the slider 5 (disposed at the lower end portion of the sewn product 49) is guided along the guide channel 55 of the guide to the slider-moving unit 21. While the slide fastener 1 is being sewn to the pair of fabric pieces 7,7, the guide 20 is in raised position, as shown in FIG. 10, so as not to obstruct the movement of the gripper mechanism 18.
The slider-moving unit 21, as shown in FIGS. 10 and 11, is disposed immediately downstream of the sewn-product guide 20 for linear movement to move the slider 5 from the bottom end stop (not shown) of the sewn slide fastener 1 toward the top end stops (not shown) to couple the opposed stringers 4,4 through a predetermined length. As a result, the slider 5 has been moved to the region where the slide fastener 1 is sewn to the fabric pieces 7,7.
The thus partly closed product 49 is discharged out of the apparatus, and then the slider 5 can be moved all the way to the top end stops of the slide fastener 1 smoothly to provide a fully closed concealed slide fastener 1 sewn to a pair of fabric pieces 7,7.
As better shown in FIGS. 14 to 17, the slider-moving unit 21 includes a slider catch 56 of a generally C-shape opening backwardly for receiving the slider 5, and a retainer 57 pivotally mounted on a lower portion of the catch 56 for retaining the slider 5 in the catch 56. The catch 56 has a support rod 58 extending substantially downardly (FIGS. 14, 16, and 17) from the lower portion of the catch 56 at an angle thereto and terminating in a block on which an air cylinder 59 is pivotally mounted. Piston rod 60 of the air cylinder 59 is pivotally connected to the retainer 57. As the piston rod 60 of the air cylinder 59 projects (FIGS. 17), the retainer 57 is pivotally moved counterclockwise from the position of FIG. 16 to the position of FIG. 17 to push the slider body 5 against the catch 56, thus preventing the slider 5 from being removed from the catch 56. On the contrary, as the piston rod 60 of the air cylinder 59 is retracted (FIG. 16), the retainer 57 is pivotally moved clockwise from the position of FIG. 17 to the position of FIG. 16 so that the slider 5 can be removed from the catch 56.
As shown in FIG. 11, a slide 62 is slidably mounted on a pair of parallel horizontal guide rails 61,61 which is supported by the base (of the apparatus) beneath the table 13. An endless belt 66 is wound around a pair of small-sized upper pulleys 63,64 and a large-sized lower pulley 65 (all of the pulleys are rotatable on the base) and is fixed to the slide 62. The two small-sized pulleys 63, 64 are disposed between the two guide rails 61,61 and are spaced away from each other along the guide rails 61, while the large-sized pulley 65 is disposed below the guide rails 61.
The large-sized pulley 65 has a coaxial pinion 70 meshing with a rack 68 formed on a piston rod 69 of an air cylinder 67 which is pivotally supported by the base. As the pinion 70 and thus the large-sized pulley 65 is rotated counterclockwise in response to extension of the rack piston rod 69 of the air cylinder 67, the slider 62 is moved forwardly leftwardly away from the sewing station 14 along the guide rails 61,61. Reversely, as the large-sized pulley 65 is rotated clockwise in response to shrinking of the racked piston rod 69 of the air cylinder 67, the slider 62 is then moved backwardly, i.e., rightwardly toward the sewing station 14 along the guide rails 61,61.
The slider catch 56 is pivotally mounted on the slide 62 and is reciprocable, in response to the reciprocating movement of the slide 62, for pulling the slider 5 forwardly along the opposed stringers 4,4 to close the sewn slide fastener 1 while the opposite end portions of the slide fastener 1 is held in position in a manner described below.
The slide 62 has a pair of parallel support rods 71, 71 extending downwardly from a lower end portion of the slide 62 and interconnected at their lower ends by a horizontal connector 72. An air cylinder 73 is pivotally supported centrally on the horizontal connector 72, and a piston rod 74 of the air cylinder 73 is pivotally connected to the slider catch 56. As the piston rod 74 of the air cylinder 73 is retracted (FIG. 15), the catch 56 is pivotally moved counterclockwise from the position of FIG. 16 to the position of FIG. 15 below the table 13 so as not to impede not only the movement of the gripper mechanism 18 but the discharging of the sewn-product 49. Reversely, as the piston rod 74 of the air cylinder 73 is extended, the catch 56 is pivotally moved clockwise from the position of FIG. 15 to the position of FIGS. 16 and 17 to project above the upper surface of the table 13. The slider 5 is received in the catch 56 (FIG. 16) and is then retained therein by the retainer 57 (FIG. 17), whereupon the forward or downstream movement of the catch 56 is started.
As shown in FIG. 11, the brake 75 is supported on the pair of guide rails 61,61 at a fixed position adjacent to their upstream ends to temporarily stop the forward movement of the sewn product 49 to thereby facilitate the forward movement of the slider 5 on the sewn slide fastener 1 by the slider-moving unit 21.
As better shown in FIGS. 18A and 18B, the brake 75 includes a bracket 76 fixed to the guide rails 61,61, an air cylinder 77 supported by the bracket 76, and a pressing member 79, in the form of a thin plate (FIGS. 20A to 20G), to which a piston rod 78 of the air cylinder 77 is connected. As the piston rod 78 of the air cylinder 77 is extended, the pressing member 79 is raised in the direction of an arrow h from the position of FIG. 18A to the position of 18B for pressing the bottom end portion of the slide fastener 1 against the lower surface of the product guide 20. To the contrary, as the piston rod 78 of the air cylinder 77 is retracted, the pressing member 79 is returned to its original or lowered position (FIG. 18A) for releasing the sewn product 49.
The manner in which a concealed slide fastener 1 is sewn to a pair of fabric pieces 7,7 on the apparatus of FIGS. 9-17 and 18A-18B will be described hereinbelow in connection with FIGS. 19A-19F and 20A-20G.
As shown in FIG. 19A, before the start of sewing work, a pair of fabric pieces 7,7 is introduced into the sewing station 14 (only the two sewing needles 11,11 are illustrated in FIGS. 19A-19F), while a concealed slide fastener 1 is fully opened by moving the slider 5 and then the uncoupled stringers 4,4 are turned upside down through the entire length of the slide fastener 1 except the bottom end portion thereof. Thus, the two turned stringers 4,4 assume twisted positions in mirror symmetry. The concealed slide fastener is introduced into the sewing station 14, with the opposed stringers 4,4 superimposed over the respective fabric pieces 7,7.
More specifically, in introducing the fabric pieces 7,7 into the sewing station 14, each fabric piece 7 passes over the respective guide rod 23 and then through the gap between the corresponding guide plate 22 and the upper surface of the table 13, as shown in FIG. 9. On the other hand, the concealed slide fastener 1 is opened manually and is then placed over the guide plate 24 while turning the uncoupled stringers 4,4 upside down, as shown in FIG. 9. Then the leading end portion of each stringer 4 is introduced into the sewing station 14 via the respective track body 25. In the sewing station 14, the leading end portion of each stringer 4 is superimposed over the respective fabric piece 7 in such a manner that the coupling elements 3 are erected with the head portions 10 directed downwardly. At that time, as shown in FIG. 11, the gripper mechanism 18 is disposed at a position near the presser foot 9 in the sewing station 14, with each gripper 29 open. The sewn-product guide 20 is in raised position so as not to interfere with the gripper mechanism 18, as shown in FIG. 11. The slide-moving unit 21 is in retracted position near the sewing station 14, the slider catch 56 being retracted below the table 13. The brake 75 is also lowered or retracted below the table 13.
When a start button (not shown) is depressed, the presser foot 9 and the sewing needles 11,11 are lowered to start sewing work. As the sewing work progresses, both the leading end portion of each fabric piece 7 and the leading end portion of the corresponding stringer 4 are advanced between the upper and lower grip members 33, 30 of the respective gripper 29, as shown in FIG. 9B. The arrival of the leading ends of the fabric pieces 7,7 and the stringers 4,4 is detected by a photosensor (not shown) disposed at a suitable position in the sewing station 14. The photosensor is responsive to this arrival to issue a command signal to the air cylinder 36, wherupon the piston rod 35 is extended to cause each gripper 29 to grip the superimposed end portions of the respective fabric piece 7 and the corresponding stringer 4, as shown in FIG. 20A. The grippers 29 pull the sewn product 49 forwardly to discharge the same from the sewing station 14 under a constant tension smaller than the tension under which the sewn product 49 is advanced by the feed dog (not shown) of the sewing machine 15. This discharging tension is automatically controlled by the non-illustrated servo motor that is the drive source for moving the slider 41 of the gripper mechanism 18.
When the grippers 29,29 as the sewing work further progresses, are removed from the region where both the sewn-product guide 20 and the slider-moving unit 21 are located, the sewn-product guide 20 is lowered and the slider catch 56 of the slider-moving unit 21 projects above the upper surface of the table 13, as shown in FIGS. 20B and 20C.
Subsequently, when the slider 5 disposed at the bottom end portion of the slide fastener 1 arrives at the slider detector 26, the detector 26 is pivotally moved upwardly to actuate the microswitch 27 associated therewith, whereupon the microswitch 27 issues a command signal to the sewing machine 15 to start back tucking. The sewing threads are cut and the presser foot 9 is then raised to terminate the operation of the sewing machine 15. As shown in FIG. 19C, the sewn stitches 12 extend from the leading end of the slide fastener 1 and terminate just short of the slider 5 disposed at the bottom end portion of the slide fastener 1, thus leaving the bottom end portions of the opposed stringers 4,4 not sewn, and hence floating, from the fabric pieces 7,7.
After the sewing operation of the sewing machine 1 is stopped, the gripper mechanism 18 is continued to discharge the sewn product 49 that has been removed from the sewing station 14.
With continued discharging of the sewn product 49 by the gripper mechanism 18, the bottom end portion of the sewn slide fastener 1, including the slider 5, is introduced into the sewn-product guide 20. Then the slider 5 of the sewn slide fastener 1 is blocked or caught by the slider catch 56 of the slider-moving unit 21, as shown in FIG. 20D. This blocking is detected by a photosensor (not shown) which then issues a command signal to energize the air cylinder 59, (FIGS. 16 and 17), causing the retainer 57 to pivot to keep the slider body 5 in the catch 56.
Upon receipt of the slider 5 in the catch 56, the forward movement of the gripper mechanism 18 is stopped and the operation of the brake 75 is started. Thus, the leading end of the sewn product 49 is held in position by the grippers 29, 29 and the bottom end portion of the slide fastener 1 is held in position by the brake 75, giving the concealed slide fastener 1 a constant tension.
While the sewn product 49 is thus kept from moving, as shown in FIGS. 19E and 20E, the slider-moving unit 21 is moved fowardly by the action of the air cylinder 67 (FIG. 11) to pull the slider 5 along the uncoupled stringers 4,4 to partly close the sewn slide fastener 1. This pulling is continued until the slider 5 is moved into the region where each stringer 4 and the corresponding fabric piece 7 are sewn. Then, as shown in FIG. 20F, the retainer 57 is returned to its original or retracted position to release the slider 5 and the slider catch 56 is retracted below the table 13, during which time the brake 75 is continued to be operative.
Thereafter, as shown in FIGS. 19F and 20G, the brake 75 is rendered inoperative to release the trailing end of the sewn product 49, while the gripper mechanism 18 is continued to discharge the sewn product 49. More specifically, in discharging the sewn product 49, when the contact member 48 on the slide 41 of the gripper mechanism 18 hits the actuator of the microswitch 47, a command signal is issued from the switch 47 to stop the servo motor which drives the endless belt 44. The discharging of the sewn product 49 of the gripper mechanism 18 is terminated. Then the connector 31 is pivotally moved on the slide 41 to direct downwardly, during which time the stacker 19 is pivotally moved, by the action of the air cylinder 52, forwardly of the base beneath the table 13, as shown in FIG. 13. The grippers 29 at the end portion of the connector 31 are opened to release the sewn product 49, which thus falls onto the transverse pipe 50 of the stacker 19. The stacker 19 and the gripper mechanism 18 are returned to their original or upstream positions. The slider-moving unit 21 is also returned to its original or upstream position near the station 14, during which time the slide-moving unit 21 remains retracted below the table 13. And the product guide 20 is returned to its raised position. Now the apparatus is in condition for start of the next cycle of the sewing operation, and a single cycle has been completed.
FIGS. 21 and 22 show the sewn product including the concealed slide fastener 1 sewn to the pair of fabric pieces 7,7 according to the present invention. In this sewn product, the opposed coupling element rows 3,3 can be coupled smoothly and quickly by manually moving the slider 5 toward the top end stops (not shown), as shown in FIG. 23, during which time the opposed stringers 4,4 are progressively turned back in mirror symmetry.
In the sewn product obtained by the present method, since the slider is disposed into the region where each concealed fastener stringer and the corresponding fabric piece are sewn, smooth and quick coupling of the opposed stringers can be achieved simply by manually pulling the slider. Accordingly, the present method is particularly useful for the case in which a plurality of concealed slide fasteners are sewn to successive pairs of the fabric pieces and in which the sewn products are temporarily stacked and then supplied one after another to a finishing station where the opposed fastener stringers of each concealed slide fastener are coupled by manually moving the slider.
With the apparatus constructed according to the present invention, partly because the slider-moving unit is retractable below the upper surface of the table so as not to interfere with the gripper mechanism, it is possible to sew a plurality of concealed slide fasteners successively to successive pairs of fabric pieces without impeding the sewing and discharging operations, causing an improved rate of production.
The apparatus of the invention is especially useful in the sewing of concealed slide fasteners, as described above. However, it is clear that exposed slide fasteners may as well be sewn with the apparatus of the invention. Such assembly is illustrated in FIGS. 24A-24E. As there shown, tapes 2',2' of stringers 4',4' are aligned for sewing along stich lines 12',12' located further from the coupling element rows 3',3', then in the concealed slide fasteners embodiment of FIGS. 19A-F. An exposed type fastener is employed, so that coupling element rows 3' face downwardly, toward the fabric 7', 7' in the initial setup shown in FIG. 24A. As a result, when the sewing is completed the fabric 7',7' does not meet, leaving the coupling element rows and tapes exposed as shown in FIGS. 24D and 24E. The apparatus and method are in other respects the same, providing a substantially improved, more rapid system for fastener sewing and assembly.
Although various modifications may be suggested to those versed in the art, it should be understood that we wish to embody within the scope of the patent granted hereon, all such embodiments as reasonably and properly come within the scope of our contribution to the art; and intend to be limited only by the hereinafter appended claims. | An improved method and apparatus for assembling fastening elements to fabric pieces including sewing separated fastener stringer tapes to respective fabric pieces pulling the sewn element downstream as the sewing proceeds, and partially combining the separated stringer tapes by pulling the slider downstream through a portion of the length of the fastener elements while retarding movement of the stringer tapes at their upstream ends. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a bridge sleeper supporting pad to be interposed between a bridge beam and a bridge sleeper so as to receive the bridge sleeper laid on the bridge beam in a railway track.
2. Description of the Related Art
As disclosed in Japanese Unexamined Patent Publication JP-A 2005-113984, a bridge sleeper adapted for placement on a bridge beam having a rivet has been conventionally known.
As disclosed in JP-A 2005-113984, it is necessary to form a recess tailored to fit with a projection of the rivet on a top end of the bridge beam on a back face of the bridge sleeper, which requires a lot of labor in processing.
Also known is a bridge sleeper in which an enhancing plate made of wood is fitted into a back face of the bridge sleeper at a position where it is laid on a bridge beam, in such a manner that substantially a half of a thickness of the enhancing plate projects downward from the bridge sleeper, and this enhancing plate is laid in abutment with the bridge beam. However, also on the back face of the enhancing plate, it is necessary to form a recess tailored to fit with a projection of a rivet on a top end of the bridge beam, so that time and labor are required in processing. In replacing with a new enhancing plate when the enhancing plate decays from the back face, it is necessary to form a recess tailored to fit with the projection of the rivet of the bridge beam on the back face of the new enhancing plate, so that it also takes time and labor in processing.
SUMMARY OF THE INVENTION
The present invention resolves such a problem, and it is an object of the present invention to provide a bridge sleeper supporting pad for eliminating a necessity of forming a recess tailored to fit with a projection of a rivet of a bridge beam on a back face of a bridge sleeper or enhancing plate.
In order to achieve this object, subject matters of the present invention are as follows.
1. A bridge sleeper supporting pad to be interposed between a bridge beam and a bridge sleeper, wherein in a main bag produced by using a synthetic resin sheet as a material, a first reaction solution as a base material and a second reaction solution as a curing agent are accommodated, external pressure from outside the main bag causes the first reaction solution and the second reaction solution to be mixed each other, the main bag is provided with a sub bag in a communicative manner, the sub bag includes a plurality of compartments formed therein, and the neighboring compartments are communicable each other. 2. The bridge sleeper supporting pad according to 1, wherein the compartments of the sub bag are partitioned by a sealed portion having an easily peeled sealed portion. 3. The bridge sleeper supporting pad according to 1, wherein each of the compartments of the sub bag is divided into two halves by an easily peeled sealed portion at a middle part of the each compartment, and the neighboring compartments communicate each other via a path formed in the sealed portion on a downstream position of the each compartment. 4. The bridge sleeper supporting pad according to 1, wherein an inner bag is provided in the main bag, the inner bag being made from the synthetic resin sheet and designed so that at least a part thereof opens under application of the external pressure, the main bag contains one of the first reaction solution as the base material and the second reaction solution as the curing agent, and the inner bag provided in the main bag contains one of the second reaction solution as the curing agent and the first reaction solution as the base material. 5. The bridge sleeper supporting pad according to 2, wherein an inner bag is provided in the main bag, the inner bag being made from the synthetic resin sheet and designed so that at least a part thereof opens under application of the external pressure, the main bag contains one of the first reaction solution as the base material and the second reaction solution as the curing agent, and the inner bag provided in the main bag contains one of the second reaction solution as the curing agent and the first reaction solution as the base material. 6. The bridge sleeper supporting pad according to 3, wherein an inner bag is provided in the main bag, the inner bag being made from the synthetic resin sheet and designed so that at least a part thereof opens under application of the external pressure, the main bag contains one of the first reaction solution as the base material and the second reaction solution as the curing agent, and the inner bag provided in the main bag contains one of the second reaction solution as the curing agent and the first reaction solution as the base material. 7. The bridge sleeper supporting pad according to 1, wherein a first inner bag and a second inner bag are provided in the main bag, each of the first and second inner bags being made from the synthetic resin sheet and designed so that at least a part thereof opens under application of the external pressure, the first inner bag contains the first reaction solution as the base material, and the second inner bag contains the second reaction solution as the curing agent. 8. The bridge sleeper supporting pad according to 2, wherein a first inner bag and a second inner bag are provided in the main bag, each of the first and second inner bags being made from the synthetic resin sheet and designed so that at least a part thereof opens under application of the external pressure, the first inner bag contains the first reaction solution as the base material, and the second inner bag contains the second reaction solution as the curing agent. 9. The bridge sleeper supporting pad according to 3, wherein a first inner bag and a second inner bag are provided in the main bag, each of the first and second inner bags being made from the synthetic resin sheet and designed so that at least a part thereof opens under application of the external pressure, the first inner bag contains the first reaction solution as the base material, and the second inner bag contains the second reaction solution as the curing agent.
According to the bridge sleeper supporting pad of the above configuration, the external pressure applied from outside the main bag allows curing of the mixture solution of the first reaction solution and the second reaction solution in the main bag, and excess compounds of the first reaction solution and the second reaction solution can be introduced to the sub bag, so that the thickness of the bridge sleeper supporting pad can be adjusted to a desired thickness. Even when there is the projection of the rivet on the top face of the bridge beam, by interposing the bridge sleeper supporting pad between the bridge beam and the bridge sleeper, it is possible to make the bridge sleeper supporting pad adapt to the projection of the rivet, so that there is no need to form the recess suited for the projection of the rivet of the bridge beam on the back face of the bridge sleeper or enhancing plate. Further, by forming the plurality of compartments partitioned by the sealed portion with the inside thereof being easily peeled, when a load of the bridge sleeper or rail is applied on the bridge sleeper supporting pad, the bridge sleeper supporting pad is strongly pressed, and unnecessary compounds of the first reaction solution and the second reaction solution tend to flow into the sub bag as a surplus. At this time, a pressure of the unnecessary compounds of the first reaction solution and the second reaction solution exerted on the sealed portion causes the sealed portion to open and sequentially pushes open the compartments, whereby the unnecessary compounds of the first reaction solution and the second reaction solution can be removed from the main bag.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows exploded perspective views of a main bag, a first inner bag, a second inner bag, and a glass fiber cloth constituting a bridge sleeper supporting pad in a first embodiment of the present invention;
FIG. 2A shows a plan view of the first inner bag, and FIG. 2B shows a plan view of the second inner bag;
FIG. 3 shows an enlarged section view of the first or second inner bag;
FIG. 4 shows an explanatory view illustrating orientation of resin;
FIG. 5 shows an explanatory view illustrating a combined state of a resin part of straight-chain low-density polyethylene and a resin part of polybutane-1 in a heat sealed portion;
FIG. 6 shows an enlarged view of a relevant part of a sealing edge of the heat sealed portion on a short side;
FIG. 7 shows an enlarged view of a relevant part of the sealing edge of the heat sealed portion on a long side;
FIG. 8 shows a perspective view of the bridge sleeper supporting pad;
FIG. 9 shows a front view illustrating a state of the bridge sleeper supporting pad being used;
FIG. 10 shows a front view illustrating a state of the bridge sleeper supporting pad after completion of use;
FIG. 11 shows a perspective view illustrating the state of the bridge sleeper supporting pad after completion of use;
FIG. 12 shows exploded perspective views of a main bag, an inner bag, and a glass fiber cloth constituting a bridge sleeper supporting pad in a second embodiment of the present invention;
FIG. 13 shows a plan view of a bridge sleeper supporting pad in a third embodiment of the present invention;
FIG. 14 shows a plan view of a bridge sleeper supporting pad in a fourth embodiment of the present invention;
FIG. 15 shows a front view illustrating a state of a bridge sleeper supporting pad being used for describing another embodiment of the present invention; and
FIG. 16 shows a front view illustrating the state of the bridge sleeper supporting pad after completion of use.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 to 11 illustrate a first embodiment of the preset invention.
In FIGS. 1 to 11 , a main bag 1 has a rectangular planar shape, and a sub bag 2 is integrally provided in continuation with a long side of the main bag 1 . A heat sealed portion 3 closes four peripheral sides. In terms of volume, the main bag 1 is made larger than the sub bag 2 , and in the sub bag 2 a plurality of compartments 5 partitioned in a longitudinal direction of the main bag 1 by a sealed portion 4 are formed. The closest compartment 5 to the main bag 1 is separate from the main bag 1 , and one end of the sealed portion 4 dividing the compartment 5 from the main bag 1 is separate from one heat sealed portion 3 on the long side, and whereby a path 6 allowing communication between the main bag 1 and the sub bag 2 is formed. A middle part of the sealed portion 4 between the neighboring compartments 5 , 5 is formed as an easily peeled sealed portion 4 a so as to project toward the compartment 5 positioned upstream.
The main bag 1 accommodates a first inner bag 7 having almost the same dimension as the inside of the main bag 1 and a second inner bag 8 smaller than the first inner bag 7 . The above main bag 1 integral with the sub bag 2 , the first inner bag 7 and the second inner bag 8 are made from a synthetic resin sheet.
The first and the second inner bags 7 and 8 also have a rectangular planer shape as is the case with the main bag 1 , and produced by sealing four sides. Among the main bag 1 (including the continuing sub bag 2 ), the first and the second inner bags 7 and 8 , the main bag 1 is formed of commonly used sheet materials such that an inner layer is formed of a film material having low melting point, such as polyethylene and an outer layer is formed of a film material having higher melting point than the inner layer, such as nylon, and produced by heat sealing the inner layers of the two sheet materials at their four sides.
As is the case with the main bag 1 , the first and the second inner bags 7 and 8 are basically made of an inner layer formed from a film material having low melting point, and an outer layer formed from a film material having higher melting point than the inner layer, however, the film material forming the inner layer 9 is made by blending straight-chain low-density polyethylene and polybutene-1, as the straight-chain low-density polyethylene, those having a density ranging from 0.915 to 0.950 are used, and a ratio of blending straight-chain low-density polyethylene and polybutene-1 is set within a range of 70:30 to 98:2. And it is found that, when the first and the second inner bag 7 and 8 are produced by heat sealing using the film material obtained by blending straight-chain low-density polyethylene and polybutene-1, a difference arises in sealing strength between a heat sealed portion in a direction (X) extending perpendicularly to a film flow direction (direction of an arrow A) and a heat sealed portion in a direction (Y) extending parallel with the film flow direction (direction of the arrow A). In other words, the strength in a width direction along the film flow direction (direction of the arrow A) of the heat sealed portion in the perpendicular direction (X) tends to be smaller than the strength in the width direction extending perpendicularly to the film flow direction (direction of the arrow A) of the heat sealed portion in the parallel direction (Y). This is ascribable to the following facts. The resin to be a material for the inner layer 9 of the first and the second inner bags 7 and 8 is obtained by blending straight-chain low-density polyethylene and polybutene-1. In laminating the inner layer 9 of a film material obtained by blending and the outer layer 10 formed of nylon or polyethyleneterephthalate, uniaxial orientation appears between straight-chain low-density polyethylene and polybutene-1 under action of a processing speed. In other words, a film is formed while the resin of straight-chain low-density polyethylene and the resin of polybutene-1 are irregularly aligned. This state is shown in FIG. 4 illustrating resin 11 of straight-chain low-density polyethylene and resin 12 of polybutene-1. In this manner, since the inner layer 9 has uniaxial orientation, when two film materials each having a bilayer structure are overlaid and the peripheries are heat sealed so as to produce the four-side sealed inner bags 7 and 8 , as shown in FIG. 5 , three patterns of facing combination are provided: a straight-chain low-density polyethylene resin part 11 and a straight-chain low-density polyethylene resin part 12 ; a polybutene-1 resin part 12 and a polybutene-1 resin part 12 ; and a straight-chain low-density polyethylene resin part 11 and a polybutene-1 resin part 12 . Since the same kinds of resins are heat sealed in the combination of the straight-chain low-density polyethylene resin part 11 and the straight-chain low-density polyethylene resin part 11 , and in the combination of the polybutene-1 resin part 12 and the polybutene-1 resin part 12 , heat sealing strength is obtained within characteristics of the resin. On the contrary, in a part where the straight-chain low-density polyethylene resin part 11 and the polybutene-1 resin part 12 oppose each other, different kinds of resins face each other, so that heat sealing strengths of individual characteristics are not revealed. Such conditions are mixed in the heat sealing face. Heat seal characteristics coming from uniaxial orientation and the above three patterns of combination, and heat sealing direction cause the following phenomenon.
In a sealing edge in the width direction along the film flow direction (direction of the arrow A) of the heat sealed portion in the direction (X) perpendicular to the film flow direction (direction of the arrow A), the above three patterns of combinations appear irregularly (see FIG. 6 ). On the other hand, in the sealing edge in the width direction extending perpendicularly to the film flow direction (direction of the arrow A) of the heat sealed portion in the direction (Y) parallel to the film flow direction (direction of the arrow A), either one of the three patterns of combinations appears (see FIG. 7 ).
In measurement of the heat sealing strength, it is well known that a sealing width of an object is in direct proportion to strength, and the wider the sealing width, the larger strength the object has. In the sealing edge in the width direction along the film flow direction (direction of the arrow A) of the heat sealed portion in the direction (X) perpendicular to the film flow direction (direction of the arrow A), since the three patterns of combinations appear irregularly, a percentage in the sealing width occupied by the combination of the straight-chain low-density polyethylene resin part 11 and the straight-chain low-density polyethylene resin part 11 , and the combination of the polybutene-1 resin part 12 and the polybutene-1 resin part 12 increasing the strength is less than 100%, and presence of the combination of the straight-chain low-density polyethylene resin part 11 and the polybutene-1 resin part 12 in the sealing edge decreases the heat sealing strength. In the width direction extending perpendicularly to the film flow direction (direction of the arrow A) of the heat sealed portion in the direction (Y) parallel to the film flow direction (direction of the arrow A), since molecules are oriented uniaxially, there arise three cases of appearances: the combination of the straight-chain low-density polyethylene resin part 11 and the straight-chain low-density polyethylene resin 11 appears on the heat sealing edge, the combination of the polybutene-1 resin part 12 and the polybutene-1 resin part 12 appears on the heat sealing edge, and the combination of the straight-chain low-density polyethylene resin part 11 and the polybutene-1 resin part 12 appears on the heat sealing edge. In comparison with the sealing strength in the width direction along the film flow direction (direction of the arrow A) of the heat sealed portion in the direction (X) perpendicular to the film flow direction (direction of the arrow A), the strength is larger when the combination of the straight-chain low-density polyethylene part 11 and the straight-chain low-density polyethylene part 11 appears or when the combination of the polybutene-1 resin part 12 and the polybutene-1 resin part 12 appears, while the strength is smaller when the combination of the straight-chain low-density polyethylene resin part 11 and the polybutene-1 resin part 12 appears. However, since the sealing strength is determined from the strength of the sealing edge, when the combination of the straight-chain low-density polyethylene resin part 11 and the polybutene-1 resin part 12 appears, the strength is small and hence peeling occurs. However, when the combination of the straight-chain low-density polyethylene resin part 11 and the straight-chain low-density polyethylene resin part 11 or the combination of the polybutene-1 resin part 12 and the polybutene-1 resin part 12 appears in the next instant, the sealing strength increases. Totally, the sealing strength in the width direction extending perpendicularly to the film flow direction (direction of the arrow A) of the heat sealed portion in the direction (Y) parallel to the film flow direction (direction of the arrow A) is stronger than that in the width direction along the film flow direction (direction of the arrow A) of the heat sealed portion in the direction (X) perpendicular to the film flow direction (direction of the arrow A). For appearance of such characteristics, as the straight-chain low-density polyethylene as the material of the inner layer 9 , those having a density ranging from 0.915 to 0.950 are preferred, and the ratio of blending straight-chain low-density polyethylene and polybutene-1 is preferably within the range of 70:30 to 98:2 as described above. Outside these ranges, it is difficult to achieve the object of the present invention by realizing clear difference between the sealing strength in the width direction along the film flow direction (direction of the arrow A) of the heat sealed portion in the direction (X) perpendicular to the film flow direction (direction of the arrow A) and the sealing strength in the width direction extending perpendicularly to the film flow direction (direction of the arrow A) of the heat sealed portion in the direction (Y) parallel to the film flow direction (direction of the arrow A).
Utilizing the aforementioned nature, in the present embodiment, two film materials each having the bilayer structure are overlaid and the peripheries are heat sealed to produce the four-side sealed first and the second inner bags 7 and 8 having a rectangular planar shape. In such a case, the sealing strength in the width direction along the film flow direction (direction of the arrow A) of the heat sealed portion 13 in the direction (X) perpendicular to the film flow direction (direction of the arrow A), namely on the short side, is made smaller than the sealing strength in the width direction extending perpendicularly to the film flow direction (direction of the arrow A) of the heat sealed portion 14 in the direction (Y) parallel to the film flow direction (direction of the arrow A), namely on the longitudinal side, so that the sealed portion peels in the width direction of the heat sealed portion 13 on the short side upon increase in an inner pressure of the first and the second inner bags 7 and 8 . More specifically, of the heat sealed portions 13 opposing each other on the short side, the widthwise dimension of one of the heat sealed portions 13 on the short side is made smaller than that of the other of the heat sealed portions 13 so that the sealed portion quickly peels in the width direction of the one of the heat sealed portions 13 .
In brief, by forming a part having a narrow heat sealing width at an appropriate position in one of the heat sealed portions 13 opposing each other on the short side, the part having the narrow heat sealing width will quickly peel and provide an opening when the inner pressure is increased by application of the external pressure (force of pushing and pressing) on the first and the second inner bags 7 and 8 .
In the first inner bag 7 manufactured in the manner as described above, a first reaction solution as a base material is introduced via one opening side of the first inner bag 7 , and the first inner bag 7 is hermetically sealed, while in the second inner bag 8 , a second reaction solution as a curing agent is introduced via one opening side of the second inner bag 8 and the second inner bag 8 is hermetically sealed. The first inner bag 7 containing the first reaction solution as the base material and the second inner bag 8 containing the second reaction solution serving as the curing agent are introduced into the main bag 1 via one opening side of the main bag 1 , while one glass fiber cloth 15 having roughly a size of the inside of the outer bag 1 is put inside the main bag 1 so as to be along one side of the inner bag 7 , and then one opening side of the main bag 1 is hermetically sealed. The sub bag 2 formed in continuation with the main bag 1 is provided for removing excess compounds of the first reaction solution and the second reaction solution contained therein at a time of usage.
A bridge sleeper supporting pad 16 shown in FIG. 8 made of the main bag 1 housing the first inner bag 7 containing the first reaction solution as the base material and the second inner bag 8 containing the second reaction solution as the curing agent is laid on a bridge beam 17 of an iron bridge so as to be located under a bridge sleeper 18 extending perpendicularly to a longitudinal direction of the bridge beam 17 , as shown in FIGS. 9 to 11 . When the bridge sleeper supporting pad 16 is placed on the bridge beam 17 , an external pressure is applied from outside the main bag 1 of the bridge sleeper supporting pad 16 with the bridge sleeper 18 and the rail 19 floating, thereby causing the parts of the second inner bags 7 and 8 where the heat sealing width is narrow to peel and open, to mix the first reaction solution and the second reaction solution contained in the main bag 1 , whereby the bridge sleeper supporting pad 16 is placed on a predetermined position of the bridge beam 17 . Then on the bridge sleeper supporting pad 16 , the bridge sleeper 18 and the rail 19 are placed, and the bridge sleeper 18 is secured onto the bridge beam 17 with a hook 20 hooked on the back face of the bridge beam 17 . The sub bag 2 of the bridge sleeper supporting pad 16 projects from the bridge sleeper 18 , and as the bridge sleeper 18 and the rail 19 are placed on the bridge sleeper supporting pad 16 , the bridge sleeper supporting pad 16 is strongly pushed, and unnecessary compounds of the first reaction solution and the second reaction solution tend to flow into the sub bag 2 . At this time, unnecessary compounds of the first reaction solution and the second reaction solution firstly flow into the compartment 5 located closest to the main bag 1 from the path 6 . Then the unnecessary compounds flow from the compartment 5 located closest to the main bag 1 to the next compartment 5 as the sealed portion 4 a in the middle part of the sealed portion 4 partitioning the neighboring compartments 5 , 5 is peeled under a pressure by the unnecessary compounds of the first reaction solution and the second reaction solution. In this manner, the unnecessary compounds of the first reaction solution and the second reaction solution sequentially flow into the plurality of compartments 15 and the unnecessary compounds of the first reaction solution and the second reaction solution are removed from the main bag 1 . With lapse of time in this condition, compounds of the first reaction solution and the second reaction solution in the bridge sleeper supporting pad 16 complete curing. That is, an interval between the bridge beam 17 and the bridge sleeper 18 , namely a height of the rail 19 is adjusted by the thickness of a cured product of the compounds of the first reaction solution and the second reaction solution in the bridge sleeper supporting pad 16 . The compounds of the first reaction solution and the second reaction solution wrap around the glass fiber cloth 15 so that the strength of the cured product of compounds increases. The bridge beam 17 has a protrusion 17 a of the rivet in its upper end. The bridge sleeper supporting pad 16 has flexibility originating from the compounds existing therein in early stage of work, and the back face of the bridge sleeper supporting pad 16 conforms with the protrusion 17 a by the weight of the bridge sleeper 18 and the rail 19 placed on the bridge sleeper supporting pad 16 .
Concrete examples of the first reaction solution as the main material contained in the first inner bag 7 include compounds having epoxy group, compounds having isocyanate group, compounds of unsaturated diacid (glycol and maleic anhydride, fumaric acid), compounds such as acrylic acid or acrylate, compounds having silanol group, and compounds having amino group, and concrete examples of the second reaction solution as the curing agent contained in the second inner bag 8 include compounds such as polyamine, acid anhydride, polyphenol, or the like, compounds having hydroxyl group, compounds such as peroxide, compounds having isocyanate group, and compounds such as formaldehyde. And the second reaction solution suited for the first reaction solution contained in the first inner bag 7 is contained in the second inner bag 8 , and for example, when a compound having epoxy group is used as the first reaction solution contained in the first inner bat 7 , polyamine, acid anhydride, polyphenol or the like compound is used as the second reaction solution contained in the second inner bag 8 ; when a compound having isocyanate group is used as the first reaction solution, a compound having hydroxyl group is used as the second reaction solution; when a compound of unsaturated diacid (glycol and maleic anhydride, fumaric acid) or a compound such as acrylic acid or acrylate is used as the first reaction solution, peroxide or the like compound is used as the second reaction solution; when a compound having silanol group is used as the first reaction solution, a compound having isocyanate group is used as the second reaction solution; and when a compound having amino group is used as the first reaction solution, formaldehyde or the like compound is used as the second reaction solution. The combination of the first reaction solution as the base material to be contained in the first inner bag 7 and the second reaction solution as the curing agent to be contained in the second inner bag 8 is appropriately selected. In brief, the combination may be such that the first reaction solution as the base material and the second reaction solution as the curing agent mingle with each other and turn to resin and cure.
A quantity ratio between the first reaction solution as the base material and the second reaction solution as the curing agent differs depending on the kind of reaction solutions, and the sizes of the first inner bag 7 and the second inner bag 8 are determined in correspondence with the used quantity.
The sealed portion 4 a is sealed using a sealing agent not spontaneously resolving by the contained compounds of the first reaction solution and the second reaction solution, and the sealing agent is appropriately selected from synthetic rubber adhesive, natural rubber adhesive, acrylic adhesive, percoat sealing agent, hot melt resin and the like. Instead of using such a sealing agent, an easy-to-peel tape maybe used to simplify the sealing. In the illustrated embodiment, the sealed portion 4 a is formed to project toward the upstream compartment 5 in order to facilitate peeling by efficiently receiving the pressure by the unnecessary compounds of the first reaction solution and the second reaction solution flowing into the compartment 5 .
Next, the second embodiment shown in FIG. 12 will be explained. In the first embodiment, the first inner bag 7 containing the first reaction solution as the base material and the second inner bag 8 containing the second reaction solution as the curing agent are accommodated in the main bag 1 , however, in the second embodiment, the first reaction solution as the base material or the second reaction solution as the curing agent is directly contained in the main bag 1 , and only one inner bag 21 containing the second reaction solution as the curing agent or the first reaction solution as the base material is accommodated in the main bag 1 . The inner bag 21 used in the second embodiment is also designed to be openable by application of the external pressure as is the case with the first and the second inner bags 7 and 8 of the first embodiment. Other configuration is as same as that of the first embodiment.
Two embodiments have been described in the above, and it is also possible to accommodate an inner bag containing a curing accelerator in the main bag 1 as necessary. Also this inner bag is designed to be openable by application of the external pressure as is the case with the first and the second inner bags 7 and 8 of the first embodiment. In the first embodiment, the curing accelerator may be directly accommodated in the main bag 1 .
Further, as a measure of opening the inner bag by the external pressure, a method of making a part having smaller strength in the sealed portion enclosing the inner bag and opening the part by the external pressure can be exemplified, as well as the method of using straight-chain low-density polyethylene and polybutene-1 as described above, and thus the measure is not limited to the method of using straight-chain low-density polyethylene and polybutene-1.
Next, a third embodiment shown in FIG. 13 will be explained. In the third embodiment, like the sub bag 2 explained in the first embodiment, at the middle part in the short side direction of the main bag 1 of the each compartment 5 partitioned in the longitudinal direction of the main bag 1 , the each compartment 5 is divided into two halves by an easily peeling sealed portion 22 as is the case with the sealed portion 4 a , and neighboring compartments 5 , 5 communicate each other via a path 23 formed in the sealed portion 4 on the downstream position of the each compartment 5 . In the third embodiment, the easily peeling sealed portion 4 a is absent in the middle part of the sealed portion 4 partitioning the neighboring compartments 5 , 5 . Therefore, in the bridge sleeper supporting pad 16 of the third embodiment, unnecessary compounds of the first reaction solution and the second reaction solution from the main bag 1 pass through the path 6 , and an inner pressure thereof opens the sealed portion 22 in the each compartment 5 , whereby the unnecessary compounds of the first reaction solution and the second reaction solution flow into the plurality of compartments 5 .
Next, a fourth embodiment shown in FIG. 14 will be explained. In the fourth embodiment, an interior of the sub bag 2 is formed with a plurality of compartments 25 partitioned by sealed portions 24 in the short side direction of the main bag 1 , and the each compartment 25 is divided by an easily peeling sealed portion 26 as is the cases with the sealed portion 4 a and the sealed portion 22 , with the each component 25 being divided into two halves at the middle part in the longitudinal side direction of the main bag 1 of the each compartment 25 . Also, neighboring compartments 25 , 25 communicate each other via a path 27 formed in the sealed portion 24 on downstream side of the each compartment 25 . Therefore, in the bridge sleeper supporting pad 16 of the fourth embodiment, unnecessary compounds of the first reaction solution and the second reaction solution from the main bag 1 pass through the path 6 , and an inner pressure thereof opens the sealed portion 26 in the each compartment 25 , whereby the unnecessary compounds of the first reaction solution and the second reaction solution flow into the plurality of compartments 25 .
Further, in the above third and fourth embodiments, like the second embodiment, the first reaction solution as the base material or the second reaction solution as the curing agent may be directly contained in the main bag 1 , and only one inner bag containing the second reaction solution as the curing agent or the first reaction solution as the base material may be accommodated in the main bag 1 .
The aforementioned bridge sleeper supporting pad 16 may be used in the states shown in FIGS. 15 and 16 , as well as the case of newly providing a rail 19 in the manner as shown in FIGS. 9 to 11 . That is, in the use states shown in FIGS. 15 and 16 , at a position on the back face of the bridge sleeper 18 where a bridge beam 17 is to be laid, an enhancing plate 28 made of wood is fitted so that a substantially half of its thickness protrudes downward from the bridge sleeper 18 . And when the enhancing plate 28 decays from the back side, the decayed part is removed and the back face of the enhancing plate 28 is made flat, and in this condition, the bridge sleeper supporting pad 16 , is interposed between the bridge bream 17 and the enhancing plate 28 . | The invention aims at providing a bridge sleeper supporting pad for eliminating necessity of a recess to fit a projection of a rivet of a bridge beam, on a back face of a bridge sleeper or enhancing plate. For this, the invention provides a bridge sleeper supporting pad interposed between a bridge beam and bridge sleeper, including a main bag, first inner bag and second inner bag in the main bag, wherein the first inner bag contains a first reaction solution, the second inner bag contains a second reaction solution, the respective first and second inner bags are designed so that at least a part thereof opens under external pressure, the main bag is provided in communication with a sub bag, and the sub bag includes a plurality of compartments formed therein, the respective compartments partitioned by a sealed portion having a sealed portion with an inside easily peeled. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is directed to wellbore drilling top drive systems; such systems including apparatus for sensing deflection of a top drive main shaft; and methods of their use.
2. Description of Related Art
The prior art discloses a variety of top drive systems; for example, and not by way of limitation, the following U.S. patents present exemplary top drive systems and components thereof: U.S. Pat. Nos. 4,458,768; 4,807,890; 4,984,641; 5,433,279; 6,276,450; 4,813,493; 6,705,405; 4,800,968; 4,878,546; 4,872,577; 4,753,300; 6,007,105; 6,536,520; 6,679,333; 6,923,254—all these patents incorporated fully herein for all purposes.
Certain typical prior art top drive drilling systems have a derrick with a top drive which supports and rotates tubulars, e.g., drill pipe. The top drive is supported from a travelling block beneath a crown block. A drawworks on a rig floor raises and lowers the top drive. In many cases, a top drive is secured to a dolly that moves on a guide track in the derrick.
A top drive has a main drive shaft that is rotated by one or more motors. This main drive shaft supports significant weights, including, during certain operations, the weight of a drill string. For effective and efficient operations, it is important that the top drive main shaft remain aligned with a load supported on the top drive main shaft and/or with a well center of a well above which the top drive is positioned. Misalignment can result from incorrect positioning of dolly guide tracks or incorrectly positioning a top drive on a dolly, either laterally or at an angle to a well center line. Misalignment can also result if a dolly retract system does not position the top drive over well center.
In the past, efforts to maintain alignment of a top drive main shaft have included various mechanical position or attitude adjustment apparatuses and arrangements of hydraulic cylinders to relieve bending loads caused by shaft misalignment. In the past, due to the relative high stiffness of a top drive main shaft, it has not been obvious to use a sensor to detect top drive main shaft deflection. This was also not obvious because the main shafts are so stiff that detecting damaging bending was beyond economical sensor resolution.
BRIEF SUMMARY OF THE INVENTION
The present invention, in certain aspects, provides a top drive system for wellbore operations above a well, e.g., above a well center of a well, the top drive system including: a main body; a motor (or motors) for rotating the main shaft; a main shaft extending from the main body, the main shaft having a top end and a bottom end, the main shaft having a gear system driven by the motor apparatus so that driving the gear system results in rotation of the main shaft; and sensing apparatus for sensing bending of the main shaft (which can be caused by misalignment between the main shaft and the direction of a load being supported by the main shaft). In one aspect (as may be the case in any system according to the present invention), the main shaft has a relatively long slender central section to allow bending deflection without damaging stress.
The present invention discloses, in certain aspects, a top drive system for wellbore operations above a well, the top drive systems including: a main body; a main shaft extending from the main body, the main shaft having a top end and a bottom end, the main shaft having a main shaft flow bore therethrough from top to bottom through which drilling fluid is flowable; a main shaft housing enclosing a portion of the main shaft, the main shaft having a non-loaded position relative to the main shaft housing; and sensing apparatus located for sensing bending of the main shaft away from the non-loaded position. In one particular aspect, a top drive system's main shaft has been reduced (e.g. from one typical shaft that has an outer diameter of 13.75 inches) to a shaft with an diameter of 9 inches, rendering the shaft more flexible yet with sufficient strength to handle expected loads, e.g. a 2500 kps load.
The present invention discloses, in certain aspects, methods for sensing deflection of a main shaft of a top drive system, the top drive system as any described or referred to herein, the method including sensing with sensing apparatus position of the main shaft. In one particular aspect, a top drive system's main shaft has been reduced (e.g. from one typical shaft that has an outer diameter of 13.75 inches) to a shaft with an diameter of 9 inches, rendering the shaft more flexible yet with sufficient strength to handle expected loads, e.g. a 2500 kps load.
Certain embodiments of this invention are not limited to any particular individual feature disclosed here, but include combinations of them distinguished from the prior art in their structures, functions, and/or results achieved. Features of the invention have been broadly described so that the detailed descriptions that follow may be better understood, and in order that the contributions of this invention to the arts may be better appreciated. There are, of course, additional aspects of the invention described below and which may be included in the subject matter of the claims to this invention. Those skilled in the art who have the benefit of this invention, its teachings, and suggestions will appreciate that the conceptions of this disclosure may be used as a creative basis for designing other structures, methods and systems for carrying out and practicing the present invention. The claims of this invention are to be read to include any legally equivalent devices or methods which do not depart from the spirit and scope of the present invention.
What follows are some of, but not all, the objects of this invention. In addition to the specific objects stated below for at least certain preferred embodiments of the invention, there are other objects and purposes which will be readily apparent to one of skill in this art who has the benefit of this invention's teachings and disclosures. It is, therefore, an object of at least certain preferred embodiments of the present invention to provide:
New, useful, unique, efficient, non-obvious top drive systems and methods of their use; and
Such systems with a sensor apparatus for sensing bending of a top drive main shaft which could cause damage to the main shaft or to related components.
The present invention recognizes and addresses the problems and needs in this area and provides a solution to those problems and a satisfactory meeting of those needs in its various possible embodiments and equivalents thereof. To one of skill in this art who has the benefits of this invention's realizations, teachings, disclosures, and suggestions, other purposes and advantages will be appreciated from the following description of certain preferred embodiments, given for the purpose of disclosure, when taken in conjunction with the accompanying drawings. The detail in these descriptions is not intended to thwart this patent's object to claim this invention no matter how others may later attempt to disguise it by variations in form, changes, or additions of further improvements.
The Abstract that is part hereof is to enable the U.S. Patent and Trademark Office and the public generally, and scientists, engineers, researchers, and practitioners in the art who are not familiar with patent terms or legal terms of phraseology to determine quickly from a cursory inspection or review the nature and general area of the disclosure of this invention. The Abstract is neither intended to define the invention, which is done by the claims, nor is it intended to be limiting of the scope of the invention in any way.
It will be understood that the various embodiments of the present invention may include one, some, or all of the disclosed, described, and/or enumerated improvements and/or technical advantages and/or elements in claims to this invention.
Certain aspects, certain embodiments, and certain preferable features of the invention are set out herein. Any combination of aspects or features shown in any aspect or embodiment can be used except where such aspects or features are mutually exclusive.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
A more particular description of embodiments of the invention briefly summarized above may be had by references to the embodiments which are shown in the drawings which form a part of this specification. These drawings illustrate certain preferred embodiments and are not to be used to improperly limit the scope of the invention which may have other equally effective or equivalent embodiments.
FIG. 1 is a schematic view of a top drive system in a derrick according to the present invention.
FIG. 2A is a side view of a top drive system according to the present invention.
FIG. 2B is a cross-section view of a top drive system of FIG. 2A .
FIG. 3 is a cross-section view of a top drive system according to the present invention.
FIG. 4A is a side view of a sensor system according to the present invention.
FIG. 4B is a cross-section view of the sensor system of FIG. 4A along line 4 B- 4 B of FIG. 4A .
FIG. 4C is a partial cross-section view of the sensor system of FIG. 4A along line 4 C- 4 C of FIG. 4A .
Presently preferred embodiments of the invention are shown in the above-identified figures and described in detail below. Various aspects and features of embodiments of the invention are described below and some are set out in the dependent claims. Any combination of aspects and/or features described below or shown in the dependent claims can be used except where such aspects and/or features are mutually exclusive. It should be understood that the appended drawings and description herein are of preferred embodiments and are not intended to limit the invention or the appended claims. On the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the invention as defined by the appended claims. In showing and describing the preferred embodiments, like or identical reference numerals are used to identify common or similar elements. The figures are not necessarily to scale and certain features and certain views of the figures may be shown exaggerated in scale or in schematic in the interest of clarity and conciseness.
As used herein and throughout all the various portions (and headings) of this patent, the terms “invention”, “present invention” and variations thereof mean one or more embodiment, and are not intended to mean the claimed invention of any particular appended claim(s) or all of the appended claims. Accordingly, the subject or topic of each such reference is not automatically or necessarily part of, or required by, any particular claim(s) merely because of such reference. So long as they are not mutually exclusive or contradictory any aspect or feature or combination of aspects or features of any embodiment disclosed herein may be used in any other embodiment disclosed herein.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 illustrates a top drive system 10 according to the present invention which is structurally supported by a derrick 11 . The system 10 has a plurality of components including: a swivel 13 , a top drive 14 according to the present invention (any disclosed herein), a main shaft 16 , a housing 17 , a drill stem 18 /drillstring 19 and a drill bit 20 . The components are collectively suspended from a traveling block 12 that allows them to move upwardly and downwardly on a dolly 26 on rails 22 connected to the derrick 11 for guiding the vertical motion of the components. Torque generated during operations with the top drive or its components (e.g. during drilling) is transmitted through the dolly 26 via the rails 22 to the derrick 11 . The main shaft 16 extends through the motor housing 17 and connects to the drill stem 18 . The drill stem 18 is typically threadedly connected to one end of a series of tubular members collectively referred to as the drillstring 19 . An opposite end of the drillstring 19 is threadedly connected to a drill bit 20 .
During operation, a motor apparatus 15 (shown schematically) encased within the housing 17 rotates the main shaft 16 which, in turn, rotates the drill stem 18 /drillstring 19 and the drill bit 20 . Rotation of the drill bit 20 produces an earth bore 21 with a well center 23 . Fluid pumped into the top drive system passes through the main shaft 16 , the drill stem 18 /drillstring 19 , the drill bit 20 and enters the bottom of the earth bore 21 . Cuttings removed by the drill bit 20 are cleared from the bottom of the earth bore 21 as the pumped fluid passes out of the earth bore 21 up through an annulus formed by the outer surface of the drill bit 20 and the walls of the bore 21 . Pipe handling apparatus 28 can be suspended from the top drive.
A shaft deflection sensing apparatus 24 connected to the housing 17 has a sensor 25 (or multiple sensors 25 ) to sense deflection of the main shaft 16 .
The sensor 25 (or sensors) can be (as is true for any embodiment herein) any known sensor for detecting bending of the main shaft away from the direction it assumes when it is not supporting a load (often this is a direction in which the main shaft is aligned with the well center). In one aspect, the sensor(s) are inductive proximity distance sensors. Optionally, the sensor(s) may be (but are not limited to) capacitative proximity sensors, ultrasonic distance sensors, photoelectric sensors, or laser distance-measuring devices. In certain cases, if the expected direction of an anticipated excessive load is known, a single sensor can be used to provide a sufficient warning of undesirable shaft bending deflection to an operator. If the direction of such a load is not known, two or more distance sensors are used. Alternatively, or in addition to these sensors, the sensor(s) may be a sensor (or sensors) 24 a , (shown schematically, FIG. 1 ) mounted on the outer surface of the main shaft, and/or a sensor (or sensors) 24 b within the main shaft, directly measuring main shaft deflection and transmitting this data, e.g. via telemetry, wirelessly or via electrical slip ring(s).
FIGS. 2A and 2B illustrate a top drive system 100 according to the present invention (which may be used as the top drive system 10 , FIG. 1 ) which has supporting bails 104 suspended from a becket 102 . Motors 120 which rotate a main shaft 160 are supported on a main body 130 . One motor may be used. A bonnet 110 supports a gooseneck 106 and a washpipe 110 a through which fluid is pumped to and through the system 100 and through a flow channel 163 through a main shaft 160 . Within the bonnet 110 are an upper packing box 115 (connected to the gooseneck 106 ) for the washpipe; and a lower packing box 117 for the washpipe. A main gear housing 140 encloses a bull gear 142 . A ring gear housing 150 encloses a ring gear 152 and associated components.
A drag chain system 170 encloses a drag chain 172 and associated components including hoses and cables. This drag chain system 170 can be used instead of a rotating head and provides rotation for reorientation of a link adapter 180 and items connected thereto.
Bolts releasably secure the bonnet 110 to the body 130 . Removal of these bolts permits removal of the bonnet 110 . Bolts 164 through a load shoulder 168 releasably secure the main shaft 160 to a quill 190 . The quill 190 is a transfer member between the main shaft 160 and the bull gear 142 and transfers torque between the bull gear 142 and the main shaft 160 . The quill 190 also transfers the tension of a tubular or string load on the main shaft to thrust bearings 191 (not to the bull gear 142 ). One or more seal retainer bushings 166 are located above the load shoulder 168 . Removal of the bonnet 110 and bolts through the load shoulder 168 securing the main shaft 160 to a quill 190 , permits removal of the main shaft 160 from the system 100 without exposing or disturbing the inner components of the gear box or the main thrust bearings 191 . Upper quill bearings 144 are above a portion of the quill 190 .
As shown in FIG. 2B , the system 100 is movable on a mast or part of a derrick 139 (like the derrick 11 and on its rails 22 ) by connection to a movable apparatus like a dolly 134 . Ends of links 133 are pivotably connected to arms 131 , 132 of a body 130 . The other ends of the links 133 are pivotably connected to the dolly 134 . This structure permits the top drive and associated components to be moved up and down, and toward and away from a well centerline (e.g. like a line in line with the well center 23 , FIG. 1 ), as shown by the structure in dotted line (toward the derrick when drill pipe is connected/disconnected while tripping; and to the well center during drilling). Known apparatuses and structures are used to move the links 133 and to move the dolly 134 .
Upper parts of the bails 104 extend over and are supported by arms 103 of the becket 102 . Each bail 104 has two spaced-apart lower ends 105 pivotably connected by pins to the body 130 . Such a use of two bails distributes the support load on the main body and provides a four-point support for this load, economically reducing bending moments within the main body and thus provide a more stable platform for the bearings 191 .
The quill 190 rests on main thrust bearings 191 which support the quill 190 , the main shaft 160 , and whatever is connected to the main shaft 160 (including whatever load is borne by the main shaft 160 during operations, e.g. drilling loads and tripping loads). The body 130 houses the main thrust bearings 191 and contains lubricant for the main thrust bearings 191 . An annular passage provides a flow path for lubricant from the gear housing 140 to the thrust bearings.
Shafts 122 of the motors 120 drive couplings 123 rotatably mounted in the body 130 which drive drive pinions 124 in the main gear housing 140 . The drive pinions 124 drive the bull gear 142 which is connected to the quill 190 with connectors 192 .
The bull gear 142 is within a lower portion 146 of the gear housing 140 which holds lubricant for the bull gear 142 and bearings and is sealed with seal apparatus 148 so that the lubricant does not flow out and down from the gear housing 140 . Any suitable known rotary seal 148 may be used.
The ring gear housing 150 which houses the ring gear 152 also has movably mounted therein two sector gears 154 each movable by a corresponding hydraulic cylinder apparatus 156 to lock the ring gear 152 . With the ring gear 152 unlocked (with the sector gears 154 backed off from engagement with the ring gear 152 ), items below the ring gear housing 150 (e.g. a pipe handler and a link adapter) can rotate. The ring gear 152 can be locked by the sector gears 154 to act as a backup to react torque while drill pipe connections are being made to the drillstring. The ring gear 152 is locked when a pipe handler is held without rotation (e.g. when making a connection of a drill pipe joint to a drillstring). An hydraulic motor (not shown), via interconnected gearing, turns the ring gear to, in turn, rotate the link adapter 180 and whatever is suspended from it; i.e., in certain aspects to permit the movement of a supported tubular to and from a storage area and/or to change the orientation of a suspended elevator, e.g. so that the elevator's opening throat is facing in a desired direction. Typical rig control systems are used to control this motor and the apparatuses 156 and typical rig power systems provide power for them.
In a variety of prior top drive systems a rotating head with a plurality of passageways therethrough is used between some upper and lower components of the system to convey hydraulic and pneumatic power used to control system components beneath the rotating head. Such a rotating head typically rotates through 360 degrees infinitely. Such a rotating head may, according to certain aspects of the present invention, be used with system according to the present invention; but, in other aspects, a drag chain system 170 is used below the ring gear housing 150 and above the link adapter 180 to convey fluids and signals to components below the ring gear housing 150 . The drag chain system 170 does not permit infinite 360 degree rotation, but it does allow a sufficient range of motion in a first direction or in a second opposite direction to accomplish all the functions to be achieved by system components suspended from the link adapter 180 (e.g. an elevator and/or a pipe handler), in one aspect with a range of rotative motion of about three-quarters of a turn total, 270 degrees.
Optionally, instead of a typical rotating head or a drag chain system according to the present invention, a variety of known signal/fluid conveying apparatuses may be used with systems according to the present invention; e.g., but not limited to, wireless systems or electric slip ring systems, in combination with simplified fluid slip ring systems.
A sensing apparatus 194 has sensors 196 for sensing the position of the main shaft 160 . The main shaft is above a well center 197 of a well 198 .
Drilling loads (the load of the drillstring, bit, etc.) pass through a threaded connection 160 a at the end of the main shaft 160 to the main shaft 160 . Tripping loads (the load, e.g., of tubular(s) being hauled and manipulated into and out of the well) pass through the link adapter 180 and through a load ring 161 , not through the threaded connection of the main shaft and not through any threaded connection so that threaded connections of the top drive are isolated from tripping loads.
FIG. 3 shows a top drive system 200 according to the present invention which has a main shaft 202 rotated by a gear system 204 driven by motors 206 (shown partially). Deflection sensors 210 secured to an extension of main shaft housing 212 are positioned to sense the location of the main shaft 202 with respect to a center line of the main shaft housing 212 .
A link adapter 218 is above an IBOP 219 . The IBOP 219 and a drill string 208 (shown schematically) are supported by the main shaft 202 at a threaded connection 202 a . Drilling loads pass through the threaded connection 202 a to the main shaft 202 . Tripping loads pass through the link adapter 218 and through a load ring 202 b (not through a threaded connection of the top drive).
FIGS. 4A-4C illustrate a sensor system 300 according to the present invention which can be used to sense top drive main shaft deflection from a normal un-loaded position relative to the housing, thus measuring bending deflection and stress. The systems 300 are mounted to an extension body 302 with an upper flange 304 to facilitate connection of the systems 300 to the main shaft housing 204 a ( FIG. 3 ).
The sensor systems 300 have bodies 312 disposed in channels 306 through the body 302 which house sensors 311 . Retainers 313 releasably secure the sensor bodies 312 to the body 302 .
As shown, six sensors 311 are spaced-apart roughly equally around the body 302 which encompasses a main shaft 320 of a top drive system. The holes 308 provide passages for hydraulic fluid for the rotating head.
A control system 330 has an electronic circuit 332 which is in communication with the sensors 311 and monitors outputs in real-time from the sensors 311 which can indicate, in real-time, acceptable deflection and undesirable deflection of the main shaft 320 . If undesirable deflection is detected, the control system 330 sends a warning to an operator (e.g., but not limited to, a visual and/or audible warning to a driller's console 340 ).
In one embodiment of the present invention, the system warns an operator of undesirable loading on the main shaft in any direction. Sensors are positioned in a radial array around the main shaft in an annular space between the main shaft and a main shaft support housing. In one aspect, the sensors 311 are inductive proximity distance sensors mounted with respect to the top drive main shaft so that they switch state when the top drive main shaft 320 is deflected (bent) beyond a pre-determined safe amount. The sensors can switch state from open-circuit to close-circuit, or vice-versa. The state of the sensors is monitored by an electronic circuit and, when a switched state of the sensors is detected (e.g. when an unsafe side load or bending moment is externally applied to the top drive main shaft), the control system 330 sends a warning to an operator allowing correction of the loading condition before significant damage can occur (including significant fatigue damage to main shaft material). Alternatively, the sensors 311 are analog distance sensors and the control system 330 evaluates and transmits the amount of shaft deflection to warn an operator of an unsafe condition and/or to calculate cumulative fatigue damage (for reporting and/or warning).
In one aspect, the positions of the sensors are adjusted radially relative to the main shaft until each detects the presence of the main shaft and then each is advanced an additional amount towards the main shaft that equates to a desired main shaft deflection alarm point. This alarm point is based on an allowable deflection of the main shaft at the elevation of the sensors. When the main shaft deflects beyond this alarm point, the sensor opposite the deflection direction will no longer detect the presence of the main shaft and will open the electrical circuit, causing the sensors' monitoring circuit to send the alarm to the top drive operator. Should a sensor or wire in the sensing system fail, the electrical circuit will open, again tripping the alarm. Because the allowable deflection of the main shaft is small, the sensors are, preferably, positioned and held in place with precision, without radial free-play or backlash. Each sensor, as shown in FIG. 4C , has an inductive proximity sensor head 311 a which will close a circuit when it detects the metal of the main shaft 320 within a sensing range, e.g. about 4 mm. The electrical circuit remains closed so long as the main shaft is within the pre-set sensing range.
A support adapter 312 rigidly supports the sensor member 311 and allows for fine radial adjustment of the relative position of the member 311 with respect to the main shaft 320 . Use of such an adapter 312 permits sensor removal and replacement while a top drive system with the main shaft 320 is fully assembled (which can reduce maintenance down time). A wave spring 315 which applies axial force on the adapter 312 reduces or eliminates radial backlash between a keeper 313 and the adapter 312 .
A swivel nut 314 is held by the keeper 313 and a snap ring 316 which restrain the swivel nut 314 from outward radial movement and assists in maintaining the adapter's and sensor's radial position relative to the normal unloaded position of the top drive main shaft. Rotation of the swivel nut 314 relative to the adapter 312 translates the inductive proximity sensor member 311 axially (toward or away from the main shaft 320 ). A jam nut 317 prevents the swivel nut 314 from rotating freely and reduces or eliminates backlash (unrestrained axial motion of a sensor) between the adapter 312 and the swivel nut 314 .
The present invention, therefore, provides in some, but not in necessarily all, embodiments a top drive system for wellbore operations for a well with a well center on a well center line, the top drive system including: a main body; a motor apparatus; a main shaft extending from the main body, the main shaft having a top end and a bottom end, the main shaft having a main shaft flow bore therethrough from top to bottom through which drilling fluid is flowable; a quill connected to and around the main shaft; a gear system interconnected with the quill, the gear system driven by the motor apparatus so that driving the gear system drives the quill and thereby drives the main shaft, the main shaft passing through the gear system; and sensing apparatus for sensing bending of the main shaft away from its normal (unloaded) position.
The present invention provides, therefore, in some, but in not necessarily all, embodiments a top drive system for wellbore operations above a well, the top drive system having: a main body; a main shaft extending from the main body, the main shaft having a top end and a bottom end, the main shaft having a main shaft flow bore therethrough from top to bottom through which drilling fluid is flowable; sensing apparatus located for sensing bending of the main shaft away from the non-loaded position, in one aspect the sensing apparatus on or in a main shaft housing enclosing a portion of the main shaft, the main shaft having a non-loaded position relative to the main shaft housing. Such a system may, according to the present invention, have one, or some, in any possible combination, of the following: the sensing apparatus located on the main shaft housing; the sensing apparatus on the main shaft; the sensing apparatus including an apparatus body connected to the main shaft housing, a plurality of sensors extending through the apparatus body, each sensor having a sensor head adjacent an exterior surface of the main shaft, each sensor for sensing deflection of the main shaft with respect to the sensor head; each sensor is an inductive proximity distance sensor; wherein each sensor is removably located in the apparatus body; wherein each sensor is an analog distance sensor; wherein the sensors are spaced-apart around the apparatus body and each sensor is supported by a support which allows fine radial adjustment of the position of the sensor's sensor head with respect to the main shaft; a control system in communication with each sensor for monitoring sensor output; wherein the control system provides an operator with an indication of main shaft deflection in real-time; wherein the control system provides an operator with a warning of undesirable main shaft deflection in real-time; wherein the sensing apparatus has at least one sensor that is one of capacitative proximity sensor, ultrasonic distance sensor, photoelectric sensor, laser distance-measuring sensor, and inductive proximity distance sensor; wherein the sensing apparatus senses main shaft deflection in real-time; and/or wherein the main shaft has an outer diameter of about nine inches.
The present invention provides, therefore, in certain embodiments, a top drive system for wellbore operations above a well, the top drive system including:
a main body;
a main shaft extending from the main body, the main shaft having a top end and a bottom end, the main shaft having a main shaft flow bore therethrough from top to bottom through which drilling fluid is flowable;
a main shaft housing enclosing a portion of the main shaft, the main shaft having a non-loaded position relative to the main shaft housing;
sensing apparatus located for sensing bending of the main shaft away from the non-loaded position;
an apparatus body connected to the main shaft housing;
a plurality of sensors extending through the apparatus body, each sensor having a sensor head adjacent an exterior surface of the main shaft;
each sensor for sensing deflection of the main shaft with respect to the sensor head;
each sensor is an inductive proximity distance sensor;
wherein each sensor is removably located in the apparatus body;
a control system in communication with each sensor for monitoring sensor output;
wherein the control system provides an operator with an indication of main shaft deflection in real-time; and
wherein the control system provides an operator with a warning of undesirable main shaft deflection in real-time.
The present invention provides, therefore, methods for sensing deflection of a main shaft of a top drive system, the top drive system as any described or referred to herein, the top drive system having a main body and a main shaft, the method including sensing with the sensing apparatus position of the main shaft. Such a method may include one or some, in any possible combination, of the following: wherein a control system in communication with each sensor for monitoring sensor output and wherein the control system provides an operator with an indication of main shaft deflection in real-time, the method further including providing, with the control system, in real-time an indication of main shaft deflection; wherein the control system provides an operator with a warning of undesirable main shaft deflection in real-time, the method further including providing such a warning; and/or wherein the sensing apparatus includes an apparatus body connected to the main shaft housing, a plurality of sensors extending through the apparatus body, each sensor having a sensor head adjacent an exterior surface of the main shaft, each sensor for sensing deflection of the main shaft with respect to the sensor head, wherein each sensor is removably located in the apparatus body, and wherein the sensors are spaced-apart around the apparatus body and each sensor is supported by a support which allows fine radial adjustment of the position of the sensor's sensor head with respect to the main shaft, the method further including radially adjusting the position of each sensor head with respect to the main shaft
In conclusion, therefore, it is seen that the present invention and the embodiments disclosed herein and those covered by the appended claims are well adapted to carry out the objectives and obtain the ends set forth. Certain changes can be made in the subject matter without departing from the spirit and the scope of this invention. It is realized that changes are possible within the scope of this invention and it is further intended that each element or step recited in any of the following claims is to be understood as referring to the step literally and/or to all equivalent elements or steps. The following claims are intended to cover the invention as broadly as legally possible in whatever form it may be utilized. The invention claimed herein is new and novel in accordance with 35 U.S.C. §102 and satisfies the conditions for patentability in §102. The invention claimed herein is not obvious in accordance with 35 U.S.C. §103 and satisfies the conditions for patentability in §103. This specification and the claims that follow are in accordance with all of the requirements of 35 U.S.C. §112. The inventor may rely on the Doctrine of Equivalents to determine and assess the scope of the invention and of the claims that follow as they may pertain to apparatus not materially departing from, but outside of, the literal scope of the invention as set forth in the following claims. All patents and applications identified herein are incorporated fully herein for all purposes. It is the express intention of the applicant not to invoke 35 U.S.C. §112, paragraph 6 for any limitations of any of the claims herein, except for those in which the claim expressly uses the words ‘means for’ together with an associated function. In this patent document, the word “comprising” is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. A reference to an element by the indefinite article “a” does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one and only one of the elements. | A top drive system for wellbore operations, the top drive system including motor apparatus, a main shaft driven by the motor apparatus, and sensing apparatus for sensing bending of the main shaft; and, in certain aspects, the system providing information regarding the extent of main shaft bending and/or for warning an operator of an undesirable amount of main shaft bending. This abstract is provided to comply with the rules requiring an abstract which will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure and is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims, 37 C.F.R. 1.72(b). | 4 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority under 35 USC §119 to provisional application serial No. 60/372,241, filed Apr. 12, 2002, and provisional application serial No. 60/345,511, filed Jan. 7, 2002.
FIELD OF THE INVENTION
[0002] The present invention discloses a process for creating an improved surface that can serve as a base or underlayer, a planarization layer, a spacer layer, a dielectric layer, an adhesive layer, and an encapsulation layer in magnetic recording head devices. More particularly, the present invention relates generally to the design and manufacture of magnetic recording read/write transducers having one or more of these layers, using a polymer precursor to ceramic that provides improved heat transfer, mechanical hardness, smoothness, performance and longevity. The material can also be used to improve static discharge protection. This invention also has applicability to semiconductors, MEMs and other electronic devices which, through the use of the materials of this invention in one or more of these layers, can be improved.
BACKGROUND OF THE INVENTION
[0003] The information storage industry is driven by market demands to increase continually the capacity and performance of disk drives for storing information. Driven by and reflecting this demand, the amount of storage capacity in a typical disk drive is doubling every year. To meet this capacity demand without increasing costs by adding more disks and heads, disk and tape drive suppliers are continually increasing the areal density of the stored information. Read and write transducer design and processing are key technologies wherein continuous improvement is required to achieve these capacity increases.
[0004] The inductive write element includes a coil layer embedded in an insulation stack, the insulation stack being located between the first and second pole piece layers. A gap between the first and second pole piece layers is formed by a gap layer at the air-bearing surface (ABS) of the write head. The pole pieces are connected at a back gap. A rapidly changing current, which corresponds to coded data, is conducted through the coil layer which produces magnetic fields in the pole pieces. The magnetic fields fringe across the gap at the ABS in proximity to a moving magnetic medium such as a disk or tape. The fringing magnetic fields set the magnetic orientation at given locations on the disk or tape. The varying orientations correspond to the coded data. In this manner, data is written on the magnetic storage medium.
[0005] The read element that reads the data from the disk is sandwiched between two shields but isolated from them by a read gap on each side. During a read operation, the read element flies in proximity to the disk so that the read element senses the magnetic orientation of the given disk location. Various read-element technologies are employed in modem disk and tape drives, such as Anisotropic Magnetoresistive, Giant Magnetoresistive (GMR), and Current-Perpendicular-to-Plane GMR (CPP-GMR) heads. They are generally similar in usage in that the resistance of the read element changes in response to an external magnetic field, such as the field from the encoded data on the disk. In each of these methods, as well as other methods not described here, a sense current is passed through the read element and attached electronics are used to sense the change in resistance. Generally, it is desirable to operate at a higher current because that generally produces more signal amplitude.
[0006] In disk drive recording heads, the read element and the write element are typically fabricated together in a merged device on a wafer, such as ceramic AlTiC. They are separated from the ceramic by a dielectric underlayer, such as alumina. Further, after fabrication, they are protected from outside damage by encapsulating the entire device in a dielectric, such as alumina. In tape heads, a merged device can be used or a separate read device and write element can be fabricated. In this case, the read head and the write head are both individually processed on a ceramic wafer and protected by the underlayer and encapsulation layer described above. An additional layer (referred to herein as a ‘wear cap’ or ‘capping substrate’), generally but not always made from the same material as the substrate, is bonded to the tape head on the side opposite the substrate to provide for tape bearing surface (TBS) fabrication and to protect the relatively soft reader and writer elements from wear since the moving media is generally in contact with the tape recording head elements.
[0007] Use of conventional materials in the production of MRTs and other devices can cause various types of problems. For example, during definition of the ABS or TBS and the final geometry of the read/write transducer, several mechanical or chemo-mechanical polishing (“lapping”) processes can be used. This lapping can remove material at a differential rate. The pole material is relatively soft and tends to erode faster than the neighboring dielectric. The dielectric is softer than the ceramic substrate the device is fabricated on, so it erodes faster than the substrate. Tape heads can suffer from an additional source of erosion in this area during operation as the tape moves in close proximity to the tape head. Contact between the moving tape and the tape head during writing and reading of data can further erode the softer layers. This erosion leads to increasing recession of the poles over the life of the tape head, which is undesirable because it increases the distance between the disk or tape and the read/write transducer, in turn leading to reduced performance. In tape heads, the increasing distance over the life of the product also leads to reduced reliability in the field.
[0008] The read sense current used in the read element increases the temperature of the element substantially over that of the surrounding environment. The heat is dissipated through neighboring layers (the gap layers, the shields, the underlayer) and eventually into the surrounding air. This heat shortens the lifetime (for example, through electromigration) and reduces the performance of the sensor and limits how much current can be passed through it. The heating also causes stress in the read element as the neighboring materials may expand at different rates. In some disk drives, the read sense current is often left on whenever the particular head is active, even when it is writing instead of reading data.
[0009] Similarly, the write current used in the write element increases the temperature of the write coil. This heat is dissipated through neighboring layers. This heating effect causes stress in the write element as the neighboring materials expand at different rates. This stress can cause residual magnetization to remain in the shields and write poles after the write operation is finished. This residual magnetization can then relax to a net zero magnetization at a later time and produce a noise spike (“read after write noise” or “popcorn noise”) during a later read operation. In addition, the differential expansion, if any, of the pole material compared to the neighboring materials can cause the pole tip to protrude outward from the slider body. This pole-tip-protrusion can lead to contact with the moving magnetic medium in proximity to it. This can cause damage to the recording layer and lead to loss of data. In addition, the contact with the disk can cause additional heating due to the contact energy.
[0010] There is a continued need for improved materials, that can be deposited using methods and processes that are readily available, which can provide superior heat dissipation, mechanical hardness, electrostatic discharge protection and surface smoothness, for use in the above described devices.
SUMMARY OF THE INVENTION
[0011] Accordingly, the present invention solves the above needs through the use of a polymer precursor to ceramic. Unlike conventional methods and materials for constructing the base or underlayer, read and write gaps, planarization layers, spacer layers, and adhesive and encapsulation layers for magnetic recording transducers, polymer precursors to ceramic can be used in these layers, and converted to ceramic to provide the desired properties.
[0012] In a preferred embodiment, the polymer precursors to ceramic have the chemical formula [CR] n , more fully defined below.
[0013] These polymer precursors offer a surface having increased hardness and/or thermal conductivity. The ceramic can be processed to provide exceptional surface smoothness, with or without subsequent polishing operations. Use of this material and the method of applying the material also result in a more efficient and improved ease of manufacturing in some steps, as is clear to those skilled in the art. For example, for the base layer of a magnetic recording head, a dielectric that is spun on and then baked, having sufficient smoothness for subsequent processing, reduces the amount of processing required as compared to a dielectric layer formed from conventional materials, which requires a lengthy vacuum sputtering process followed by a separate chemomechanical planarization step.
[0014] Further, the ceramic can provide improved static discharge protection since the electrical conductivity of the ceramic used in the present invention can be controlled to enhance charge dissipation.
[0015] Further, the ceramic can be used as an adhesive layer between the device and the ‘wear cap’ for a tape head.
[0016] When applied to the method for making magnetic recording transducers, the increased thermal conductivity of the ceramic extends the lifetime of the read sensor at higher currents which allows improved performance. The improved surface also reduces the heat buildup and associated deleterious effects in the write element. The mechanical hardness of these layers also improves the slider processing, decreasing pole tip recession and pole smearing. Used as an adhesive layer between the device and the wear cap in tape heads, the surface offers a strong bond, improved thermal conductivity and a harder surface compared to the epoxies currently used. These improvements can be used singly or jointly to good effect.
[0017] It is an object of the present invention, therefore, to provide a method for making a high-performance surface that must withstand challenge by a variety of deleterious conditions, and that has superior hardness, and thermal conductivity, and is more efficient to produce than current methods for such surfaces.
[0018] Another object of the present invention is to provide a method and material which can improve the performance and longevity of read/write sensors in several ways which can be used singly or jointly.
[0019] Another object of the present invention is to provide a material and method for depositing the material that will improve the heat conduction between a shield and a slider body.
[0020] Another object of the present invention is to provide a material and method for depositing the material that will improve the heat conduction between an MR sensor and shields.
[0021] Another object of the present invention is to provide a material and method for depositing the material that will improve the heat conduction between a write element and neighboring structures that can act as heat sinks, including read element shields and a slider body.
[0022] Another object of the present invention is to provide a material and method for depositing the material that will increase the mechanical hardness of the underlayer, read and write gap layers, and the encapsulation layer.
[0023] Another object of the present invention is to provide a material and methods for decreasing the roughness of the underlayer, the gap layers and the encapsulation layer.
[0024] Another aspect of the present invention is to provide the design for single or for multiple magnetic recording head assemblies.
[0025] These and other aspects of this invention will be obvious to one skilled in the art by reading the following description in conjunction with the accompanying drawings forming a part of this specification.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Before explaining the disclosed embodiment of the present invention in detail, it is to be understood that the invention is not limited in its application to the details of the particular arrangement shown, because the invention is capable of other embodiments. Also, the terminology used herein is for the purpose of description and not of limitation.
[0027] [0027]FIG. 1 is a labeled view from the air bearing surface of an exemplary magnetic recording transducer suitable for use in a disk drive.
[0028] [0028]FIG. 2 is a labeled cross-sectional view of an exemplary magnetic recording transducer suitable for use in a disk drive.
[0029] [0029]FIG. 3 is a labeled cross-sectional view of an exemplary magnetic recording read transducer suitable for use in a tape drive that uses separate read and write elements.
[0030] [0030]FIG. 4 is a labeled cross-sectional view of an exemplary magnetic recording write transducer suitable for use in a tape drive that uses separate read and write elements.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0031] In accordance with the principles of the present invention, certain layers in magnetic recording transducers and other electronic devices such as semiconductors and MEMs devices can be formed from polymer precursors to ceramic (PPTC). In a preferred embodiment, the underlayer, read and write gap layers, planarization layers, and encapsulation are all made from PPTC, but these layers can be used independently or in combination depending on the device requirements. As will be understood by one skilled in the art, these layers may be called by different names in other electronic devices, but the methods and materials described herein are equally applicable to use in other devices where the layers provide a similar function and/or purpose.
[0032] As used herein, the term “bottom surface” will denote the layer over which the polymer precursor is to be applied; this will depend on which layer (underlayer, encapsulation, read, write, and the like) is to be formed from the polymer precursor.
[0033] Also in a preferred embodiment, the PPTC is applied to the device in a fashion similar to photoresist application methods familiar to those skilled in the art (spin-on), but other methods, including, but not limited to, spraying, dipping or wiping the device or substrate can be used. In each case, the PPTC is converted to ceramic using any of several methods such as baking in an inert atmosphere, such as an argon atmosphere, at temperatures ranging from about 20° C. to about 1800° C. for time periods from 5 min to 60 hours. Preferably, for the underlayer, and in devices such as MEMs and semiconductors, the baking is carried out a temperature of about 300° C.-600° C., more preferably 350° to 450° C., for about 1-2 hours. Other methods such as exposure to radiation, such as IR or UV radiation, exposure to a plasma, such as a hydrogen plasma, or baking under an active atmosphere are also suitable.
[0034] The polymer precursor can be converted to different ceramics, such SiC, SiN, or diamond-like carbon or diamond, depending on the polymer precursor used and the properties desired, without changing the intent of this present invention.
[0035] As used herein, the term “polymer precursor to ceramic” refers to the use of organo-metallic polymer precursors that can be used to make ceramics, as that term is understood in the art.
[0036] In a preferred embodiment, the term “polymer precursor to ceramic” refers to polymers described in U.S. Pat. No. 5,516,884, expressly incorporated herein by reference. These polymers are in liquid form and are represented by the formula
[CR] n
[0037] where R is the same or different and is selected from the group consisting of hydrogen, a saturated linear or branched—chain hydrocarbon containing 1-30 carbon atoms, and an unsaturated ring hydrocarbon containing 5 to 14 carbon atoms in the ring, each in unsubstituted or substituted form. R can also be a halogen, a Group 4 metal, and a Group 13 through Group 16 element. The lower limit for n is about 8. Where substituted, the substituent groups can be a halogen, nitro, cyano, alkoxy, carboxy, aryl, hydroxy, heterocyclic alkyl, or heterocyclic aryl groups; a halogen, a Group 4 metal, and a Group 13 through Group 16 element. The polymer comprises tetrahedrally hybridized carbon atoms linked to each other by three carbon-carbon single bonds into a three-dimensional continuous random network backbone, with one R group linked to each of said carbon atoms.
[0038] The term “polymer precursor to ceramic” thus embraces both silicon and non-silicon based polymer precursors which, when heated at the appropriate temperature, are converted to a ceramic material, as that term is understood in the art. Examples of preferred polymers of the above formula include [SiC] n where n is greater than 20 and [CH] n where n is greater than 8.
[0039] The hardness of diamond-like carbon varies substantially depending on its crystal structure, from as low as 40 kg/mm 2 up to 10,000 kg/mm 2 (the latter value for crystalline diamond). One of the beneficial features of the diamond-like carbon produced by this polymer precursor is that the hardness can be controlled within certain ranges for ease in future processing. For example, if a particular diamond-like carbon surface needs to be lapped smoother than as-deposited, for example in formation of a read gap, then the hardness of that particular layer can be controlled so that it is more readily lappable by conventional means. Hardness is controlled through the conversion process, with increasing hardness provided with the use of higher temperatures and a longer conversion time. In this preferred embodiment, the hardness of a layer, such as an encapsulation layer, that did not need to be lapped would be about 1500-10,000 kg/mm 2 whereas a layer that did require lapping would be about 800-1200 kg/mm 2 . This is as compared to conventional materials, which typically have a hardness between 50-500 kg/mm 2 . However, there is a trade-off to having ceramics of lesser hardness, as the processing conditions for ceramics of lower hardness can currently also result in lower values for thermal conductivity.
[0040] Similarly, the thermal conductivity of the material is dependent on the polymer and the conversion method used. Typical values range from about 100 J/m °K up to 2000 J/m °K. In the preferred embodiment, the thermal conductivities greater than about 800 J/m °K are used. This is as compared to conventional materials, such as alumina, which has a thermal conductivity in the range of 20-50 J/m °K, typically 36 J/m°K.
[0041] The roughness of the converted polymer can be also be controlled by processing means, such as controlling the spinning speed, length of spin time, and use of bottom surface pretreatments such as prewetting the surface with an appropriate solvent, such as tetrohydrofuran, seeding the surface with seed crystals, such as diamond seed crystals, or controlled roughening of the bottom surface, such as abrading the surface with a lapping slurry. Typically, a roughness of less than 5 nm R a is desirable for baselayers. For read gaps, roughnesses of 0.5 nm R a and smoother are required for the latest sensors. A subsequent chemomechanical polishing step can be used to achieve this roughness. This is compared with conventional materials, in which a roughness between 10 to 2000 nm can be observed. The conventional materials always require a subsequent smoothing step, such as chemomechanical polishing, to meet the required smoothness described above.
[0042] As discussed above, the electrical conductivity of the ceramic used in the present invention can be controlled to enhance charge dissipation. In an additional preferred embodiment, the properties of the polymer precursor are chosen (for example, through the use of boron or phosphorous atoms attached to the backbone) to be slightly conductive, in the range 10 8 to 10 10 ohm-cms so that any static charge from tribo-charging processes or other charge transfer processes, has a larger possibility of being dissipated without harming the sensitive transducer elements.
[0043] In a preferred embodiment for tape heads, the PPTC can be used as an adhesive layer because it bonds very strongly with the substrate and wear cap materials. The advantage to this approach is not just the strong bond between the device and the wear cap, but that the bond material is thermally conductive and very hard, in opposition to the softer, thermally resistive epoxies now used. A preferred ceramic for use in the adhesive layer is diamond-like carbon.
[0044] The substrate is prepared using standard methods and materials known in the art, and the PPTC is applied and converted to ceramic by any of the above described methods. Additional suitable methods of conversion include those described in U.S. Pat. No. 5,516,884. In a preferred embodiment of forming the underlayer, the PPTC is spun-on in a manner similar to photoresist and converted by baking in an argon atmosphere at temperatures between 300° C. and 600° C., more preferably 350° to 450° C., for 2 hours. The thickness of the underlayer ranges between 1 and 6 microns. Different spin speeds, polymer viscosities, and surface preparations can be used to obtain layers of varying thicknesses The ceramic can be polished using chemomechanical planarization (CMP) or mechanical planarization (MP) depending on the device requirements. The shields may be deposited and patterned in the conventional way. The thickness of the shields in this embodiment is between 1 and 3 microns.
[0045] In a preferred embodiment, the PPTC is spun-on, converted, and then lapped back using CMP or MP to planarize the shields and provide a thermally conductive path around them. However, the conventional process for shield planarization, in which a soft dielectric such as Al 2 O 3 is deposited and chemomechanically lapped back to expose the shields can be used without substantial detrimental effect since the areas where the Al 2 O 3 will reside is not in the direct heat dissipation path. However, where the Al 2 O 3 is exposed on the ABS or TBS, it may recede as it does in the conventional method.
[0046] The PPTC can be spun-on and converted in a similar fashion as previously described to form the first read gap layer. A typical read gap thickness in current state of the art for disk heads is between 30 to 70 nm, with a preferred embodiment being in the range of 40 nm to 55 nm. A typical read gap thickness for tape heads is between 70 to 200 nm, with a preferred embodiment being in the range of 70 to 120 nm. Due to requirements of preserving the first shield material, the temperature of the conversion step of the read gap layer generally must be between 20 to 300° C. In one embodiment, a preferred range is 150 to 250° C. In an additional embodiment, the preferred conversion range is 150 to 200° C. In an additional embodiment, a radiation source, such as a UV source, is used for the conversion of the read gap to avoid overheating the shields. The read sensor and conducting leads are formed in the typical fashion. To form the second read gap, the PPTC is again spun on and converted to ceramic. Due to requirements of preserving the sensor material, the temperature of the conversion step often must be lower than for the conversion of the first read gap layer or underlayer. For AMR sensors, such as currently generally used in tape heads, the preferred temperature is between 20 to 200° C., with one preferred embodiment between 150 to 200° C. For GMR-based sensors, such as currently generally used in disk heads, the preferred temperature range is between 20 to 110° C. In additional preferred embodiment, the temperature range is 40 to 90° C. Due to the lower temperatures required, in the most preferred embodiment, a radiation source, such as a UV source, is used for the conversion. For “CPP-MR” sensors, the read gaps would typically be formed of a conductive metal and not of the PPTC material.
[0047] For any layer deposited subsequent to the sensor deposition, such as, in the conventional design used as exemplary here, the second read gap, write gap, and encapsulation layers, the conversion is performed such that the read sensor temperature remains in the range 20 to 110° C. In a preferred embodiment, the read sensor temperature remains in the range 40 to 90° C.
[0048] The second read shield is then formed in the standard way, known to one skilled in the art, and can be planarized in the same manner as the first shield. The write gap is then formed in a similar manner as the read gaps, as described above. The write gap thickness in current tape head designs is between 150 to 400 nm; in disk heads the write gap thickness is between 100 to 250 nm. In the design used as exemplary in this disclosure, the write gap is formed after the read sensor, so the conversion is performed such that the read sensor temperature remains in the range 20to 110° C. In a preferred embodiment, the read sensor temperature is in the range 40 to 90° C. during the conversion of the write gap. The remainder of the write element is then formed in the typical way, known to one skilled in the art. After the write element is completed and the electrical interconnects are fabricated, the PPTC encapsulation layer can be spun-on in the method of the present invention as described above. In some designs, the encapsulation may require two or more iterations to achieve the desired thickness, such as 2-20 microns. In a preferred embodiment, the conversion is performed such that the read sensor temperature remains in the range 20 to 110° C. In a preferred embodiment, the read sensor temperature is in the range 40 to 90° C. during the conversion of the encapsulation. In the most preferred embodiment, a radiation source, such as a UV source, is used for the conversion. The encapsulation layer is polished back to allow contact to the electrical interconnects to the read and write transducers.
[0049] In an embodiment specific to tape heads, after the encapsulation layer is converted to ceramic, it is polished, if necessary, to provide a flat surface for the bonding of the protective wear cap. In this embodiment, an adhesive layer of the PPTC is applied to the wear cap or to the top surface of the tape head and the two pieces are placed in contact. The thickness of the bondlayer is between 0.2 and 3 microns. In a preferred embodiment, the thickness is between 1 and 2 microns. The PPTC is then converted to ceramic. For AMR-based tape heads, one preferred temperature range is between 20 to 200° C., with an additional more preferred embodiment between 150 to 200° C. This conversion process bonds the wear cap tightly to the encapsulation. The PPTC and wear cap are chosen for their hardness and good mutual adhesion properties, such as polymer precursor to diamond and AlTiC wafer. They are also chosen for the suitability to be further processed to form a tape bearing surface. Depending on the outgassing characteristics of the PPTC, channels or holes are provided in the appropriate positions in the wear cap to accommodate the outgassing.
[0050] In another embodiment specific to tape heads, the wear cap can be formed entirely of one or more layers of the converted PPTC, applied repeatedly as described above as often as required to achieve the required thickness of the wear cap (such as 10 mils), without the bonding operation.
[0051] In another embodiment specific to tape heads, the PPTC could be formed on a sacrificial substrate, such as Si, that would be chemically or mechanically removed to leave the entire underlayer and wear cap composed of the converted PPTC
[0052] Referring now to the figures, FIGS. 1 - 4 , FIG. 1 provides a labeled view from the air bearing surface of an exemplary magnetoresistive read/write head 5 suitable for use in a disk drive. FIG. 2 is a cross section of the read/write head, while FIGS. 3 and 4 refer to transducer having separate read 6 (FIG. 3) and write 7 (FIG. 4) elements. The read/write head 5 comprises a magnetic field sensor 26 to read the data and a magnetic field generator to write data on the disk. The magnetic field generator typically includes two poles, the top pole 10 and the bottom pole 14 that are separated by a write gap 46 . A magnetic field is generated when poles 10 and 14 are excited by a current flowing in a coil formed by coil elements 54 shown in FIGS. 2 and 4. When write gap 46 is in proximity to the magnetic media, a magnetic field generated by poles 10 and 14 creates selected magnetic orientations in selected locations on the magnetic media.
[0053] The magnetic field sensor 26 (also shown in FIGS. 2 and 3) is positioned between two shield elements, the top shield 18 and the bottom shield 22 . The sensor 26 is separated from the shield elements 18 and 22 by a layer or layers 30 referred to as the “read gap”.
[0054] A planarizing layer or layers 42 , shown in FIGS. 2 and 4, is used to form an insulator upon which the write coils 54 are formed.
[0055] The read/write head 5 shown in FIGS. 1 and 2, or the separate read 6 and write 7 elements shown in FIGS. 3 and 4 are formed on a substrate 34 that comprises a ceramic, typically made of AlTiC, which is then coated with an underlayer 38 , also referred to as a base layer. After fabrication, the read/write head 5 or separate read 6 and write 7 elements are further protected with an encapsulation layer 50 . In the case of tape heads an additional layer referred to as a capping substrate 58 is used to protect the relatively soft reader and writer elements from wear, as described above. An adhesive layer 60 provides adherence of the capping substrate to the encapsulation layer.
[0056] Fabrication of the magnetic recording transducer is standard and known in the art, with the exception of application of the underlayer, planarization layer, read and write gaps and encapsulation layers as applied as described in the present invention.
[0057] Other similar head structures can be used (such as those described in U.S. Pat. Nos. 6,105,238, 6,081,408 and 6,278,591, expressly incorporated herein by reference), or a device wherein the order of fabrication of the writer and reader is reversed, with the PPTC materials and methods described herein.
EXAMPLE
[0058] In an experiment to replace the current alumina baselayer with a layer of diamond-like carbon film, the [H-C] n polymer was fabricated in the manner described in U.S. Pat. No. 5,516,884, where n was greater than 200. Using ultrasonic agitation, the polymer was dissolved in a solvent, tetrahydrofuran, at an approximate concentration of 1 g/ml. The polymer was aerosolized with compressed dry air and sprayed onto a 6 inch Al/TiC wafer, spinning at 1000 rpm, for 10 seconds. The rate of addition of the polymer in the spray was undetermined. After the spray operation was completed, the wafer was spun up to 2500 rpm for 5 minutes in order to improve thickness uniformity and partially evaporate the solvent. The wafer was then placed in a vacuum chamber for 2 hours to complete the solvent evaporation. The wafer was then baked in a nitrogen atmosphere at 400° C. for 2 hours. The ramp up rate was 1 C/min; the ramp down rate was uncontrolled.
[0059] Although the present invention has been described with reference to preferred embodiments, numerous modifications and variations can be made and still the result will come within the scope of the invention. No limitation with respect to the specific embodiments disclosed herein is intended or should be inferred. | The invention discloses a process for creating an improved surface that serves as a base or underlayer, planarization layer, read layer, write layer and encapsulation material for use in generic devices that require superior heat dissipation, mechanical hardness and surface smoothness. More particularly, the invention discloses an improved material, a polymer precursor to ceramic, for use in such devices, and methods for making magnetic recording transducers, semiconductors and microelectronic mechanical system transducers using this material. The material provides improved heat dissipation, mechanical hardness, and surface smoothness. The invention also discloses devices made with such material by the disclosed methods. | 6 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to the papermaking arts. More specifically, the present invention relates to through-air-drying (TAD) fabrics used in the manufacture of bulk tissue and towel, and of nonwoven articles and fabrics.
[0003] 2. Description of the Prior Art
[0004] Soft, absorbent disposable paper products, such as facial tissue, bath tissue and paper toweling, are a pervasive feature of contemporary life in modern industrialized societies. While there are numerous methods for manufacturing such products, in general terms, their manufacture begins with the formation of a cellulosic fibrous web in the forming section of a paper machine. The cellulosic fibrous web is formed by depositing a fibrous slurry, that is, an aqueous dispersion of cellulose fibers, onto a moving forming fabric in the forming section. A large amount of water is drained from the slurry through the forming fabric, leaving the cellulosic fibrous web on the surface of the forming fabric.
[0005] The cellulosic fibrous web is then transferred to a through-air-drying (TAD) fabric or belt by means of an air flow, brought about by vacuum or suction, which deflects the web and forces it to conform, at least in part, to the topography of the TAD fabric or belt. Downstream from the transfer point, the web, carried on the TAD fabric or belt, passes through a through-air dryer, where a flow of heated air, directed against the web and through the TAD fabric or belt, dries the web to a desired degree. Finally, downstream from the through-air dryer, the web may be adhered to the surface of a Yankee dryer and imprinted thereon by the surface of the TAD fabric or belt, for further and complete drying. The fully dried web is then removed from the surface of the Yankee dryer with a doctor blade, which foreshortens or crepes the web and increases its bulk. The foreshortened web is then wound onto rolls for subsequent processing, including packaging into a form suitable for shipment to and purchase by consumers.
[0006] As noted above, there are many methods for manufacturing bulk tissue products, and the foregoing description should be understood to be an outline of the general steps shared by some of the methods. For example, the use of a Yankee dryer is not always required, as, in a given situation, foreshortening may not be desired, or other means, such as “wet creping”, may have already been taken to foreshorten the web.
[0007] It should be appreciated that TAD fabrics may take the form of endless loops on the paper machine and function in the manner of conveyors. It should further be appreciated that paper manufacture is a continuous process which proceeds at considerable speeds. That is to say, the fibrous slurry is continuously deposited onto the forming fabric in the forming section, while a newly manufactured paper sheet is continuously wound onto rolls after it is dried.
[0008] Those skilled in the art will appreciate that fabrics are created by weaving, and have a weave pattern which repeats in both the warp or machine direction (MD) and the weft or cross-machine direction (CD). Woven fabrics take many different forms. For example, they may be woven endless, or flat woven and subsequently rendered into endless form with a seam. It will also be appreciated that the resulting fabric must be uniform in appearance; that is, there are no abrupt changes in the weave pattern to result in undesirable characteristics in the formed paper sheet. In addition, any pattern marking imparted to the formed tissue will impact the characteristics of the paper.
[0009] Contemporary papermaking fabrics are produced in a wide variety of styles designed to meet the requirements of the paper machines on which they are installed for the paper grades being manufactured. Generally, they comprise a base fabric woven from monofilament and may be single-layered or multi-layered. The yarns are typically extruded from any one of several synthetic polymeric resins, such as polyamide and polyester resins, used for this purpose by those of ordinary skill in the paper machine clothing arts.
[0010] The present application is concerned, at least in part, with the TAD fabrics or belts used on the through-air dryer of a bulk tissue machine although it may have other applications beyond this. However, the present application is primarily concerned with a TAD fabric.
[0011] Such fabric may also have application in the forming section of a bulk tissue or towel machine to form cellulosic fibrous webs having discrete regions of relatively low basis weight in a continuous background of relatively high basis weight. Fabrics of this kind may also be used to manufacture nonwoven articles and fabrics, which have discrete regions in which the density of fibers is less than that in adjacent regions whereby the topography of the nonwoven article is changed, by processes such as hydroentanglement.
[0012] The properties of absorbency, strength, softness, and aesthetic appearance are important for many products when used for their intended purpose, particularly when the fibrous cellulosic products are facial or toilet tissue, paper towels, sanitary napkins or diapers.
[0013] Bulk, cross directional tensile, absorbency, and softness are particularly important characteristics when producing sheets of tissue, napkin, and towel paper. To produce a paper product having these characteristics, a fabric will often be constructed so that the top surface exhibits topographical variations. These topographical variations are often measured as plane differences between strands in the surface of the fabric. For example, a plane difference is typically measured as the difference in height between a raised weft or warp yarn strand or as the difference in height between MD knuckles and CD knuckles in the plane of the fabric's surface. Often, the fabric surface will exhibit pockets in which case plane differences may be measured as a pocket depth.
[0014] Additionally, drying capability of an industrial fabric is very essential for its use in processes such as TAD. Typically, a standard TAD fabric design in the papermaking industry for making paper towel, which is a 5-shed, 3×2 weave pattern. This design exhibits higher sheet caliper and absorbency, which allows lower sheet basis weight. The other design that is typically used in toilet tissue production is a 5-shed, 4×1 weave pattern which has demonstrated to result in a higher sheet softness. Both designs have proven to be robust in the hot, humid, TAD environment with better sheet properties. Fabric designers realize that pocket depth formed by the weave pattern is also important so multilayer thicker fabrics have been tried. However, these multilayer designs pose some serious drawbacks, such as increased fabric water content as they generally carry more water, which results in higher drying time. The primary mechanism for producing low density high caliper tissue webs with the TAD process is the pocket depth of the fabric. Therefore, it is the pocket depth of the fabric that dictates the caliper of the tissue web. A close study of the designs discussed above showed that both warp and weft yarns are primarily responsible for the creation of the depth of the pocket, thus limiting sheet caliper generation. Particularly, in single layer designs, the weft yarns show better control of pocket depth than the warp yarns. It is therefore observed that changing the profile of the weft yarns to a triangle or substantially triangular shaped cross-section instead of the conventional round yarns results in an increase of pocket depth, leading to higher sheet caliper and other desirable sheet characteristics.
[0015] The present invention provides an improved TAD fabric which exhibits favorable characteristics for the formation of tissue paper and related products.
SUMMARY OF THE INVENTION
[0016] Accordingly, the present invention is a TAD fabric, although it may find application in the forming, pressing and drying sections of a paper machine. As such, it is a papermaker's fabric which comprises a plurality of warp yarns interwoven with a plurality of weft yarns.
[0017] The present invention is preferably a TAD fabric comprising a plurality of warp yarns interwoven with a plurality of weft yarns to produce a paper-side surface pattern characterized by pockets of higher depth and volume for the same mesh and count. In the fabric according to the present invention, the weft yarns have a triangular cross-section or substantially triangular shaped cross-section and are oriented with their flat surface facing a machine side surface of the fabric. The points interlacing with the warp as they pass over and under the triangular shaped weft yarns produce increased pocket depth and volume in the TAD fabric.
[0018] It is therefore an object of the present invention to increase pocket depth and pocket volume of an industrial fabric in order to improve sheet properties such as sheet caliper, bulk and absorbency in TAD or other sheet forming type processes that utilize a TAD or structured fabric to imprint a pattern into the sheet.
[0019] It is another object of the present invention to increase the air permeability of the fabric and thus a more efficient operation.
[0020] It is a further object of the present invention to improve sheet drying rate and therefore reduce energy consumption.
[0021] It is yet another object of the present invention to improve the cleanability of the fabric.
[0022] The present invention will now be described in more complete detail with frequent reference being made to the drawing figures, which are identified below.
BRIEF DESCRIPTION OF THE DRAWING
[0023] For a more complete understanding of the invention, reference is made to the following description and accompanying drawings, in which:
[0024] FIG. 1A shows a paper side view and a surface depth view highlighting the relative pocket sizes on the paper side surface of a preferred embodiment of the present invention.
[0025] FIGS. 1B and 1C show cross-sectional views of a fabric incorporating the teachings of the present invention;
[0026] FIG. 1D shows a cross-sectional view of a standard TAD fabric; and
[0027] FIG. 2 shows a “house” shaped cross-section of a yarn.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] The present invention is preferably a TAD fabric having improved pocket depth and pocket volume on the paper side surface of the fabric. The pocket sizes are a function of the weave pattern, mesh count, and yarns used in the pattern. Pocket sizes can be characterized by an MD/CD dimension and/or by a pocket depth. The pockets are formed/bounded by weft yarns and warp yarns which are raised from the base plane of the fabric surface, produced by the weave pattern utilized. Pocket size and depth affect resultant sheet properties such as absorbency amongst others.
[0029] FIG. 1A shows a paper side view and a surface depth view highlighting the relative pocket sizes on the paper side surface of a preferred embodiment of the present invention. As shown in FIG. 1A a fabric 50 according to this embodiment may be formed using weft yarns 20 having a triangular cross-section. While we refer to weft yarns as having a triangular cross-section in reality the cross-section would be that shown in FIG. 1B . As can be seen therein the weft yarns 20 have a somewhat or substantially triangular cross-section with slightly rounded edges 22 . While an equilateral triangular shape is shown having sides 24 , other triangular shapes suitable for the purpose may also provide the desired results. In FIG. 1A the triangular weft yarns 20 are shown to run horizontally and the warp yarns 10 run vertically. Weft yarns 20 may be oriented within fabric 50 in a manner such that a flat surface or side 24 of the triangle is facing the machine side of fabric 50 and a pointed side of the triangle is facing the paper or surface side of fabric 50 , with the points interlacing with the warp yarns 10 as they pass over and under the triangular weft yarns 20 producing increased pocket depth. FIG. 1C also shows the warp yarn 10 contour for the fabric pattern according to this embodiment. Note as to warp yarns 10 they are shown having a circular cross-section. Other shaped cross-sections suitable for the purpose are possible. As seen in this contour, the fabric 50 has deeper pockets 30 , 40 , which are correspondingly highlighted on the paper side surface of fabric 50 . It can be observed that the raised weft yarns 20 and raised warp yarns 10 indicated in the paper side surface of the fabric 50 form the pockets 30 , 40 at points where they interweave with each other or points interlacing with the warp as they pass over and under the triangular weft yarns 20 , producing increased pocket depths.
[0030] Orientation of the triangular weft yarns in this manner (flat surface facing the machine side) will also greatly change the bottleneck profile for both the 5-shed weave designs discussed in the background of the invention. This means, for a given mesh and count, the air permeability of the fabric will also increase. Therefore, by keeping the same mesh and count, the fabric according to the present invention will maintain its robustness in the hot, humid TAD environment, as well as result in increased sheet caliper and absorbency or softness, overcoming the drawbacks of the prior art.
[0031] In this regard for point of comparison, there is shown in FIG. 1D a cross-sectional view of a standard TAD fabric woven in the same weave pattern as that shown in FIG. 1B with, however, using yarns having circular cross-section yarns. The weft yarns have been designated 20 ′ and the warp yarns designated 10 ′. If one compares the pocket areas formed on FIG. 1D at 30 ′ and 40 ′ to the pockets 30 and 40 in FIG. 1B one can see that the pockets created are larger in the latter due to the substantially triangular shaped cross-section yarns. This can be seen, for example, in the open area between adjacent yarns which has been designated “X” in FIG. 1B and “Y” in FIG. 1D . Accordingly for the same linear density of yarns, larger pockets are formed in the fabric shown in FIG. 1B with the attendant advantages.
[0032] Note the fabric according to the present invention may be formed using any weave pattern, such as for example, plain, twill, sheet surface having floats weft or warp dominant or combinations thereof. The present invention is intended to cover other fabric patterns having different sizes and shapes of pockets, different pocket depths, and different yarn contours. Accordingly, the present invention should not be construed as being limited to the preferred embodiment disclosed above.
[0033] The fabric according to the present invention preferably comprises only monofilament yarns, preferably of polyester, nylon, polyamide, or other polymers. Any combination of polymers for any of the yarns can be used as will be appreciated by one of ordinary skill in the art. The CD yarns of the fabric may have a triangular cross-sectional yarns of different sizes and may alternate with yarns having different non-triangular cross-sections such as circular or other shapes. Such alternation can be single or in pairs or other combinations of yarns in even or odd numbers in a manner suitable for the purpose Similarly, the MD yarns may have a circular cross-section with one or more different diameters. Further, in addition to triangular and circular cross-sectional shapes, other shapes are envisioned such as the “house” shaped yarn 60 shown in FIG. 2 . Moreover some of the yarns, including the MD yarns may have other cross-sectional shapes such as a rectangular cross-sectional shape or a non-round cross-sectional shape such as triangular or substantially triangular.
[0034] Modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the scope of the present invention. The claims to follow should be construed to cover such situations. | A through-air-drying (TAD) fabric for producing tissue paper and related products on a papermaking machine comprising a plurality of warp yarns interwoven with a plurality of weft yarns to produce pockets on a paper-side surface of the fabric. The weft yarns have a substantially triangular cross-section and are oriented with their flat surface facing a machine side surface of the fabric. The points interlacing with the warp as they pass over and under the weft yarns produce an increased pocket depth and volume in the TAD fabric. | 3 |
FIELD
[0001] This disclosure relates generally to cutting balloons utilized in balloon angioplasty and particularly to cutting balloons whose cutting action is assisted in one or more ways to increase the cutting action while at the same time allowing for reduced pressure within the cutting balloon.
BACKGROUND
[0002] Coronary artery disease (CAD) affects millions of Americans, making it the most common form of heart disease. CAD most often results from a condition known as atherosclerosis, wherein a waxy substance forms inside the arteries that supply blood to the heart. This substance, called plaque, is made of cholesterol, fatty compounds, calcium, and a blood-clotting material called fibrin. As the plaque builds up, the artery narrows, making it more difficult for blood to flow to the heart. As the blockage gets worse, blood flow to the heart slows, and a condition called angina pectoris, or simply angina, may develop. Angina is like a squeezing, suffocating, or burning feeling in the chest. The pain usually happens when the heart has an extra demand for blood, such as during exercise or times of emotional stress. In time, the narrowed or blocked artery can lead to a heart attack. A number of medicines can be used to relieve the angina pain that comes with CAD, but these medicines cannot clear blocked arteries. A moderate to severely narrowed coronary artery may need more aggressive treatment to reduce the risk of a heart attack.
[0003] Balloon angioplasty is a technique for mechanically widening narrowed or obstructed arteries, the latter typically being a result of atherosclerosis. An empty and collapsed balloon on a guide wire, known as a balloon catheter, is passed into the narrowed locations and then inflated to a fixed size using water pressures some 75 to 500 times normal blood pressure (6 to 20 atmospheres). The balloon is carefully inflated, first under low pressure, and then under higher pressure, until the narrowed area is widened. The balloon inflation crushes the fatty deposits it expands against, opening up the blood vessel for improved blood flow. The balloon is then deflated and withdrawn. Although the narrowing is improved in a majority of patients following balloon dilation, over time, the artery can again become narrow in as many as 15% to 20% of cases, requiring further balloon dilation. A stent may or may not be inserted at the time of balloon dilation to ensure the vessel remains open.
[0004] Percutaneous coronary intervention (PCI) is a therapeutic procedure to treat the stenotic (narrowed) coronary arteries of the heart due to CAD. These stenotic segments are caused by the buildup of plaque that forms due to atherosclerosis. PCI is usually performed by an interventional cardiologist.
[0005] PCI includes the use of balloons, stents, and atherectomy devices. PCI is accomplished with a small balloon catheter inserted into an artery in the groin or arm, and advanced to the narrowing in the coronary artery. The balloon is then inflated to enlarge the narrowing in the artery. When successful, PCI allows more blood and oxygen to be delivered to the heart muscle and can relieve the chest pain of angina, improve the prognosis of individuals with unstable angina, and minimize or stop a heart attack without having the patient undergo open heart coronary artery bypass graft (CABG) surgery.
[0006] Balloon angioplasty is also called percutaneous transluminal coronary angioplasty (PTCA). Both PCI and PTCA are non-surgical procedures. Balloon angioplasty can also be used to open narrowed vessels in many other parts of the body. Peripheral angioplasty (PA) refers to the use of a balloon to open a blood vessel outside the coronary arteries. It is commonly done to treat atherosclerotic narrowing of the abdomen, leg, and renal arteries. PA can also be done to treat narrowing in veins. Often, PA is used in conjunction with peripheral stenting and atherectomy. For example, doctors can perform carotid angioplasty to open narrowed carotid arteries, which are the arteries that supply blood to the brain. A stroke most often occurs when the carotid arteries become blocked and the brain does not get enough oxygen. Balloon angioplasty can also be performed in the aorta (the main artery that comes from the heart), the iliac artery (in the hip), the femoral artery (in the thigh), the popliteal artery (behind the knee), and the tibial and peroneal arteries (in the lower leg). The use of fluoroscopy assists the doctor in the location of blockages in the coronary arteries as the contrast dye moves through the arteries. A small sample of heart tissue (biopsy) may be obtained during the procedure to be examined later under the microscope for abnormalities.
[0007] A cutting balloon (CB) is an angioplasty device used in PCI and PTCA and is a proven tool for the mechanical challenges of complex lesions that are often resistant to conventional balloon angioplasty. A CB has a special balloon with small blades that are activated when the balloon is inflated. The CB typically has three or four atherotomes (microsurgical blades) bonded longitudinally to its surface, suitable for creating discrete longitudinal incisions in the atherosclerotic target coronary segment during balloon inflation. Cutting balloon angioplasty (CBA) features three or four atherotomes, which are 3-5 times sharper than conventional surgical blades. The atherotomes, which are fixed longitudinally on the outer surface of a non-complaint balloon, expand radially and deliver longitudinal incisions in the plaque or target lesion, relieving its hoop stress. With the CBA, the increase in the vessel lumen diameter is obtained in a more controlled fashion and with a lower balloon inflation pressure than PCI and PTCA procedures utilizing conventional balloons. This controlled dilation could reduce the extent of vessel wall injury and the incidence of restenosis.
[0008] The advantage of CBA is its ability to reduce vessel stretch and vessel injury by scoring the target coronary segment longitudinally rather than causing an uncontrolled disruption of the atherosclerotic plaque or target lesion. The atherotomes deliver a controlled fault line during dilation to ensure that the crack propagation ensues in an orderly fashion. The CB also dilates the target vessel with less force to decrease the risk of a neoproliferative response and restenosis. The unique design of the CB is engineered to protect the vessel from the edges of the atherotomes when it is deflated. This minimizes the risk of trauma to the vessel as the balloon is passed to and from the target coronary segment. With CBA, balloon inflation pressures can still range between 14-16 atmospheres, though lower inflation pressures are recommended.
[0009] Angioplasty balloons that employ a woven mesh, cutting strings, or wires are also known in the art. These balloons have been shown to be more flexible and safer than balloons employing cutting blades and edges. The scoring elements can, for example, be in the form of a single wire or a plurality of wires wrapped around a dilation balloon in a helical configuration. Other angioplasty cutting balloon catheter assemblies have a catheter equipped with an inflatable balloon with an interior cavity and an expandable covering around the balloon. The expandable covering may be in the form of a mesh coating having a cross-hatched pattern. The mesh coating may be made of plastic or metal fibers, where at least some of the fibers have cutting edges. In operation, the cutting edges abrade the stenosis, plaque, or lesions along the vessel walls when the catheter assembly is reciprocally moved longitudinally or rotationally after inflation of the balloon.
SUMMARY
[0010] These and other needs are addressed by the various aspects, embodiments, and configurations of the present disclosure. The disclosure is generally directed to the use of vibrations to enhance the performance of cutting balloons, particularly in angioplasty, in treating lesions, occlusions and plaque.
[0011] A method, according to this disclosure, can perform balloon angioplasty by the steps of:
[0012] (a) inserting an assisted cutting balloon into a target coronary segment partially occluded with plaque, the assisted cutting balloon having one or more cutting devices positioned on an exterior of the dilation balloon; and
[0013] (b) inflating the dilation balloon and vibrating the one or more cutting devices while the cutting balloon is inserted into the target coronary segment.
[0014] The expanding and vibrating dilation balloon can crush softer portions of the plaque, and/or the vibrating wire abrasive can cut the harder or calcified portions of the plaque.
[0015] An assisted cutting balloon for performing balloon angioplasty, according to this disclosure, can include:
[0016] (a) a dilation balloon;
[0017] (b) one or more cutting devices operably positioned on an exterior of the dilation balloon;
[0018] (c) a laser light source terminating at a distal end in the interior of the dilation balloon; and
[0019] (d) a contrast medium for inflating the dilation balloon.
[0020] As the dilation balloon is inflated with the contrast medium and/or after inflation, the laser light source can transmit pulsed laser light into the contrast medium creating shockwaves that propagate through the contrast medium, thereby causing the cutting device(s) to vibrate and assist in the cracking or abrading of the surrounding plaque in contact with the balloon.
[0021] The contrast material commonly exhibits a high degree of optical absorption to the laser light. When a laser fiber or fibers inserted into the balloon interior emit optical energy into the contrast material, the material is believed to experience a rapid rate of energy absorption, creating the shockwave.
[0022] An assisted cutting balloon for performing balloon angioplasty, according to this disclosure, can include:
[0023] (a) a dilation balloon;
[0024] (b) one or more cutting devices operably positioned on an exterior of the dilation balloon; and
[0025] (c) a flexible wire waveguide connected at a distal end to the cutting device(s) and at a proximal end to an ultrasonic apparatus.
[0026] The ultrasonic apparatus can transmit ultrasonic waves through the flexible wire waveguide to the cutting device(s) causing the cutting device(s) to vibrate as and/or after the dilation balloon is inflated, thereby assisting in the cracking or abrading of the surrounding plaque in contact with the balloon.
[0027] The cutting device(s) can be a wire abrasive bound to an exterior of the dilation balloon.
[0028] In one application, wire or braid material is constructed with a diamond abrasive or other types of abrasive cutting material and is wrapped around a dilation balloon in a helical or other type of configuration. The wire or braided material is vibrated using high, low, or even ultrasonic waves transmitted to the wire or braided material via local or remote methods, substantially enhancing the ability to cut or abrade the plaque.
[0029] The guide wire can be inserted into a vasculature system and moved past the target coronary segment, and the assisted cutting balloon translated over the guide wire to the target coronary segment.
[0030] In one procedure, the dilation balloon can be inflated with a contrast medium. Specifically, a laser fiber and the assisted cutting balloon are translated along over the guide wire to the target coronary segment, with the distal end of the laser fiber terminating in the middle of the dilation balloon. A laser generator connected to a proximal end of the laser fiber emits laser light from the distal end of the laser fiber at a very short pulse duration, thereby creating shockwaves that propagate through the contrast medium as the dilation balloon is inflating, causing the cutting device(s) to vibrate. The vibrations cause the cutting device(s) to cut or abrade harder or calcified portions of the plaque as the dilation balloon is inflating. The laser generator typically generates 308 nm laser light at pulse durations ranging from 120-140 nsec. While other types of laser generators can be employed, a common laser generator is an excimer laser.
[0031] To assist positioning within the body, the assisted cutting balloon, guide wire, and laser fiber can be enclosed in a multi-lumen catheter.
[0032] In another procedure, an ultrasonic apparatus having a flexible wire waveguide connected at a proximal end to the ultrasonic apparatus and connected at a distal end to the cutting device(s) transmits ultrasonic waves through the flexible wire waveguide to the cutting device(s), causing the cutting device(s) to vibrate. The vibrating cutting device(s) cut the harder or calcified portions of the plaque as and/or after the dilation balloon is inflated.
[0033] In any of the above procedures, the balloon is commonly inflated to pressures ranging between about 1-30 atmospheres, 5-25 atmospheres, and 10-20 atmospheres.
[0034] The present disclosure can provide benefits relative to conventional cutting balloons. The use of vibration, at low, medium, or high frequencies, can enhance dramatically the performance of cutting balloons. Cutting device(s), particularly the wire or braid materials constructed with diamond abrasives or other type of abrasive cutting materials, can cut, abrade, or otherwise modify plaque, particularly calcified or hard plaque, while leaving surrounding soft tissue and compliant balloon material substantially unaltered and undamaged. This can be a very effective method to assist in cracking or modifying plaque in arteries. The disclosure can avoid the need to inflate balloons to very high pressures (e.g., from about 15 to about 30 atms), thereby permitting the use of lower pressures (e.g., typically no more than about 10 atms and even more typically no more than about 7.5 atms).
[0035] As used herein, “at least one,” “one or more,” and “and/or” are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions “at least one of A, B and C,” “at least one of A, B, or C,” “one or more of A, B, and C,” “one or more of A, B, or C,” and “A, B, and/or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B and C together. When each one of A, B, and C in the above expressions refers to an element, such as X, Y, and Z, or class of elements, such as X1-Xm, Y1-Yn, and Z1-Zo, the phrase is intended to refer to a single element selected from X, Y, and Z, a combination of elements selected from the same class (e.g., X1 and X2) as well as a combination of elements selected from two or more classes (e.g., Y1 and Z3).
[0036] It is to be noted that the term “a” or “an” entity refers to one or more of that entity. As such, the terms “a” (or “an”), “one or more,” and “at least one” can be used interchangeably herein. It is also to be noted that the terms “comprising,” “including,” and “having” can be used interchangeably.
[0037] “Contrast medium” or “contrast media” is generally any substance used to change the imaging characteristics of a patient, thereby providing additional information such as anatomical, morphological, and/or physiological. Contrast media can, for example, provide information regarding vasculature, vascular integrity, and/or qualitative assessment of vasculature function or operation. Positive contrast agents increase the attenuation of tissue, blood, urine, or outline spaces such as the gastrointestinal lumen or subarachnoid space. Two primary types of positive contrast agents are barium sulfate agents and various halogenated (e.g., iodated) compounds. Negative contrast agents normally decrease attenuation by occupying a space, such as the bladder, gastrointestinal tract, or blood vessels. Negative contrast agents are typically gases, such as carbon dioxide and nitrous oxide. Another type of contrast media, namely MRI contrast agents, uses typically superparamegnetism. Finally, ultrasound contrast media, namely sonagraphic contrast agents, are typically composed of gas bubbles (air or perfluor gases) stabilized by a shell of phospholipids, surfactants, albumin, or polymers.
[0038] The term “means” as used herein shall be given its broadest possible interpretation in accordance with 35 U.S.C., Section 112, Paragraph 6. Accordingly, a claim incorporating the term “means” shall cover all structures, materials, or acts set forth herein, and all of the equivalents thereof. Further, the structures, materials or acts and the equivalents thereof, shall include all those described in the summary of the invention, brief description of the drawings, detailed description, abstract, and claims themselves.
[0039] “Ultrasound” refers to sound or other vibrations having an ultrasonic frequency, which is commonly a frequency above about 20 thousand cycles per second (20,000 Hz).
[0040] It should be understood that every maximum numerical limitation given throughout this disclosure is deemed to include each and every lower numerical limitation as an alternative, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this disclosure is deemed to include each and every higher numerical limitation as an alternative, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this disclosure is deemed to include each and every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
[0041] The preceding is a simplified summary of the disclosure to provide an understanding of some aspects of the disclosure. This summary is neither an extensive nor exhaustive overview of the disclosure and its various aspects, embodiments, and configurations. It is intended neither to identify key or critical elements of the disclosure nor to delineate the scope of the disclosure but to present selected concepts of the disclosure in a simplified form as an introduction to the more detailed description presented below. As will be appreciated, other aspects, embodiments, and configurations of the disclosure are possible, utilizing alone or in combination, one or more of the features set forth above or described in detail below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0042] FIG. 1 shows a schematic illustration of an embodiment of an assisted cutting balloon.
[0043] FIG. 2 shows a schematic diagram of an embodiment of an ultrasonic generator apparatus.
[0044] FIG. 3 shows a partial cross section view of a partially occluded artery with an assisted cutting balloon in place prior to inflation.
[0045] FIG. 4 shows a partial cross section view of a partially occluded artery with an assisted cutting balloon in place and inflated.
[0046] FIG. 5 shows a partial cross section view of a partially occluded artery with an assisted cutting balloon after deflation and ready for removal.
[0047] FIG. 6 shows a schematic illustration of another embodiment of an assisted cutting balloon.
[0048] FIG. 7 shows a schematic diagram of an embodiment of a laser generator apparatus.
[0049] The accompanying drawings are incorporated into and form a part of the specification to illustrate several examples of the present disclosure. These drawings, together with the description, explain the principles of the disclosure. The drawings simply illustrate preferred and alternative examples of how the disclosure can be made and used and are not to be construed as limiting the disclosure to only the illustrated and described examples. Further features and advantages will become apparent from the following, more detailed, description of the various aspects, embodiments, and configurations of the disclosure, as illustrated by the drawings referenced below.
DETAILED DESCRIPTION
[0050] FIG. 1 shows a schematic illustration of an embodiment of an assisted cutting balloon. Referring now to FIG. 1 , Assisted Cutting Balloon 10 includes a Dilation Balloon 12 , which may be any conventional angioplasty balloon such as commonly used by interventional cardiologists or radiologists, and a Wire Abrasive 14 mounted, attached, affixed, or otherwise bound, in a helical configuration, to the exterior of Dilation Balloon 12 . Wire Abrasive 14 may be one wire strand or many wire strands wrapped or braided together. The wire may be composed of any suitable material, with one or more metal and/or plastic fibers being typical. Diamond material or any other suitable abrasives may be used as an abrasive bonded to the wire. Diamond wire impregnated with diamond dust is relatively inexpensive and is readily available in various diameters and lengths. Multiple configurations of Dilation Balloon 12 may be used with different types of cutting wire or string wrap patterns or braids, such as diamond, cross-hatch, woven or unwoven mesh, reverse helical, longitudinal, radial, etc., around the exterior of the Dilation Balloon 12 and with different types of abrasive coated wire or cutting blades or atherotomes in a variety of geometrical shapes bonded or applied to Dilation Balloon 12 . Other cutting balloon configurations known to those of skill in the art may be employed as the Dilation Balloon 12 . Guide Wire 30 is inserted into the vasculature system of the subject and past Target Coronary Segment 32 (see FIG. 3 ). Assisted Cutting Balloon 10 is translated over Guide Wire 30 to Target Coronary Segment 32 .
[0051] FIG. 2 shows a schematic diagram of an embodiment of an ultrasonic generator apparatus. Referring now to FIG. 2 , Ultrasonic Apparatus 16 includes a Piezoelectric Converter And Acoustic Horn 18 that operates with a resonant frequency. Piezoelectric Converter And Acoustic Horn 18 is driven by Ultrasonic Generator 20 at an adjustable resonant frequency or set of plural frequencies. The frequencies can be temporally fixed or varied during Assisted Cutting Balloon 12 operation. This ensures that resonance of Piezoelectric Converter And Acoustic Horn 18 is achieved despite minor alterations in the resonant frequency of the system. In addition, Ultrasonic Generator 20 has adjustable input power dial settings.
[0052] Flexible Wire Waveguide 22 is connected to Piezoelectric Converter And Acoustic Horn 18 at a Proximal End 24 and fixed tightly into the radiating face of Piezoelectric Converter And Acoustic Horn 18 ensuring a rigid connection between the two. Distal End 26 of Flexible Wire Waveguide 22 is rigidly connected to a Proximal End 28 of Wire Abrasive 14 (see FIG. 1 ). Other local or remote methods may be used to transmit high, low, or ultrasonic waves to Flexible Wire Waveguide 22 such as.
[0053] FIG. 3 shows a partial cross section view of a partially occluded artery with an assisted cutting balloon in place prior to inflation. Referring now to FIG. 3 , Assisted Cutting Balloon 10 has been translated over Guide Wire 30 to Target Coronary Segment 32 . The interior of Artery 34 is partially occluded with deposits of Plaque 36 .
[0054] FIG. 4 shows a partial cross section view of a partially occluded artery with an assisted cutting balloon in place and inflated. Referring now to FIG. 4 , as Dilation Balloon 12 is inflated, Ultrasonic Apparatus 16 is powered on. Flexible Wire Waveguide 22 causes Wire Abrasive 14 to vibrate. Thus, as Wire Abrasive 14 of Dilation Balloon 12 comes into contact with Plaque 36 , Dilation Balloon 12 crushes the softer portions of Plaque 36 and the cutting action of Wire Abrasive 14 , which is enhanced due to the vibration imparted via Flexible Wire Waveguide 22 , cuts the harder or calcified portions of Plaque 36 . The enhanced cutting action reduces the inflation pressure necessary to 5 to 10 atmospheres which reduces the chance for damage to Artery 34 .
[0055] FIG. 5 shows a partial cross section view of a partially occluded artery with an assisted cutting balloon after deflation and ready for removal. Referring now to FIG. 5 , Striations 38 can be seen in crushed Plaque 36 due to the cutting action of Wire Abrasive 14 . Assisted Cutting Balloon 10 is now ready for removal over Guide Wire 30 .
[0056] FIG. 6 shows a schematic illustration of another embodiment of an assisted cutting balloon. Referring now to FIG. 6 , Assisted Cutting Balloon 50 includes a Dilation Balloon 52 , which may be any conventional angioplasty balloon such as commonly used by interventional cardiologists or radiologists, and a Wire Abrasive 54 mounted over or attached to Dilation Balloon 52 . Wire Abrasive 54 may be one wire strand or many wire strands braided together. Diamond material or any other suitable abrasives may be used as an abrasive bonded to the wire. Diamond wire impregnated with diamond dust is relatively inexpensive and is readily available in various diameters and lengths. Multiple configurations of Dilation Balloon 52 may be used with different types of wire wrap patterns or braids, such as diamond or cross-hatch, helical, etc., and with different types of abrasive coated wire or cutting blades in a variety of geometrical shapes bonded or applied to Dilation Balloon 12 . Guide Wire 70 is inserted into the subject and Assisted Cutting Balloon 50 is translated over Guide Wire 70 to a target coronary segment, such as Target Coronary Segment 32 shown in FIG. 3 .
[0057] FIG. 7 shows a schematic diagram of an embodiment of a laser generator apparatus. Referring now to FIG. 7 , a laser light source such as Laser Apparatus 56 includes a Laser Generator 58 controlled by a Computer 60 . Flexible Cladding 62 shields Laser Fiber 64 , which may be a single fiber or multiple fibers. Flexible Cladding 62 runs parallel with Guide Wire 70 and both may be enclosed in a multi-lumen catheter along with Assisted Cutting Balloon 10 . Distal End 66 (see FIG. 6 ) of Flexible Cladding 62 terminates in the middle of Dilation Balloon 52 . Laser Fiber 64 extends a short distance from Distal End 66 . When Assisted Cutting Balloon 50 has been translated over Guide Wire 70 to a target coronary segment, it will appear like that shown in FIG. 3 , where the interior of Artery 34 of Target Coronary Segment 32 is partially occluded with deposits of Plaque 36 .
[0058] Substituting now Assisted Cutting Balloon 50 for Assisted Cutting Balloon 10 shown in FIG. 4 , Dilation Balloon 52 is inflated with Contrast Medium 68 . Contrast Medium 68 may be one of many different compounds as found in the ACR Manual of Contrast Media, Version 8, 2012. As Dilation Balloon 52 is inflated, Laser Apparatus 56 is activated, which, in one embodiment, may be an excimer laser that emits 308 nm laser light at very short pulse durations (120-140 nsec.) from Laser Fiber 64 . Contrast Medium 68 exhibits a very high absorption to this laser light. Due to the high absorption and short pulse width of the laser light, shockwaves are created that propagate through the volume of Contrast Medium 68 within Dilation Balloon 52 . The shockwaves assist in the cracking, crushing, or modification of Plaque 36 by Dilation Balloon 52 . The shockwave also causes Wire Abrasive 54 to vibrate. Thus, as Wire Abrasive 54 of Dilation Balloon 52 comes into contact with Plaque 36 , Dilation Balloon 52 , assisted by the shockwaves as well as by inflation, crushes the softer portions of Plaque 36 , and the cutting action of Wire Abrasive 54 , which is enhanced due to the vibration imparted via the shockwaves traveling through the volume of Contrast Medium 68 , cuts the harder or calcified portions of Plaque 36 . Dilation Balloon 52 is then deflated and ready for removal as shown in FIG. 5 . Striations 38 will also be seen in crushed Plaque 36 due to the cutting action of Wire Abrasive 54 .
[0059] A number of variations and modifications of the disclosure can be used. It would be possible to provide for some features of the disclosure without providing others.
[0060] For example in one alternative embodiment, cutting blades may be used instead of abrasive wire.
[0061] In another example, other Assisted Cutting Balloon 12 vibrating mechanisms may be employed. Examples include mechanically induced vibration (e.g., by a micro-vibration motor), electrically induced vibration, electromechanically induced vibration (e.g., by a micro-electromechanical system), magnetically induced vibration, electromagnetically induced vibration, and vibration induced by other sound or acoustical frequencies.
[0062] In another example, the vibration source may be positioned either remotely, as discussed and shown above, or locally, such as in the proximity of the balloon itself, or a combination thereof. Micro-components can be positioned in or near the balloon in the catheter itself whereby attenuation of vibrations remotely generated is reduced. For example, a micro-vibration motor, micro-electromechanical system, or micro-piezoelectric transducer can be positioned in the catheter in proximity to the balloon.
[0063] The present disclosure, in various aspects, embodiments, and configurations, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various aspects, embodiments, configurations, subcombinations, and subsets thereof. Those of skill in the art will understand how to make and use the various aspects, embodiments, and configurations, after understanding the present disclosure. The present disclosure, in various aspects, embodiments, and configurations, includes providing devices and processes in the absence of items not depicted and/or described herein or in various aspects, embodiments, and configurations hereof, including in the absence of such items as may have been used in previous devices or processes, e.g., for improving performance, achieving ease and\or reducing cost of implementation.
[0064] The foregoing discussion of the disclosure has been presented for purposes of illustration and description. The foregoing is not intended to limit the disclosure to the form or forms disclosed herein. For example, in the foregoing Detailed Description, various features of the disclosure are grouped together in one or more, aspects, embodiments, and configurations for the purpose of streamlining the disclosure. The features of the aspects, embodiments, and configurations of the disclosure may be combined in alternate aspects, embodiments, and configurations other than those discussed above. This method of disclosure is not to be interpreted as reflecting an intention that the claimed disclosure requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed aspects, embodiments, and configurations. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the disclosure.
[0065] Moreover, though the description of the disclosure has included descriptions of one or more aspects, embodiments, or configurations and certain variations and modifications, other variations, combinations, and modifications are within the scope of the disclosure, e.g., as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative aspects, embodiments, and configurations to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter. | A dilation balloon is wrapped in one or more patterns with a wire or braided material having diamond abrasive or other abrasive material bonded thereto. The wire or braided material is vibrated in one or more ways to enhance the cutting action of the wire abrasive. The wire abrasive may be vibrated using high, low, or even ultrasonic waves transmitted to the wire abrasive via local or remote methods. Alternatively, the dilation balloon may be dilated with a contrast media that exhibits a high absorption to laser light. The contrast material is lased with a laser fiber or fibers inserted into the balloon interior, creating a substantial shockwave that vibrates the balloon and assists in the cracking or abrading of the surrounding plaque in contact with the dilation balloon. The cutting balloon may employ the abrasive coated wires described above or cutting blades. | 0 |
FIELD
The present disclosure relates to diagnostic systems for electronic control systems, and more particularly, to control systems and methods for detecting an out of range condition for sensors of the electronic control systems.
BACKGROUND
The background description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure.
Direct injection gasoline engines are currently used by many engine manufacturers. In a direct injection engine, highly pressurized gasoline is injected via a common fuel rail directly into a combustion chamber of each cylinder. This is different than conventional multi-point fuel injection that is injected into an intake tract or cylinder port.
Gasoline-direct injection enables stratified fuel-charged combustion for improved fuel efficiency and reduced emissions at a low load. The stratified fuel charge allows ultra-lean burn and results in high fuel efficiency and high power output. The cooling effect of the injected fuel and the even dispersion of the air-fuel mixture allows for more aggressive ignition timing curves. Ultra lean burn mode is used for light-load running conditions when little or no acceleration is required. Stoichiometric mode is used during moderate load conditions. The fuel is injected during the intake stroke and creates a homogenous fuel-air mixture in the cylinder. A fuel power mode is used for rapid acceleration and heavy loads. The air-fuel mixture in this case is a slightly richer than stoichiometric mode which helps reduce knock.
Direct-injected engines are configured with a high-pressure fuel pump used for pressurizing the injector fuel rail. A pressure sensor is attached to the fuel rail for control feedback. The pressure sensor provides an input to allow the computation of the pressure differential information used to calculate the injector pulse width for delivering fuel to the cylinder. Errors in the measured fuel pressure at the fuel rail result in an error in the mass of the fuel delivered to the individual cylinder.
SUMMARY
The present disclosure provides a method and system by which an error from the pressure sensor in the fuel rail may be quantified and used for closed-loop control. This will result in the proper mass of fuel being delivered to the individual cylinder. This may also allow for diagnostics of the fuel rail pressure sensor.
In one aspect of the invention, a method includes generating a time-based diagnostic, generating an event-based diagnostic, synchronizing the time-based diagnostic and the event-based diagnostic to obtain a diagnostic result and generating a fault signal in response to the diagnostic result.
In a further aspect of the invention, a control module for determining a sensor error includes a time-based diagnostic module generating a time-based diagnostic for a sensor and an event-based diagnostic module generating an event-based diagnostic for the sensor. A synchronizing module synchronizes the time-based diagnostic and the event-based diagnostic to obtain a diagnostic result. A fault indicator module generates a fault signal in response to the diagnostic result.
Further areas of applicability of the present disclosure will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the disclosure, are intended for purposes of illustration only and are not intended to limit the scope of the disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
The present disclosure will become more fully understood from the detailed description and the accompanying drawings, wherein:
FIG. 1 is a functional block diagram of a control system that adjusts engine timing based on vehicle speed according to some implementations of the present disclosure;
FIG. 2 is a functional block diagram of the fuel injection system according to the present disclosure;
FIG. 3 is a block diagram of the control system of FIG. 1 for performing the method of the present disclosure;
FIG. 4 is a flowchart of a method for determining a pressure sensor error; and
FIG. 5 is a plot of a time-based error versus an event-based error over time.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following description of the preferred embodiment is merely exemplary in nature and is in no way intended to limit the disclosure, its application, or uses. As used herein, the term module refers to an application specific integrated circuit (ASIC), an electronic circuit, a processor (shared, dedicated, or group) and memory that execute one or more software or firmware programs, a combinational logic circuit, and/or other suitable components that provide the described functionality. As used herein, the term boost refers to an amount of compressed air introduced into an engine by a supplemental forced induction system such as a turbocharger. The term timing refers generally to the point at which fuel is introduced into a cylinder of an engine (fuel injection) is initiated.
Referring now to FIG. 1 , an exemplary engine control system 10 is schematically illustrated in accordance with the present disclosure. The engine control system 10 includes an engine 12 and a control module 14 . The engine 12 can further include an intake manifold 15 , a fuel injection system 16 having fuel injectors (illustrated in FIG. 2 .), an exhaust system 17 and a turbocharger 18 . The exemplary engine 12 includes six cylinders 20 configured in adjacent cylinder banks 22 , 24 in a V-type layout. Although FIG. 1 depicts six cylinders (N=6), it can be appreciated that the engine 12 may include additional or fewer cylinders 20 . For example, engines having 2, 4, 5, 8, 10, 12 and 16 cylinders are contemplated. It is also anticipated that the engine 12 can have an inline-type cylinder configuration. While a gasoline powered internal combustion engine utilizing direct injection is contemplated, the disclosure may also apply to diesel or alternative fuel sources.
During engine operation, air is drawn into the intake manifold 15 by the inlet vacuum created by the engine intake stroke. Air is drawn into the individual cylinders 20 from the intake manifold 15 and is compressed therein. Fuel is injected by the injection system 16 , which is described further in FIG. 2 . The air/fuel mixture is compressed and the heat of compression and/or electrical energy ignites the air/fuel mixture. Exhaust gas is exhausted from the cylinders 20 through exhaust conduits 26 . The exhaust gas drives the turbine blades 25 of the turbocharger 18 which in turn drives compressor blades 27 . The compressor blades 27 can deliver additional air (boost) to the intake manifold 15 and into the cylinders 20 for combustion.
The turbocharger 18 can be any suitable turbocharger such as, but not limited to, a variable nozzle turbocharger (VNT). The turbocharger 18 can include a plurality of variable position vanes 27 that regulate the amount of air delivered into the engine 12 based on a signal from the control module 14 . More specifically, the vanes 27 are movable between a fully-open position and a fully-closed position. When the vanes 27 are in the fully-closed position, the turbocharger 18 delivers a maximum amount of air into the intake manifold 15 and consequently into the engine 12 . When the vanes 27 are in the fully-open position, the turbocharger 18 delivers a minimum amount of air into the intake manifold of engine 12 . The amount of delivered air is regulated by selectively positioning the vanes 27 between the fully-open and fully-closed positions.
The turbocharger 18 includes an electronic control vane solenoid 28 that manipulates a flow of hydraulic fluid to a vane actuator (not shown). The vane actuator controls the position of the vanes 27 . A vane position sensor 30 generates a vane position signal based on the physical position of the vanes 27 . A boost sensor 31 generates a boost signal based on the additional air delivered to the intake manifold 15 by the turbocharger 18 . While the turbocharger implemented herein is described as a VNT, it is contemplated that other turbochargers employing different electronic control methods may be employed.
A manifold absolute pressure (MAP) sensor 34 is located on the intake manifold 15 and provides a (MAP) signal based on the pressure in the intake manifold 15 . A mass air flow (MAF) sensor 36 is located within an air inlet and provides a mass air flow (MAF) signal based on the mass of air flowing into the intake manifold 15 . The control module 14 uses the MAF signal to determine the mass of air flowing into the intake manifold. The mass of the intake air can be used to determine the fuel supplied to the engine 12 based on the A/F ratio in response to engine start, catalyst light-off, and engine metal overheat protection. An RPM sensor 44 such as a crankshaft position sensor provides an engine speed signal. An intake manifold temperature sensor 46 generates an intake air temperature signal. The control module 14 communicates an injector timing signal to the injection system 16 . A vehicle speed sensor 49 generates a vehicle speed signal.
The exhaust conduits 26 can include an exhaust recirculation (EGR) valve 50 . The EGR valve 50 can recirculate a portion of the exhaust. The controller 14 can control the EGR valve 50 to achieve a desired EGR rate.
The control module 14 controls overall operation of the engine system 10 . More specifically, the control module 14 controls engine system operation based on various parameters including, but not limited to, driver input, stability control and the like. The control module 14 can be provided as an Engine Control Module (ECM).
The control module 14 can also regulate operation of the turbocharger 18 by regulating current to the vane solenoid 28 . The control module 14 according to an embodiment of the present disclosure can communicate with the vane solenoid 28 to provide an increased flow of air (boost) into the intake manifold 15 .
An exhaust gas oxygen sensor 60 may be placed within the exhaust manifold or exhaust conduit to provide a signal corresponding to the amount of oxygen in the exhaust gasses.
Referring now to FIG. 2 , the fuel injection system 16 is shown in further detail. A fuel rail 110 is illustrated having fuel injectors 112 that deliver fuel to cylinders of the engine. It should be noted that the fuel rail 110 is illustrated having three fuel injectors 112 corresponding to the three cylinders of one bank of cylinders of the engine 12 of FIG. 1 . More than one fuel rail 110 may be provided on a vehicle. Also, more or fewer fuel injectors may also be provided depending on the configuration of the engine. The fuel rail 110 delivers fuel from a fuel tank 114 through a high-pressure fuel pump 116 . The control module 14 controls the fuel pump 116 in response to various sensor inputs including an input signal 118 from a pressure sensor 120 . The control module 14 also controls the injectors 112 . The operation of the system will be further described below.
Referring now to FIG. 3 , the control module of FIG. 1 is illustrated in further detail. The control module 14 may include a time-based diagnostic module 210 and an event-based diagnostic module 212 . The time-based diagnostic module 210 and the event-based diagnostic module 212 may provide two different methods for diagnosing a sensor such as a pressure sensor. The time-based diagnostic module 210 generates a time-based diagnostic signal and communicates the time-based diagnostic signal to a synchronizing module 214 . The event-based diagnostic module 212 communicates an event-based diagnostic signal to the synchronizing module 214 . The synchronizing module 214 communicates a synchronized diagnostic result to a fault indicator module 216 .
The time-based diagnostic module 210 may include a timer module 250 that generates a timing signal capable of timing various time periods, including a sample time and an end time and therefore an overall time period. The timer module 250 also may time regular time intervals over which samples are to be taken. The timing signal from the timer module 250 is communicated to a sample module 252 . The sample module 252 samples the sensor signal such as the pressure sensor signal used in this example. The sample module 252 samples at the intervals provided by the timer module 252 . The sample module 252 may sample at a first rate which is different than a second rate used in the event-based diagnostic module. A sample comparison module 254 compares the samples to a comparison threshold. A counter-module 256 counts the number of comparisons that are above or below or both for a predetermined sample. Thus, the sample comparison module 254 may compare a pressure high threshold and a pressure low threshold with the sample and thus the number of counts above a high-pressure threshold or below a low-pressure threshold may be counted in the counter module 256 . In block 258 , the counts from the counter module 256 are compared to a counter-threshold which in turn may be communicated to the synchronizing module 214 .
When the time-based diagnostic module is used alone, a faulty sensor may be detected too late at high RPMs while using many faulty signals. At low RPMs the diagnostic test may pass too soon for a good sensor.
The event-based diagnostic module 212 generates an event-based diagnostic signal. An event may, for example, be an engine-synchronized event. The event signal for triggering the sample may be received at the event trigger module 270 . The event trigger module 270 may receive various types of signals including an engine synchronization event such as a camshaft or crankshaft timing signal. The sample module may sample the sensor signal such as the pressure sensor signal at a different rate than the time-based diagnostic module 210 . Of course, the same rate may also be used. The sample module 272 generates sample signals and communicates the sample signals to a sample comparison module 274 . The sample module at the second rate 272 receives an input from the first rate sample module 252 . The sample comparison module 274 compares each sample to a threshold. The thresholds may be pressure-high thresholds and pressure-low thresholds as described above. Therefore, the counter module 276 may generate a count of the number of pressure-high signals and pressure-low signals. The number of counts counted by the counter 276 is compared to a count threshold in a count threshold module 278 . The count threshold module 278 generates an event-based diagnostic and communicates the event-based diagnostic to the synchronizing module 214 .
The synchronizing module 214 may include a table that contains the current state of the time-based and event-based results. The time-based and the event-based results may start and stop at different times relative to each other. When one of the tests fails, the other test may be discontinued until desired again, or both tests may be allowed to run to completion. This depends on the desired goals for the particular product. For the event-based or engine-synchronized system, the test may pass too soon for a good sensor at high RPMs or may fail too late for a bad sensor at low RPMs. Thus, both the time-based diagnostic and the event-based diagnostic have drawbacks. Because of the different sample rates in the time-based diagnostic module 210 and the event-based diagnostic module 212 , improved results may be obtained. The synchronization module 214 may send a failure signal or a fault indicator to the fault indicator module 216 when either sensor fails a test. When both sensors pass a test, a passing sensor may be indicated with no fault. The synchronization module may also perform a balancing of the conditions in the synchronization module for a high RPM state or a low RPM state of the engine may be provided. Thus, balancing may occur based on the speed of the engine. Engine-synchronized diagnostics may be used at high RPMs while time-based may be used at low RPMs.
Referring now to FIG. 4 , a method 300 for operating this system is set forth. In step 310 , the system starts. In step 312 , it is determined whether time-based sampling is enabled. If time-based sampling is not enabled step 314 determines whether event-based sampling is enabled. If event-based sampling is enabled, step 316 generates and stores event-based diagnostic results. Referring back to step 312 , if time-based sampling is enabled, step 320 determines whether event-based sampling has been enabled. If event-based sampling has not been enabled, step 324 generates and stores time-based diagnostic results. The system is capable of one or both types of diagnostics.
Referring back to step 320 , if both time-based sampling has been enabled and event-based sampling has been enabled, step 330 generates and stores time-based diagnostic results while step 332 generates and stores event-based diagnostic results. As mentioned above, both the time-based diagnostic result and the event-based diagnostic results may take place over different time periods and may have different sampling rates. In step 334 , the time-based and event-based diagnostic results are synchronized as described above. The outputs of steps 316 and 324 are also provided to step 334 for synchronization. Synchronization may be performed when required if both event-based and time-based diagnostic results are provided. In step 336 , the synchronized diagnostic result is generated and stored. The diagnostic result may be used to generate a fault indicator or provide an indicator through an on-board diagnostic system that a particular sensor has failed. While the above example uses a pressure sensor such as a fuel rail pressure sensor, various types of pressure sensors and other types of sensors through the system may be used.
Referring now to FIG. 5 , a time-based pressure signal 412 is illustrated compared to an event-based pressure signal 410 . As can be seen, the results are different particularly early on in the timing of a transient pressure change. Later on in the timing, the two results converge. Therefore, synchronization between the time-based signal and the event-based signal is desirable to provide more accurate determination of errors.
The broad teachings of the disclosure can be implemented in a variety of forms. Therefore, while this disclosure includes particular examples, the true scope of the disclosure should not be so limited since other modifications will become apparent to the skilled practitioner upon a study of the drawings, the specification, and the following claims. | A method and control module for determining a sensor error includes a time-based diagnostic module generating a time-based diagnostic for a sensor and an event-based diagnostic module generating an event-based diagnostic for the sensor. A synchronizing module synchronizes the time-based diagnostic and the event-based diagnostic to obtain a diagnostic result. A fault indicator module generates a fault signal in response to the diagnostic result. | 5 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application 61/022,771, filed Jan. 22, 2008, which is incorporated by reference in its entirety.
BACKGROUND
[0002] Constant velocity joints connecting shafts to drive units are common components in vehicles. The drive unit typically has an output shaft or an input shaft for receiving the joint. Typically, the drive unit is an axle, transfer case, transmission, power take-off unit, or other torque device, all of which are common components in automotive vehicles. Typically, one or more joints are assembled to the shaft to form a propeller or drive shaft assembly. It is the propeller shaft assembly which is connected, for instance, at one end to the output shaft of a transmission and, at the other end, to the input shaft of a differential. The shaft may be solid or tubular with ends adapted to attach the shaft to an inner race of the joint thereby allowing an outer race connection to a drive unit. The inner race of the joint is typically press-fit, splined, or pinned to the shaft making the outer race of the joint available to be bolted or press-fit to a hub connector, flange or stubshaft of the particular drive unit. At the other end of the propeller shaft, the same typical or traditional connection is made to a second drive unit when connecting the shaft between the two drive units. Optionally, the joint may be coupled to a shaft for torque transfer utilizing a direct torque flow connection.
[0003] In many off road vehicle environments considerable torque is applied through the constant velocity joint. All terrain vehicles and utility vehicles often have drivelines that are subject to intermittent high torque values during unusual or extreme operating conditions. Such operating conditions may arise, for example, when the vehicle lands after jumping off irregular terrain. The impact upon landing generates considerable torque in the drivelines. This torque is subsequently imparted into the individual components of the constant velocity joint as the wheels of the vehicle regain traction. When the torque imparted into the constant velocity joint components exceeds design considerations, the components can experience failure. A common design response to these extreme conditions has been to increase the size of the CV joint components in order to increase their maximum torque weathering capacity.
[0004] In addition to the extreme conditions, designers are utilizing higher capacity engines in vehicle designs. These higher capacity engines increase the power passed through the drivelines and therefore increase the overload torques experienced during extreme conditions. Existing methods of compensation require continued upsizing of the drivelines in order to accommodate the increased power and resulting increased overload torques. Continued upsizing, however, results in increases in mass of the driveline components with subsequent mass increases to the vehicle itself. Upsizing, therefore, poses undesirable restrictions on vehicle designers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 is a plan view of an exemplary drive system for a typical four-wheel drive vehicle employing an exemplary constant velocity joint having torque overload protection.
[0006] FIG. 2 is a partial cross-sectional view of the exemplary constant velocity joint employing a clutch pack having an outer circumference attached to a joint stem and an inner circumference attached to a joint housing.
[0007] FIG. 3 is a partial cross-sectional view of the exemplary constant velocity joint employing a clutch pack having an inner circumference attached to the joint stem and an outer circumference attached to the joint housing.
DETAILED DESCRIPTION
[0008] Referring now to the discussion that follows and also to the drawings, illustrative approaches to the disclosed systems and methods are shown in detail. Although the drawings represent some possible approaches, the drawings are not necessarily to scale and certain features may be exaggerated, removed, or partially sectioned to better illustrate and explain the present invention. Further, the descriptions set forth herein are not intended to be exhaustive or otherwise limit or restrict the claims to the precise forms and configurations shown in the drawings and disclosed in the following detailed description.
[0009] While the invention is described with respect to a constant velocity universal joint with torque overload protection for use in an all-terrain vehicle, the following apparatus is capable of being adapted for various purposes including automotive vehicles drive axles, motor systems that use a propeller shaft, or other vehicles and non-vehicle applications that require shaft assemblies for torque transmission.
[0010] An exemplary drive system 12 for a typical four-wheel drive vehicle is shown in FIG. 1 . While a 4-wheel drive system is shown and described, the concepts herein presented could apply to a single drive unit system or multiple drive unit system, including rear wheel drive only vehicles, front wheel drive only vehicles, all wheel drive vehicles, and four wheel drive vehicles. In this example, the drive system 12 includes an engine 14 that is connected to a transmission 16 and a power take-off unit 18 . A front differential 20 has a right hand side half shaft 22 and left hand side half shaft 24 , each of which are connected to a wheel 25 and deliver power to the wheels. Attached to the ends of the right hand side half shaft 22 and left hand side half shaft 24 are constant velocity joints 10 .
[0011] A propeller shaft 26 connects the front differential 20 to a rear differential 28 . The rear differential 28 includes a rear right hand side shaft 30 and a rear left hand side shaft 32 . Attached to each side shaft 30 , 32 is a wheel 25 . Constant velocity joints 10 may be attached to the ends of the half shafts 30 , 32 that connect to the wheels 25 and the rear differential 28 .
[0012] The propeller shaft 26 , shown in FIG. 1 , is a three-piece propeller shaft that includes a plurality of Cardan joints 34 and one high-speed constant velocity joint 10 . The propeller shaft 26 includes interconnecting shafts 23 , 25 , 27 . The constant velocity joints 10 transmit power to the wheels through the propeller shaft 26 even if the wheels or the propeller shaft 26 have changed angles, such as may occur due to steering and/or raising or lowering of the suspension of the vehicle.
[0013] The constant velocity joints 10 may have any of a variety of configurations, such as a plunging tripod, a cross groove joint, a fixed ball joint, a fixed tripod joint, or a double offset joint, to name a few. The constant velocity joints 10 allow for transmission of constant velocities at angles typically encountered in the off road travel of all-terrain vehicles in both the half shafts, interconnecting shafts and propeller shafts of these vehicles. Optionally, each Cardan joint 34 may be replaced with any other suitable type of joint, including constant velocity joint types. The constant velocity universal joint with torque overload protection may be utilized for any of the above mentioned joint locations.
[0014] The shafts 22 , 23 , 24 , 25 , 27 , 30 , 32 may have a variety of configurations, such as solid or tubular with ends adapted to attach each shaft to an inner race or an outer race of a joint, thereby allowing the outer race or inner race to be connected to a hub connector 36 , a flange 38 , or stubshaft 40 , of each drive unit, as appropriate for the particular application. Thus, any of the connections identified in FIG. 1 at 10 or 34 may employ a constant velocity universal joint with torque overload protection.
[0015] Referring now to FIG. 2 , an exemplary constant velocity universal joint with torque overload protection 50 is illustrated. The constant velocity joint 50 may include a housing 52 configured to support a bearing 53 . The housing 52 may be configured to engage a propeller shaft. Bearing 53 may include an inner bearing race 54 configured to engage a journal of a drive unit and a plurality of torque transmitting balls 56 positioned between inner bearing race 54 and housing 52 . It should be understood that the constant velocity joint 50 may also be configured such that the housing 52 engages a drive unit and the inner bearing race 54 engages a propeller shaft. A ball cage 58 may be positioned between the housing 52 and inner race 54 , and retains the plurality of torque transmitting balls 56 .
[0016] The housing 52 may include a semi-spherical internal bore 60 forming a bearing cavity 61 in which bearing 53 is disposed. Bearing cavity 61 is at least partially defined by an inner surface 62 , a conical opening 64 disposed adjacent inner surface 62 , and an opposed rear-internal surface 66 . Located on an outer surface 68 of the housing 52 is at least one circumferential channel 70 extending around the entire outer periphery of the housing 52 . A boot or another protective cover may be secured to the cannel to prevent dirt and contaminants from entering the bearing cavity. The housing 52 may generally be made of a steel material, however, it should be noted that any other type of metal material, hard ceramic, plastic, or composite material, to name a few, may also be used for the housing 52 . It is desirable that the selected material be capable of withstanding the high speeds, temperatures and contact pressures of the constant velocity joint 50 for extended periods.
[0017] The housing 52 may also include a plurality of axially opposed outer ball tracks 72 located on the inner surface 62 thereof. The tracks 72 form a generally spherical shaped path within the inner surface 62 of the housing 52 . The tracks 72 may be axially opposed, such that one half of the outer ball tracks 72 open to a side of the housing 52 opposite to that of the other half of the outer ball tracks 72 in any number of patterns. Depending on the configuration of the constant velocity joint, the ball tracks all may open or axially align on the same side of the outer race. The outer ball tracks 72 may also be of a gothic or elliptical shape provided the pressure angle and conformity are maintained, or may have other configurations depending on the requirements of the particular application. The outer ball tracks 72 located on the inner surface 62 of the housing 52 may also be double offset tracks. Further, it is to be understood that the constant velocity joint 50 may be a fixed constant velocity joint, including without limitation a VL, RF, AC, DO, or a tripod joint including other fixed constant velocity joints.
[0018] The inner bearing race 54 generally has a circumferential shape. The inner bearing race 54 is arranged within the bore 60 of the housing 52 . The inner bearing race 54 includes a drive unit side 84 , an inner joint bore 86 that includes a plurality of splines 88 , and a circlip groove 90 on the inner surface 92 thereof, for axially retaining the constant velocity joint in a rotationally fixed way to a driveshaft. It should be understood, however, that axial retention of the inner bearing race 54 to a shaft may also be accomplished in other ways.
[0019] An outer surface 94 of the inner bearing race 54 may include a plurality of inner ball tracks 96 that may be axially opposed. The inner ball tracks 96 generally have a spherical shape and are aligned radially with the ball tracks 72 on the housing 52 , such that the axial angle will open in a similar or the same direction as the ball track 72 directly aligned above it on the housing 52 . The inner bearing race 54 may be made of steel, or another material, such as a metal composite, hard plastic, and ceramic, to name a few.
[0020] The ball cage 58 generally has a ring-like configuration. The ball cage 58 is arranged within the bore 60 of the housing 52 such that it is not in contact with the inner surface of the housing 54 . The cage 58 has a plurality of oblong-shaped orifices or windows 98 that extend through the cage. The number of windows 98 may match the number of ball tracks 72 , 96 on the housing 52 and inner bearing race 54 of the constant velocity joint 50 . The number of balls and windows may, however, differ. The cage 58 , along with the inner bearing race 54 , may be made of a steel material, but any other hard metal material, plastic, composite, or ceramic, to name a few, may also be used.
[0021] The balls 56 are each arranged within one each of the orifices 98 of the cage 58 and within a ball track 72 , 96 of the housing 52 and the inner bearing race 54 , respectively. Therefore, the balls 56 will be capable of rolling in the axially opposed tracks 72 , 96 aligned in the same direction. It is contemplated that a pocket region 99 may be formed between the outer ball tracks 72 and the rear internal surface 66 . The pocket region 99 may be configured to provide clearance for the inner bearing race 54 during angled positioning.
[0022] Attached to the housing 52 is a stem 100 having a housing engagement end 102 . The stem 100 includes a connector 104 arranged at the housing engagement end 102 of the stem 100 for attaching the stem to the housing 52 . The housing 52 includes a correspondingly configured connector 106 that slidably engages the connector 104 of the stem 100 . The connector 104 of the stem 100 may include a cylindrical shaped region 108 . A longitudinal axis of the cylindrically shaped region 108 substantially coincides with a longitudinal axis of the stem 100 . The connector 106 of the housing 52 similarly includes a cylindrical shaped region 110 having a longitudinal axis that substantially coincides with a longitudinal axis of the bearing 53 . The cylindrical region 110 of the housing 52 engages the cylindrical region 108 of the stem 100 when the two members are interconnected. The connector 104 of the stem 100 has a diameter sized smaller than a diameter of the connector 106 of the housing 52 to enable the two members to rotate relative to one another when connected. With the stem 100 attached to the housing 52 , the bearing 53 , the housing 52 , and the stem 100 are aligned substantially along a common axis. A stem o-ring channel 112 and an o-ring element 114 may be used to axially seal the stem 100 within the housing 52 .
[0023] Also arranged at the housing engagement end 102 of the stem 100 is a recessed region 116 configured to receive a clutch pack 118 . The stem recessed region 116 may include a generally cylindrical sidewall 122 having a longitudinal axis that substantially coincides with the longitudinal axis of the stem 100 . The sidewall 122 engages an outer circumference 124 of the clutch pack 118 . A rear wall 126 of the recessed region 116 is arranged generally perpendicular to the longitudinal axis of the stem 100 and engages a side 128 of the clutch pack 118 .
[0024] The housing 52 may include a cylindrically shaped clutch mounting flange 130 . An outer circumferential surface 132 of the flange 130 engages an inner diameter of the clutch pack 118 . Extending generally radially outward from the flange 130 is a housing surface 134 that engages a side 136 of the clutch pack 118 that is opposite the side 128 . With the stem 100 connected to the housing 52 , the cylindrical sidewall 122 and rear wall 126 of the recessed region 116 of the stem 100 , and the outer surface 132 of the clutch mounting flange 130 and the sidewall 134 of the housing 52 , together define a clutch chamber 137 in which the clutch pack 118 is disposed.
[0025] The stem 100 may be secured to the housing 52 my means of a fastener 138 . The fastener 138 extends through a bore 140 in the housing 52 . The housing 52 is free to rotate about the fastener 138 . The fastener 138 may include a threaded end 142 that engages a correspondingly threaded aperture 144 in the stem 100 . An opposite end 146 may include a head 148 configured to enable torque to be applied to the fastener 138 . For example, the fastener head 148 may include an external hex 150 that can be engaged with an appropriately sized socket wrench, or may include a recessed socket 152 configured to receive a suitably configured key, such as a hex key or Torx™ wrench. The head 148 of the fastener 138 is disposed within the bearing cavity 61 and may be accessed through the bore 86 of the inner bearing race 54 .
[0026] A biasing member 154 may be disposed between the rear internal surface 66 of the bearing housing 52 and an underside of the fastener head 148 . The biasing member 154 may include, but is not limited to, a coil spring, wave spring, leaf spring, ring of elastic material, as well as other types of biasing devices. The biasing member 154 produces a biasing force that tends to draw the stem 100 and the housing 52 toward one another, thereby causing the housing 52 and the stem 100 to exert a compressive force on the clutch pack 118 . The magnitude of the compressive force applied to the clutch pack 118 can be selectively controlled by adjusting how far the end 142 of the fastener 138 is threaded into the threaded aperture 144 of the stem 100 .
[0027] Although a variety of clutch packs 118 and attachment configurations are contemplated, one exemplary configuration contemplates the use of a plurality of slip clutch plates 156 held in compression between the stem 100 and the housing 52 . Each clutch plate 156 is splined either at the inner diameter of the plate or the outer diameter of the plate. The clutch plate spline engage a corresponding spline 157 , 159 formed on the cylindrical side wall 124 of the recessed region 116 of the stem 100 and surface 132 of clutch mounting flange 130 , respectively. Generally the clutch plates 156 are arranged such that every other clutch plate is splined at the inner diameter, for example clutch plates 158 , and the intermediate plates 160 are splined at the outer diameter. The clutch plates 156 may be slid axially relative to the stem 100 and housing 52 , but are prevented from rotating relative to the housing or the stem, depending on which component the clutch plate is splined. The torque transfer path through the constant velocity joint 50 travels from the spline 88 located in the bore 86 of the inner bearing race 54 , through torque transmitting balls 56 to housing 52 , at which point the torque is transmitted to the clutch plate 158 splined at the inner diameter to the housing 52 , across a clutch plate interface 162 to the adjoining clutch plate 160 that is splined at the outer diameter to the stem 100 , and ending at the spline 117 .
[0028] The fastener 138 may be utilized to set a torque threshold of the clutch pack 118 . When the fastener 138 is tightened, the compression force being applied by the housing 52 and the stem 100 on the clutch pack 118 increases, thereby producing a corresponding increase in the torque threshold. Conversely, loosening fastener 138 reduces the compression on the clutch pack 118 , and the corresponding torque threshold is reduced. The biasing member 154 disposed between the head 148 of the fastener 138 imparts a generally constant axial compressive load on the clutch plates 156 of the clutch pack 118 . The fastener 138 may be installed and pre-tensioned prior to assembly of the inner bearing race 54 into the housing 52 . The fastener 138 tension may also be set through the inner joint bore 86 after assembly.
[0029] The clutch pack 118 is disposed within the clutch chamber 137 and engages the outer race stem 100 and the housing 52 . The clutch pack 118 is configured such that the outer race stem 100 and the housing 52 rotate in unison below a pre-set overload torque value. When the overload torque reaches a predetermined threshold, the designed frictional resistance of the plurality of slip clutch plates 156 is overcome and independent rotation is allowed. Once the overload torque value threshold is crossed, the outer race stem 100 and the housing 52 are allowed to rotate independently, thereby preventing damaging torque from being imparted into the constant velocity joint 50 internal components. When the torque values drop below the overload threshold, the clutch pack 118 re-engages and the outer race stem 100 and housing 52 resume rotating in unison.
[0030] With reference to FIG. 3 , housing 52 and stem 100 may be configured such that the outer circumference 124 of the clutch pack 118 engages the housing and the inner circumference 133 of the clutch pack 118 . Housing 52 is a recessed region 164 configured to receive the clutch pack 118 . The housing recessed region 164 may include a generally cylindrical sidewall 166 having a longitudinal axis that substantially coincides with the longitudinal axis of the bearing 53 . The sidewall 166 engages the outer circumference 124 of the clutch pack 118 . A rear wall 168 of the recessed region 164 is arranged generally perpendicular to the longitudinal axis of the bearing 53 and engages the side 136 of the clutch pack 118 .
[0031] The stem 100 may include a cylindrically shaped clutch mounting flange 170 . An outer circumferential surface 172 of the flange 170 engages the inner diameter 133 of the clutch pack 118 . The clutch mounting flange 170 extends through a bore 173 in the housing 52 . The housing 52 is free to rotate about the clutch mounting flange 170 . Extending generally radially outward from the flange 170 is a stem side wall 174 that engages the side 128 of the clutch pack 118 that is opposite the side 136 . With the stem 100 connected to the housing 52 , the cylindrical sidewall 166 and rear wall 168 of the recessed region 164 of the stem 100 , and the outer surface 172 of the clutch mounting flange 170 and the sidewall 174 of the stem 100 , together define a clutch chamber 176 in which the clutch pack 118 is disposed.
[0032] The stem 100 may be secured to the housing 52 my means of a fastener 178 . The fastener 178 may include a threaded end 180 that engages a correspondingly threaded aperture 182 in the stem 100 . An opposite end 184 may include a head 186 configured to enable torque to be applied to the fastener 178 . For example, the fastener head 186 may include an external hex 188 that can be engaged with an appropriately sized socket wrench, or may include a recessed socket 190 configured to receive a suitably configured key, such as a hex key or Torx™ wrench. The head 186 of the fastener 178 is disposed within the bearing cavity 61 and may be accessed through the bore 86 of the inner bearing race 54 .
[0033] A biasing member 154 may be disposed between the rear internal surface 66 of the bearing housing 52 and an underside of the fastener head 186 . The biasing member 154 may include, but is not limited to, a coil spring, wave spring, leaf spring, ring of elastic material, as well as other types of biasing devices. The biasing member 154 produces a biasing force that tends to draw the stem 100 and the housing 52 toward one another, thereby causing the housing 52 and the stem 100 to exert a compressive force on the clutch pack 118 . The magnitude of the compressive force applied to the clutch pack 118 can be selectively controlled by adjusting how far the end 180 of the fastener 178 is threaded into the threaded aperture 182 of the stem 100 .
[0034] The clutch pack 118 may be attached to the housing 52 and the stem 100 in a similar manner as previously described with respect to the configuration illustrated in FIG. 2 . For example, each of the clutch plates 156 may be splined either at the inner diameter of the plate or the outer diameter of the plate. The clutch plate spline engages a corresponding spline 192 , 194 formed on the cylindrical side wall 166 of the recessed region 164 of the housing 52 and surface 172 of clutch mounting flange 170 , respectively. The clutch plates 156 may be slid axially relative to the stem 100 and housing 52 , but are prevented from rotating relative to the housing or the stem, depending on which component the clutch plates are splined. The torque transfer path through the constant velocity joint 50 travels from the spline 88 located in the bore 86 of the inner bearing race 54 , through torque transmitting balls 56 to housing 52 , at which point the torque is transmitted to the clutch plate 156 splined at the outer diameter to the housing 52 , across the clutch plate interface to the adjoining clutch plate 156 that is splined at the inner diameter to the stem, and ending at the spline 117 .
[0035] The fastener 178 may be utilized to set a torque threshold of the clutch pack 118 . When the fastener 178 is tightened, the compression force being applied by the housing 52 and the stem 100 on the clutch pack 118 increases, thereby producing a corresponding increase in the torque threshold. Conversely, loosening the fastener 178 reduces the compression on the clutch pack 118 , and the corresponding torque threshold is reduced. The biasing member 154 disposed between the head 186 of the fastener 178 imparts a generally constant axial compressive load on the clutch plates 156 of the clutch pack 118 . The fastener 178 may be installed and pre-tensioned prior to assembly of the inner bearing race 54 into the housing 52 . The fastener 178 tension may also be set through the inner joint bore 86 after assembly.
[0036] The clutch pack 118 is disposed within the clutch chamber 176 and engages the outer race stem 100 and the housing 52 . The clutch pack 118 is configured such that the outer race stem 100 and the housing 52 rotate in unison below a pre-set overload torque value. When the overload torque reaches a predetermined threshold, the designed frictional resistance of the plurality of slip clutch plates 156 is overcome and independent rotation is allowed. Once the overload torque value threshold is crossed, the outer race stem 100 and the housing 52 are allowed to rotate independently, thereby preventing damaging torque from being imparted into the constant velocity joint 50 internal components. When the torque values drop below the overload threshold, the clutch pack 118 re-engages and the outer race stem 100 and housing 52 resume rotating in unison.
[0037] With regard to the processes, systems, methods, heuristics, etc. described herein, it should be understood that, although the steps of such processes, etc. have been described as occurring according to a certain ordered sequence, such processes could be practiced with the described steps performed in an order other than the order described herein. It further should be understood that certain steps could be performed simultaneously or generally simultaneously, that other steps could be added, or that certain steps described herein could be omitted. In other words, the descriptions of processes herein are provided for the purpose of illustrating certain embodiments, and should in no way be construed so as to limit the claimed invention.
[0038] It is to be understood that the above description is intended to be illustrative and not restrictive. Many embodiments and applications other than the examples provided would be apparent to those of skill in the art upon reading the above description. The scope of the invention should be determined, not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. It is anticipated and intended that future developments will occur in the arts discussed herein, and that the disclosed systems and methods will be incorporated into such future embodiments. In sum, it should be understood that the invention is capable of modification and variation and is limited only by the following claims.
[0039] All terms used in the claims are intended to be given their broadest reasonable constructions and their ordinary meanings as understood by those skilled in the art unless an explicit indication to the contrary is made herein. In particular, use of the singular articles such as “a,” “the,” “said,” etc. should be read to recite one or more of the indicated elements unless a claim recites an explicit limitation to the contrary. | An exemplary constant velocity joint includes a first member and a second member rotatably engaging the first member. A clutch pack is disposed between and engages the first and second members. A fastener is used to attach the first member to the second member. The fastener is fixedly connected to the second member and rotatably engages the first member. The fastener exerts a biasing force for urging the first and second members into engagement with the clutch pack. | 8 |
PRIOR APPLICATIONS
This is a US national phase patent application that claims priority from PCT/FI2005/000520, filed 1 Dec. 2005, that claims priority from Finnish Patent Application. No. 20041572, filed 3 Dec. 2004.
TECHNICAL FIELD
This invention comprises a greenhouse, a greenhouse climate control system and a method of controlling greenhouse climate.
TECHNICAL BACKGROUND
Previously known greenhouses are those in which the climate is controlled by means of ventilation doors or blowers. In those, excess sun energy and excess moisture are removed from the greenhouse by means of ventilation. In optimal growing conditions, the temperature is ca 18-25° C., the air humidity ca 70-90% and the carbon dioxide concentration more than 1000 ppm. Optimal growing conditions require a good control of the air temperature, moisture and carbon dioxide concentration. It is clear that this can not be reached in an open greenhouse. As the cooling takes place by means of external air in an open greenhouse, the temperature of the greenhouse will, especially during the best growing period, rise over the goal. In summer the use of excess carbon dioxide (over the outside level of 350 ppm) does not work as the given carbon dioxide can get out from the greenhouse in connection with the ventilation. An open greenhouse is either not desired in view of the energy consumption. When excess sun energy is ventilated out daytime, heating of the greenhouse is needed at night. In addition, ventilation to remove moisture has to be performed in spring and autumn, which requires additional heating.
The inside air is almost isolated from the outside air in a closed greenhouse. Outside air is not let in from ventilation doors and it is not blown to the greenhouse with blowers but instead, extra heat is lead out technically and also the carbon dioxide needed by the plants is produced technically and its concentration is preferably raised to a level of at least 500-1500 ppm. A closed greenhouse is considered to be the ideal solution for plant growing because the climate can be controlled optimally for the growing of the plants. The use of the closed greenhouse is in first hand restricted by the bad functionality or the high costs of the earlier solutions.
Several international patents have been made for a greenhouse system, wherein the climate control is performed by means of a closed system. WO 00/76296 presents a solution that is based on the use of underground water storages. This solution is possible only in restricted situations as there usually are no underground water basins available. Furthermore, in order to decrease the need of cooling water, water heat accumulators are used in such solutions wherein approximately a half of the daily sun energy is accumulated to be used for the heating of the greenhouse at night. The size of these heat accumulators is however big, for example ca 200 cubic meters for a 1000 square meter greenhouse. The costs required by such a system are of the above reasons considerable and it has not become very general in practice.
In EP patent 0 517 432 A 1, such a heat accumulator is presented to which the daily sun energy is collected and from which a part is taken out during nights for the heating of the greenhouse and a part is lead to the cooler air at night. In this case, the size of the heat accumulator has to be ca 400 cubic meters for a 1000 square meter greenhouse. The big size of the required heat accumulator makes the whole system expensive and the system is not in common use.
References is also made to U.S. Pat. No. 4,044,078 as prior art, which presents an apparatus developed for cooling of storages, in which cold water is sprayed from above trough a grid frame against an air flow and the heated water is cooled with an external cooler. The incidence speed of the air and the water is because of the structure very small, wherefore the apparatus would be very big if used for cooling of greenhouses. Furthermore, the apparatus is not suitable for condensing moisture in the air, because there is only a water inlet but no outlet. The above mentioned facts make the solution not suitable for greenhouse use.
US 2003/0188477 A1 contains a conventional open cooling system for greenhouses, wherein dry outer air is lead to the system which is cooled down along with the evaporation of water of an ambient temperature sprayed to it. Because of the way how the air and water meet, the speed is low, leading to a weak heat exchange. As outer air is blown in the system in to the greenhouse, it is not suitable for cooling of a closed greenhouse. Neither can excess moisture be removed from the greenhouse by means of this method, but the humidification of the air to be blown inside increases the need of removing moisture from the greenhouse by ventilation.
U.S. Pat. No. 4,707,995 comprises a system for the control of the air humidity and temperature of the greenhouse, the function of which is based on the use of salt water for removing moisture. As in the foregoing solution, air is transported through of water spray and the treated water is collected and recovered outside the apparatus. The apparatus is not generally suitable for cooling of greenhouses or removal of moisture.
A similar solution is also presented in JP-publication 4148123 A 19920521. Water is sprayed from above and there are also ventilation devices in the apparatus and the air blown by them is intended to come into heat exchange contact with the sprayed water.
Also in JP-publication 2104222 A 19900417, heat exchange between water and air is used for cooling air in greenhouses. The apparatus comprises a heat exchanger working with cold groundwater with which the greenhouse is cooled from above during nights by means of inlet air and moisture is removed from the lower end of the device. The efficiency of the system is not sufficient to remove daily heat from a closed greenhouse.
THE OBJECT OF THE INVENTION
The object of this invention is such a greenhouse and a method, which can be realized in different environments, especially as a closed application and by means of which the extra investments required by a closed greenhouse is only a little part of those of the solutions above described.
SUMMARY OF THE INVENTION
The invention is concerned with a system for the control of greenhouse climate by means of cooling water. The system comprises a condenser, means for leading cooling water to the condenser and an outlet in the condenser to lead out water heated by the air of the greenhouse from the condenser. It is mainly characterized in that it furthermore comprises a pump to lead the main part of the water from the condenser back for circulation to the means and a blower to transfer warm air to be cooled down to the condenser.
The invention is also concerned with a greenhouse with a system for the control of the greenhouse climate by means of cooling water, the system comprising a condenser, means for leading cooling water to the condenser and an outlet in the condenser for leading out water warmed up by the air of the greenhouse from the condenser. The system in the greenhouse furthermore comprises a pump for leading water from the condenser mainly back for circulation to the means.
The method of the invention for controlling greenhouse climate in a greenhouse is connected to a system comprising a condenser, means for leading out cooling water to the condenser and an outlet for leading out water heated by the air of the greenhouse in the condenser from the condenser. In the steps of the method cooling water is introduced in the condenser from which it is let to meet the air introduced to the condenser for cooling of that air. The water heated up by the air of the greenhouse is removed from the condenser. The main part of the water to be removed from the greenhouse is let for circulation to the upper end of the condenser.
The advantageous embodiments of the invention have the characteristics of the independent claims. In some advantageous embodiments, the wall of the greenhouse can be a part of the structure of the condenser and of an evaporator to be connected to that.
In some advantageous embodiments, the invention is realized as a closed greenhouse.
The greenhouse of the invention does not need any ventilation doors for its normal function or other conventional ventilation systems. Instead it contains:
means for heat control in order to remove extra heat or to give extra heat means for controlling moisture to keep the moisture optimal means for introducing carbon dioxide
The following advantages are achieved with the greenhouse system of the invention:
A 20-50+% bigger yield, because of the optimal control of temperature, moisture and especially carbon dioxide concentration and because light energy better can be made use of An essentially smaller need of heating energy An essential decrease in the use of plant protecting substances In several applications, an essential saving in water based on the recovery of water evaporated by the plants in the condenser The time of yield can because of a better regulation be determined in advance and thus the end result can be optimized A better use of artificial light Essentially lower construction and use costs than those needed for earlier presented solutions for the same thing.
In the following, the invention is presented more in detail by referring to different embodiments by means of figures. The invention is not intended to be restricted to the details of these.
FIGURES
FIG. 1 presents an embodiment of the invention, wherein there is a condenser in the climate control system of the greenhouse
FIG. 2 is an embodiment of the invention, wherein there is a condenser and an evaporator in the climate control system of the greenhouse
FIG. 3 presents another such an embodiment of the invention having a condenser and an evaporator.
DETAILED DESCRIPTION OF THE INVENTION
The conditions differ essentially from each other during different seasons of the year in view of the climate control of greenhouse. The apparatuses and methods of the invention are especially useful in midsummer and also in spring and fall. In midsummer, when the radiation energy of the sun is biggest, the heat energy to be lead out from the greenhouse has its maximum and on the other hand the need for night heating is minimal.
FIG. 1 presents an embodiment of the invention, wherein there is a condenser 10 in the climate control system of the greenhouse and which explains for example the cooling of the greenhouse according to the invention.
FIG. 1 has a condenser 10 , which here is a spray condenser to the lower end of which warm air from the greenhouse is blown by means of a blower 12 , which flows upwards through the condenser 10 and is returned back to the greenhouse. Cold or cool water is lead to the means 13 in the upper end of the condenser, here a sprinkler, from the outside of the greenhouse 1 , partly from another water storage, for example from a sea, river etc. through pipe 21 to pipe 20 and as circulation water from the lower end of the condenser through pipe 20 . The cold water is lead down through small holes in the sprinkler 13 . Thin water jets with a speed of ca 2 m/s meet the air flow that is moving upwards, the speed of which most preferably is ca 5 m/s, whereby an efficient heat exchange takes place between the water and the air. The temperature of the air returning to the greenhouse lowers to a level close to the temperature of the water flowing to the condenser. The temperature and the amount of water decide the temperature and the moisture of the return air. The water collected on the bottom of the condenser is lead by means of the pump 15 again to the sprinkler 13 for effecting the heat exchange. The amount of water regulated in accordance with the amount coming from an outer water source or other water source is removed from the system back to another water system via an outlet 14 in the lower end of the condenser. The humidity of the greenhouse air condensed into the water is also removed in this way. The outlet 14 is essential, because without that the apparatus is over flown somewhere. The main part of the water goes for circulation and even if the part going to circulation often is 99%, also the other part is important during the summer, more than 5 l/m2/day, i.e. more than 10000 liters per day in a midsize Finnish garden of 2000 m2.
In the embodiment of the FIG. 2 , there is a condenser and an evaporator. The cooling of the greenhouse of the invention is explained. FIG. 2 presents a condenser 10 , here it is a spray condenser, to the lower end of which warm air from the greenhouse is blown (alternatively it is sucked from the upper end) by means of a blower 12 which air flows upwards through the condenser and is returned cooled back to the greenhouse. Cold or cooler water is lead to the sprinkler 13 in the upper end of the condenser from the outer side of the greenhouse 1 from the evaporator 16 . Cold water is lead down through small holes in the sprinkler 13 . Thin water jets with a speed of ca 2 m/s meet the upwards-moving air flow with a speed of preferably ca 5 m/s, whereby there is an efficient heat exchange between water and air. The temperature and amount of water decide the temperature and humidity of the return air. The water collected on the bottom 14 of the condenser is lead to an external evaporator 16 by means of a pump 15 .
The structure of the evaporator 16 is similar to the condenser 10 . The water warmed up in the evaporator 16 and coming from the condenser 10 is lead to a sprinkler 18 therein, and the water flowing from that down in form of showers. An air flow from the outer side flows in the evaporator 16 against the water stream which is achieved by means of a blower 17 . The outer air is most often cooler but in any case essentially dryer than the internal air, wherefore the outer air cools down the water flowing in the evaporator when evaporating. The cooled water is further lead by means of a pump to the sprinkler 13 of the condenser being inside. When necessary, water is introduced to the system in accordance with the difference in amounts concerning the evaporated amount in the evaporator and the condensed amount in the condenser.
The evaporator evaporates at least as much and usually ca twice the amount compared to what is condensed from the air humidity in the greenhouse and that is why water has to be added to the common water circulation, or in the case of an intermediate heat exchanger, to the own circulation of the evaporator (this water can e.g. be seawater). In FIG. 2 , there is also presented the place for adding water (no reference number). In principal, no outlet for water is needed in the evaporator, only an inlet, but in practice, the outlet has to be there because of dirt and accumulation of salts for continuous daily wash and cleaning. In FIG. 2 , this outlet is below the water inlet (no reference number).
It is essential for the method that the heat capacity of the water flow of the condenser is 3-6 times the capacity of the air flow; in this way, the heat exchange of the condenser is as advantageous as possible in view of the energy required for the blowing and air pumping. The effect of the heat exchange in the spray condenser is directly proportional to the amount of the circulation water, the height of the spray, the incidental speed of the air and water, and the total surface area calculated for the sprays. Because of this, it is preferable for the condenser and the evaporator of the invention that the height of the condenser is 2-4 m, the diameter of the sprays is 1-3 mm and the incidental speed of the water jets and air is 5-8 m/s. For example in a condenser with a cross section area of 1 m2, the required air flow is ca 5 m3/s and water flow ca 10 l/s.
If enough cool cooling water of 0-15 degrees is available in the vicinity of the greenhouse, the evaporator part of the system can be excluded and cool cooling water be lead directly to the sprinkler of the condenser. However, also in this case it has to be ensured that the internal water circulation in the condenser is sufficient. When there is no water of good quality suitable for watering available, the water circuits can be separated by an intermediate heat exchanger 31 as shown in the FIG. 3 . Condensation water of the internal circuit can be used for example for watering of the plants when on the contrary water from the environment of a worse quality can be used in the external circuit, i.e. in the evaporator, for example seawater. Plenty of clean water is needed for watering in greenhouses. Usually, the greenhouse plants evaporate more than 90% of the water uptaken. Thus, in areas where there is not enough water, the water evaporated from the plants can be recovered with the above mentioned apparatus to be reused.
Another embodiment of the closed greenhouse of the invention is thus presented in FIG. 3 having a condenser and an evaporator but wherein the water circuits are separated by an intermediate heat exchanger 31 .
In this case, the water coming out from the condenser 10 is cooled down by an intermediate heat exchanger 31 between the evaporator 16 and the condenser 10 and the water going to the evaporator 16 is heated. The intermediate heat exchanger 31 separates the water circulations of the condenser 10 and evaporator 16 from each other, whereby the water warmed up by the air of the greenhouse coming from the lower end of the condenser 10 in the water circulation of the condenser has been lead to the sprinkler 13 in the upper end of the condenser 10 cooled down by the water circulating in the evaporator. The water cooled down by the outer air and coming from the lower end of the evaporator 10 has been lead to the sprinkler 13 in the upper end of the evaporator 16 warmed up by the water circulating in the condenser. More water is accumulated in the condenser when the humidity of the greenhouse air is condensed into the cold water. The accumulated water is completely salt free and it can be recovered through the outlet 14 for example for watering of the plants or to moisture the air. Correspondingly, water has to be added to the evaporator (even e.g. sea water is suitable) in accordance with the thermal energy transferred from the condenser, the amount of which can be double compared to the water amount condensed in the condenser.
In different embodiments, the mantle of the condenser can be manufactured of a film or textile or the wall of the greenhouse can form a part of the structure of the system.
In a greenhouse, especially in a closed greenhouse, the regulation of the humidity is in addition to the temperature regulation a basic condition for preferable growth conditions. The plants evaporate 0.4(−1) liters of water in warm conditions per square meter in an hour. If the air circulation is 20 l/m2/s it is 72 m3/h which is the same thing as 93 kg/h. When the temperature of the air going to the spray condenser is 26 degrees and the relative humidity 80%, the air contains 17 g water/kg. So that the air humidity of the greenhouse would stay constant, moisture has to be removed from the greenhouse in an amount corresponding to the amount evaporating from the plants, 400/m2/h, which is 400/93 g/kg per cubic meter air which is 4.3 g/kg, why the moisture of the outgoing air has to be 12.7 g/kg corresponding to the condensation point of air of 18° C. Thus the ingoing temperature of the cooling water circulating in the condenser can be 18° C. at the most. If the water temperature is essentially lower and a humidity of 80% is desired to be kept in the greenhouse, the water flow has to be restricted or additional moisture has to be introduced in the greenhouse by spraying. Also in lower temperatures, when the evaporation of the plants takes place to a lower extent, the moisture of the greenhouse is regulated by regulating the temperature of the condensation surfaces of the condenser.
While the present invention has been described in accordance with preferred compositions and embodiments, it is to be understood that certain substitutions and alterations may be made thereto without departing from the spirit and scope of the following claims. | The system is for regulating the climate of the greenhouse. The warm greenhouse air is cooled by cooling water. The system has a spray condenser that includes a conduit for leading the cooling water to the condenser. The condenser has a blower to transfer warm air to be cooled to the condenser. The warm air from the greenhouse is used to warm the water sprayed from the spray condenser. The cooling water may be delivered from an evaporator that has water that is cooled by outside air blown into the evaporator. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a method for the generation of digital signatures for electronic messages.
The method can be applied especially to the signing of messages by portable devices of the microprocessor-based smart card type.
For example, it may be necessary to sign messages sent by the card to a reading terminal or to a central authority. Or again, it may be necessary to carry out a transaction (an electronic cheque transaction) and to sign this transaction so that it can be authenticated first of all by the reading terminal in which the transaction is made and then by a central authority that manages the transaction.
The method that shall be described is related to the algorithms for the generation of digital signatures published in recent years, especially by the U.S. National Institute of Standards and Technology, for example the DSA (Digital Signature Algorithm) described in the U.S. patent application Ser. No. 07/736451 filed Jul. 26, 1991 and now U.S. Pat. No. 5,231,668 and published on the 30the of Aug. 1991 in the Federal Register kept by this Institute, pages 42980-42982.
The invention is aimed at modifying the known methods, in particular to make them adaptable to microprocessor-based cards that do not have physical resources (processor, memories) sufficient to swiftly carry out mathematical operations on big numbers. The known algorithms, especially the DSA, use big numbers to generate signatures with a sufficient degree of security.
2. Description of the Related Art
In order to provide for a clear understanding of the invention, first of all a reminder shall be given of what is the DSA algorithm.
A DSA signature consists of a pair {r, s} of big numbers represented in computers by long strings of binary digits (160 digits). The digital signature is computed by means of a series of computation rules defined by the algorithm and a set of parameters used in these computations. The signature enables both the certifying of the identity of the signer (because it brings into action a secret key proper to the signer) and the integrity of the signed message (because it brings into action the message itself). The algorithm makes it possible firstly to generate signatures and secondly to check signatures.
The generation of DSA signatures brings into action a secret key. The check brings into action a public key that corresponds to the secret key but is not identical to it. Each user has a pair of keys (secret, public). The public keys may be known to all while the secret keys are never revealed. Anybody has the capacity to check the signature of a user by using the public key of this user but only the possessor of the secret key can generate a signature corresponding to the pair of keys.
The parameters of the DSA are the following:
a prime number p such that 2 L-1 <p 2 L for L ranging from 512 to 1024 (including the limits) and L=64a for a as any integer;
a prime number q such that 2 159 <q 2 160 and p-1 is a multiple of q;
a number g, q order modulo p, such that:
g=h.sup.(p-l)/q modulo p where h is any integer checking
1<h<p-1 and g>1;
a randomly or pseudo-randomly generated number x (this is the secret key, fixed for a given user);
a number y defined by the relationship
y=g x modulo p; (this is the public key linked to the secret key); the modular operations defined here below, modulo p or modulo q, shall be designated by mod p or mod q respectively;
a randomly or pseudo-randomly generated number k such that 0<k<q.
The integers p, q and g are parameters of the system that can be published and/or shared by a group of users. The secret and public keys of a signer are respectively x and y. The parameter k which is a random parameter must be regenerated for each new signature. The parameters x and k are used for the generation of signatures and must be kept secret.
In order to sign a message m (which will generally be a hashed value of an initial file M), the signer computes the signature {r, s} by:
r=(g k mod p) mod q, and
s=(m +xr)/k mod q
(where the division by k is taken to be modulo q, namely that 1/k is the number k' such that kk'=1 mod q; for example if q=5 and k=3, then 1/k=2 for 3×2=6, giving 1 mod 5).
After the fact that r and s are different from zero has been tested, the signature {r, s} is sent to the verifier. The verifier is generally the terminal into which the smart card that sends the message m and the signature {r, s} is inserted.
The verifier, which knows p, q, g (related to the application), y (related to the user) and m (the message that he has received from the card), computes:
a. w=(1/s) mod q
b. u1=mw mod q
c. u2=rw mod q
d. v= g u1 ·y u2 mod p! mod q
Now, this value g u1 .y u2 mod p! mod q is precisely equal to r if s has the value (m+xr)/s mod q.
Consequently, the terminal receives r and s and ascertains that v is really equal to r to accept the signature or reject it otherwise.
Hereinafter, the term "signer" or signer unit or proving device or smart card shall be used without distinction to designate the device that sends out the signature and that will generally be a smart card. And the term "verifier" or verifier unit or verifier device or verifier terminal or again control authority shall be used without distinction to designate the device that receives the signature and checks it to accept or reject a transaction or a message. The simplest application of the invention is the sending of the signature by means of a smart card to a reading terminal into which the card is inserted, with the terminal performing the checking function and being connected or not connected to a central management authority.
SUMMARY OF THE INVENTION
One of the aims of the present invention is to increase the security of generation and checking of digital electronic signatures, in minimizing the computation and memory means that have to be present in the smart card to produce the signatures.
It would be particularly desirable to be able to use low-cost 8-bit microprocessors in the card rather than more powerful and costlier microprocessors, despite the fact that the 8-bit microprocessors cannot easily process big numbers. However this should not be done to the detriment of security.
According to a first major aspect, the invention proposes that the checking by a verifier (terminal) of the signature sent by the signer (card) uses a step for the timing of the period of time that elapses between an instant when a data element (in principle a random data element) is sent by the verifier to the signer (the card) and the instant when the signature (using this random data element) returns to the verifier. If the time that has elapsed is excessively lengthy, it means that the computational processing of the signature by the signer has been done abnormally and the signature is rejected even if its authenticity is confirmed by the verifier.
Indirectly, this approach makes it possible, as shall be seen, to preserve the same security of signature while at the same time using small physical resources (in terms of computation power and memories) in the smart card. Small resources entail the need to modify the methods of generation and checking of signatures, but this is to the detriment of security. The timing step according to the invention restores a sufficient level of security.
This approach shall be described in detail on the basis of algorithms derived from the DSA algorithm recalled here above, but it will be understood that this first aspect of the invention is applicable with other algorithms even if they are very different from the DSA algorithm.
In brief, the first aspect of the invention consists of an electronic signature method, comprising the generation of a digital signature by a signer unit that computes this signature by using a random data element sent by a verifier unit, and the checking of the signature by the verifier which ascertains that a mathematical condition, bringing into action the signature sent and the random data element, is fulfilled, this method being characterized in that the checking of the signature sent by the signer to the verifier further uses a step for the timing of the period that elapses between an instant when the random data element is sent by the verifier to the signer and the instant when the signature using this data element returns to the verifier after computation by the signer, the signature being accepted if the time elapsed is below a defined threshold and if the mathematical condition is verified.
Preferably, the algorithm used is of the type in which the signature generation produces two values {r, s}, s being computed from r and a secret key x, and in which the checking of the signature {r, s} consists of the checking of an equality v=f(r, s)=r between r and a function f of r and of s. It is then provided according to the invention that the function f will be chosen to be sufficiently complex so that the period of the search for a value s on the basis of this equality when there is no knowledge of the secret key is far greater, even if it is performed by a powerful computer, than the period of computation and transmission by the card of the value s on the basis of r and of the secret key, this being the case even if the card uses a low-power microprocessor (a 20 MHz 8-bit microprocessor for example). Thus, by making an accurate choice of the time condition introduced by the timing, it is seen to it that this condition cannot be fulfilled when there is no knowledge of the secret key, and especially that it cannot be fulfilled by a search for s on the basis of the equality r=f(r, s).
In practice, the function f(r, s) also brings into action a message m to be signed so that it can be referenced f(r, s, m).
Preferably, the function f comprises mathematical computations followed by a complex hash function. The first part of the signature r is established by other mathematical computations followed by the same complex hash function.
This complex hash function is preferably, as shall be explained further below, a complex compression function leading to a reduction of the length of the bit strings obtained by the mathematical computations performed.
It may be recalled that a hash function is a function of logic processing of binary strings that can be used to obtain a string of characters of determined length on the basis of another string of characters of the same length or of a different length. A complex hash function may be obtained by successive operations of hashing and/or mathematical computations implying the results of several hashing operations. A compression may be obtained at the end by taking, as the result, a modular value modulo 2 e where e is the length of the string finally desired.
Furthermore, according to another major aspect of the invention, there is proposed a novel approach for the processing of the smallest numbers in the smart card, in digital signing algorithms of the type in which the signing brings into action two numbers, r and s, only the number s bringing into action the secret key of the card and the message to be sent.
This second aspect of the invention is an improvement to a method for the generation of signatures that has been described in the French patent application 93 14466. In this patent application, it is explained that, in an algorithm of this type (DSA is an example thereof), the number r depends neither on the message m sent by the card nor on the secret key contained in the card. It depends only on numbers that are unchanging for the application considered and on random numbers; for example these numbers are g, p, q and k in the DSA algorithm. It is therefore unnecessary to obtain a computation of r by the card, for this takes up a substantial amount of computation time. Rather, a certified central authority is made to carry out a computation in advance of a series of n possible values r, referenced r i , i being an index ranging from 1 to n. The values r i are stored in the card. At each new use of the card, one of the values r i is used (and this value will no longer be used at the following times). At the time of signing, the card computes only the other part of the signature s on the basis of a value r i and the secret key x of the message m, and the verifier is then sent the message m and the pair {r i , s} representing the signature that the verifier can then make the check in the manner laid down by the algorithm considered.
The numbers r i are precomputed certificates, also called "signature coupons". They form a part only of the signature to be sent and they may be prepared and stored in advance in the card. The index i represents the index of the coupon used during a given signature.
However, one of the difficulties lies in the great length of these coupons (160 bits in the DSA algorithm represented here above). They use up a substantial degree of non-volatile memory space in the card. It is not possible to save a large number of them in the card if a limited size of non-volatile memory is available. Furthermore, they entail a very lengthy computation time with an 8-bit microprocessor because it is necessary to search for these numbers in small pieces. However, if smaller signature coupons were to be used and stored, there would be the risk of the guarantee of authenticity of signature being far lower.
The invention described here makes it possible to reconcile the need for a guarantee of authenticity with the use of smaller signature coupons r i .
The invention therefore proposes a method for the generation of electronic signatures by a signer unit and for checking by a verifier unit, using a digital signature algorithm in which the signature sent by the signer comprises at least one signature coupon r i and one signature complement s that is computed on the basis of the coupon r i and of a secret key x of the card, this algorithm enabling the checking of a signature by a verifier by means of a checking formula of the following type:
v=f(r i , s)=r i
this method being characterized in that:
a. the signature coupon is established in advance by a certified authority, in two steps:
the computation of a number represented by a long binary string, by means of a mathematical formula bringing into action big binary numbers;
and the modification of the result of this computation by a complex compression function greatly reducing the length of this result,
b. a series of different coupons of small length are thus prepared in advance and stored in the signer unit (smart card with memory and microprocessor),
c. the signature generation comprises the sending of a coupon r i and a signature complement s computed on the basis of at least r i and x,
d. the signature checking algorithm comprises a mathematical computation followed by the same complex compression function as the one used to prepare the coupon, and the result is compared with the coupon for the signature check.
The compression function is preferably a complex hash function that requires a fairly lengthy computation time. This provides great security to the method of generation and checking of signatures. Hence the advantage of an efficient guarantee of authenticity of signatures is combined with the possibility of the saving in the card of only small-sized coupons, hence the possibility of saving many of them. If, in addition, the timing mentioned further above is used, it can be seen that it is possible to reinforce the guarantee of authenticity to a very high degree.
The computation of the signature s of course brings into action the message m that is to be signed in order to guarantee not only the authenticity of the signature but also the integrity of the message transmitted.
It is further possible to improve security by one or more of the following characteristics:
The formula for the computation of the coupon r i is preferably established on the basis of a random element J generated at the outset by the card and stored in the card to be reused when the coupon is be used to establish a signature.
It is possible to provide for a situation where, in order to activate the generation of a signature, the verifier terminal will send a random element a to the card and then activate the timer; it can also seen to it that the establishment of the signature complement necessarily uses this random element a and that the checking of signatures also necessitates this random factor a.
The signature complement s is preferably established by a computation bringing into action a hash function SHA(m, a) of the message and of this random factor a, the same hash function being used for the signature check.
The signature complement s is preferably established by a computation bringing into action a random element J stored in the card and having been used to establish the signature coupon. Preferably again, this computation of s brings into action a hash function SHA(x, J, i) pertaining to this random element J and to an index i representing the number of the coupon used, this same hash function having been used previously during the computation of the long binary string provided for in the computation of the corresponding coupon. This hash function preferably also brings into action the secret key x of the card.
The signature function s is preferably established by a computation bringing into action a hash function of the coupon SHA(r i ), the same hash function SHA(r i ) being used for the signature check.
Thus, according to a particular aspect of the invention, there is proposed a method for the generation of digital signatures of messages by a signer device and for the checking of these signatures by a verifier device, the signer device comprising means for the computation, communication and retaining of data elements comprising at least one electrically programmable non-volatile memory according to which there are prepared enciphered data elements constituting signature coupons r i that are loaded into the non-volatile memory and that are used by the signer device to sign messages, chiefly characterized in that:
the coupons are compressed by the application of a compression function, also called a hash function, by a certified authority before being loaded into the memory, and in that this method comprises the following exchanges:
a message m is transmitted and this message must be certified by a signature,
the signer sends a coupon r i to the verifier,
the verifier sends a random number a to the signer and activates a timer,
the signer computes the signature s of the message and sends it to the verifier,
the verifier stops the timer and ascertains that the signature has been obtained through the secret held in the card and the coupon r i received; this checking is done by checking the following equality:
v=f(r.sub.i, s, m)=r.sub.i
the verifier accepts the signature if the condition of checking v=r i is fulfilled and if the measured time does not exceed an allocated predetermined period.
To simplify the description, hereinafter, reference shall be made above all to a card for the signer or to a signer.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the invention shall appear from the following detailed description made with reference to the appended drawings, of which:
FIG. 1 describes the flow chart of a card implementing the system proposed by the present invention;
FIG. 2 describes the data elements transmitted between the card and the terminal at the time of the use of the coupon;
FIG. 3 describes the flow chart of a terminal implementing the system proposed by the present invention;
FIG. 4 shows the data elements transmitted between the card and the authority during the stage for the loading of the coupons and the organization of the memory of the card after the loading of n coupons.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
From the explanations given in the introduction, it will be understood that the main advantage of the signature coupons precomputed according to the method of the invention lies in the speed of computation of a signature by a card based on a single 8-bit microcontroller and the low memory storage requirement of the stored coupons. Typically, the signature computation can be done in 300 ms approximately, including transmission time, and each coupon may use two to four EPROM or EEPROM type memory bytes.
The invention shall be described in this example, bearing in mind that it is only an example, even if it is considered herein to be the most advantageous one
The method for the generation of signatures can be subdivided in this case into two distinct stages: the loading of the coupons by the authority that has delivered the card and then the use of these coupons by the card, before a terminal that does not know the secret x of the card.
The two stages herein make use of two different types of hash functions. It may be recalled that a hash function for the hashing of an number, represented by a string of bits, consists of the production of another string of bits of a specified length that may or may not be the same as the length of the initial string, this production being done on the basis of logic functions carried out on groups of bits of the initial string.
Simple hash functions are used, referenced SHA(ch) for the hashing of a string ch. These functions may be standard hash functions such as those published in the recent American standard SHA (Secure Hash Algorithm-FIPS PUB 180, dated Feb. 1, 1993, in Digital Signature Standard). These functions may be MDA or MD5 functions or a hashing operation based on the DES (Data Encryption Standard) algorithm.
Other functions, known as complex hash functions will also be used. Their characteristic used herein is not so much that of being a hash function as that of being a slowing-down function dictated during certain signal processing operations, and also that of being a compression function reducing the length of the signature coupons to be saved in the smart card.
This slowing-down and compression function is hereinafter referenced H(ch) for the processing of a string ch.
All sorts of slowing-down and compression functions could be used in the invention. For example, the following function has been taken as a function H(ch), where SHA(ch) designates a standard hash function:
H(ch)=SHA SHA{SHA(ch)}.sup.SHA(ch) mod p! mod 2.sup.e
where e is the length desired for the coupons, for example 16 to 40 bits, giving some bytes.
Hereinafter, we shall take up an algorithm directly inspired by the DSA algorithm to show how the original specific features of the invention are implemented. The parameters p, q, g, x, y used are those defined here above with respect to the algorithm DSA.
LOADING OF COUPONS INTO THE CARD
This is the preliminary step but of course only when a computation is made in advance, outside the card, of the first part r of the signature {r, s} and when several possible values r i are loaded into the card.
1. The card resets a counter in the non-volatile memory (EPROM or EEPROM), generates a random element J (of 10 to 20 bytes for example) records it in the non-volatile memory and sends it to the control authority that knows the secret x of the card and that makes a computation, for i=1 to n, of several values k i and several values r i :
k.sub.i ={1/(SHA(x, J, i)} mod q
and r i =H(g ki mod p); H is the slowing-down and compression function.
It may also be envisaged that the card will make a computation for each i of the value SHA(x, J, i) and will send it to the control authority; this authority computes the numbers r i .
2. The authority sends the numbers r i to the card that stores them in memory in preserving the link with the reference i. The numbers k i are not preserved.
If we refer to the algorithm DSA, k i represents the random number k, modified at each new signature. However, instead of being put out by the verifier terminal at the time of a signature, it will be recomputed at the appropriate time by the card. Since it depends on i and since a coupon with an index i is used only once, k i is renewed each time.
THE USE OF A COUPON TO SIGN A MESSAGE
When the card seeks to sign a message, the following protocol is used after the transmission of the message m (preferably in the form of a hashed function of the true message, according to a known hash function of the terminal that receives the message):
1. The card:
extracts the state i from the counter (representing the current index of the signature that will be produced);
extracts, from the non-volatile memory, the random element J, the secret x, the coupon r i corresponding to the index i;
computes I=SHA(x, J, i); this value I is none other than the modular reverse of k i used for the computation of the coupon r i ;
computes A=xSHA(r i ) mod a;
increments i (for a future signature);
sends r i to the verifier terminal; this dispatch representing the first part of the signature.
2. The terminal then generates a random element a, to activate the generation of the second part of the signature s; this dispatch constitutes so to speak the sending of a challenge to the card for the verifier terminal, at the same time, acrtivates a timer to measure the response time of the card to this challenge.
The signature s that the card must send, given the checking formula f(r i , m, s, a)=r i which is provided for in the verifier is:
s= xSHA(r.sub.i) mod q+SHA(m, a)!/k.sub.i mod q
This formula brings into action the coupon r i , the secret x of the card, the message m sent, the number k i , and the random element a sent by the verifier by way of a challenge. This formula is different from the one given by the DSA algorithm, s=(m+xr)/k, for several reasons: it must bring into action the random element to be sent by way of a challenge so that the verifier is sure that the timing computation of the signature s begins only when the random element a has reached the card. It is for this reason that a hashing of m and of the random element a, namely SHA(m, a), has been used instead of a hashing of m. Furthermore, preferably SHA(r i ) is used rather than r i to use a coupon value in the form of a string that is longer than r i which is a very short string. This increases security. But naturally, if xSHA(r i ) is used instead of xr i and SHA(m, a) is used instead of m, then the checking formula must take account thereof and it shall be seen further below that this is what is done. Other variants of signature computation can be provided for, on condition simply that the checking formula takes account of them.
3. The card computes the signature s as speedily as possible. However since, before the activation of the timer, it has already computed A=xSHA(r i ) mod q and I=1/k i =SHA(x, J, i), all that remains for it to do is to compute:
s=I.(SHA(m, a)+A) mod q
This computation can be swift even for a simple, low-cost 8-bit microcontroller, for example of the Intel 8051 type or Motorola 6805 type. Once the computation is over, the card sends back the signature s.
4. Upon reception of s, the terminal stops the timer and performs the computations for checking the authenticity of the signature. If the signature has been accurately computed according to the above formula, then it can be verified that it is necessary to have the following equality:
y.sup.(SHA(ri)/s) mod q g.sup.(SHA(m,a)/s) mod q mod p!=g.sup.ki mod p
The verifier does not possess k i . It possesses r i =H(g ki mod p); H is the slowing-down and compression function.
The equality can therefore be converted into:
G y.sup.(SHA(ri)/s) mod q g.sup.(SHA(m,a)/s) mod q mod p!=H(g.sup.ki mod p)=r.sub.i
The verifier has available r i , s, a, p, g, m, a, the simple hash function SHA, and the slowing-down and compression function H. It therefore checks the above equality.
If the equality is obtained and if the signature has been sent within a period of time smaller than a determined threshold, the signature is accepted by the verifier. If one of the two conditions is not fulfilled, it is not accepted.
By way of an example for the assessment of the duration, it is possible to give the following indications: let T be the time needed to assess H(ch) on an extremely powerful computer, possibly even the most powerful computer known today. It may be assumed that the slowing-down function H, leading to strings with a length e (H also having a function of compression) is sufficiently complex and in any case must be chosen to be sufficiently complex so that, for any value z and any existing computer, the search for a new value ch' such that z=H(ch') requires a period of time T.2 e .
Given that someone who is unaware of the secret of the card can make a search for s only by trial and error on the basis of the checking formula (i.e. by making an exhaustive search), he cannot, even with a single attempt, find an accurate value of s if it is chosen to set the time threshold at a level very much smaller than this value T.2 e , for example a millionth of this value.
This gives an indication of the methodology to be followed to choose the slowing-down function H and the threshold duration.
In general, the principles explained here above and illustrated by an example can be applied to other signature protocols. In particular they can be applied to other protocols in which a precomputation of signature coupons is possible, especially the following protocols:
Rueppel-Nyberg
"New signature schemes based on the discrete logarithm problem", in proceedings of the Eurocrypt'94 conference.
Schnorr
"Efficient identification and signatures for smart cards", in proceedings of the Crypto'89 conference.
El-Gamal
"A public-key cryptosystem and a signature scheme based on discrete logarithms", in the journal IEEE Transactions on Information Theory, Vol. IT30, No. 4, pp. 469-472.
Guillou-Quisquater
"A practical zero-knowledge protocol fitted to security microprocessors minimizing both transmission and memory", in proceedings of the Eurocrypt'88 conference and "A paradoxical identity-based signature scheme resulting from zero-knowledge", in proceedings of the Crypto'88 conference.
Other public key systems based on the discrete logarithm, where the equation (m+xr)/k mod q is replaced by another equality bringing into action m, x, r and k (as explained in the article by Horster et al, "Meta message recovery and meta blind signature schemes based on the discrete logarithm problem and their applications", in proceedings of the Asiacrypt'94 conference), or again systems using several distinct random elements k or several distinct secrets x in the same signature.
The invention can be applied to the signing of electronic cheques and can then be used to make these cheques with low-cost smart cards (resulting from the use of an 8-bit microprocessor and a non-volatile memory of limited size).
Indeed, the message m may represent a transaction performed by the card with the terminal which is, for example, the payment terminal of a tradesman. This message m is signed. The terminal checks the signature in order to accept the message and hence the transaction, but this terminal is also connected to a central management authority (a bank for example) which must itself be capable of checking the message and the authenticity of the signature before debiting the signer's account on the one hand and/or crediting the tradesman's account on the other hand.
Thus, after having performed the entire procedure of signing and signature checking described in detail here above, the terminal sends the checking authority the electronic cheque {i, r i , a, s, m}, and the authority ascertains that the signature s is the right signature, namely that:
s=SHA(x, J, i) SHA(m, a)+xSHA(r.sub.i)! mod q
and the authority credits the account of the terminal with the amount of the transaction defined in the message m.
It will be noted that, in the computation of the signature by the card, it is possible to use the expression SHA(m, i, a) instead of SHA(m, a). In this case, the formula of checking by the terminal should take account of it and should therefore be:
H y.sup.(SHA(ri)/s) mod q g.sup.(SHA(m,i,a)/s) mod q mod p!=r.sub.i
and the formula for the checking of signatures by the authority should also take account of it and be:
s=SHA(x, J, i) SHA(m, i, a)+xSHA(r.sub.i)! mod q
Referring to the figures, each smart card consists of a processing unit (CPU) 11, a communications interface 10, a random-access memory (RAM) 13 and/or a read-only memory (ROM) 14 and/or an erasable or electrically erasable and programmable read-only memory (EPROM or EEPROM) 15.
The processing unit 11 and/or the ROM 14 of the smart card contain computation programs or resources corresponding to the performance of the computation steps performed by the card during the loading of the coupons and during the signing of a message or the sending of an electronic cheque. These programs contain in particular the rules of computation for the generation of s and the rules of the use of the hash function SHA. The computation unit and the ROM programs also comprise the resources needed for the operations of multiplication, addition and modular reduction. Some of these operations can be combined (for example the modular reduction may be directly integrated into the multiplication).
Just as in the case of the DSA algorithm, the RAM of the card contains the message M and the random element a to which there are applied the hash function SHA(m, a) or SHA(m, i, a) for example. The non-volatile memory 15 typically contains the parameters q, x, J and the set of precomputed coupons (r i ). The index is in a non-volatile counter incremented at each new generation of a signature and reset during the loading of coupons.
The processing unit of the card, through address and data buses 16 and the communications interface 10, activates the operations of reading and writing in the memory 13, 14 and 15.
Each smart card is protected from the exterior by physical protection systems 17. These protection systems ought to be sufficient to prevent any unauthorized entity from obtaining the secret key x. The techniques most commonly used at the present time in this field are the integration of the chip into a safety module and the fitting out of the chips with devices capable of detecting variations in temperature, light as well as abnormal voltages and clock frequencies. Special designing techniques such as the scrambling of the memory access are also used.
The terminal for its part consists of a minimum of one processing unit (CPU) 30 and memory resources 32, 33, 34.
The CPU 30, through the address and data buses 35 and the communications interface 31, controls the operations of reading and writing in the memories 32, 33, 34.
The CPU 30 and/or the ROM 34 of the authority contain computation programs or resources enabling the implementation of the rules of computation and of the hash, slowing-down and compression, multiplication, addition, modular inversion, exponentiation and modular reduction functions needed for the computation of the coupons and for the checking of signatures. Certain of these operations (for example the multiplication and modular reduction operations) may be combined.
The entire invention has been described with reference to smart cards, but it will be understood that it can be applied when the signer unit is another object and especially when it is a portable object such as a PCMCIA card which is a type of smart card with parallel and non-serial transmission protocols or a badge, contact-free card, etc. The communication may be between the card and the terminal, either directly by means of electronic signatures or by remote, radiofrequency or infrared transmission. | Processes for generating digital signatures for electronic messages. Modifying signature-generating algorithms, such as DSAs (Digital Signature Algorithms), in order to enable smart cards with reduced calculation and storage resources to produce digital signatures with a high degree of security in spite of their reduced resources. The signature-checking terminal sends a random number a and measures the time taken by the card to send back a signal s using this random number. If the time is greater than a given duration, the signature is rejected even if the check of its authenticity is positive. In addition, part of the signature (the part which does not use the secret card key but only the public algorithm parameters) is precalculated and stored in the card in the form of signature portions produced by a compression function such that they are short. Only the second part of the signature has to be calculated by the card. The calculations to be made are simple so that the card does not require extensive calculation and memory resources. | 7 |
Cross Reference
This application is a continuation-in-part of my co-pending application, Ser. No. 331,505, filed Feb. 12, 1973, now abandoned.
Background of the Invention
This invention relates to a method and apparatus for collecting excess paint spray particles in a paint spraying operation.
The term "spray booth" is a term of art generally denoting a large sheet metal structure or housing having a so-called working area or space with which spray painting operations are carried out, an exhaust chamber with an associated stack communicating with the working area, a fan in the stack for drawing fresh air into and through the working area to maintain it well ventilated, and means between the working area and the exhaust chamber for removing paint particles from the air before the air is exhausted up the stack. In essence then, the booth structure defines an air flow passage through which air is moved at high velocity to eliminate mists created by a spray paint operation. Removal of air laden with spray mist and overspray is necessary, among other reasons, to prevent excessive or explosively high concentration of volatile solvents and other flammable materials, to protect personnel in the vicinity from exposure to toxic materials, and to maintain a clean environment for proper finishing of the ware. Current standards require a minimum air flow rate at the face of the booth of 60 cubic feet per minute per square foot, or at least 60 linear feet per minute at each point at the face of the booth for unattended booths, and 100 cfm per square foot or 100 linear feet per minute for attended booths. In order to collect the paint particles and minimize pollution of the atmosphere, especially at the high rates of air flow, the exhaust air laden with spray residue is circulated through an eliminating device or medium, which serves to remove the paint particles before the air is exhausted into the atmosphere.
Eliminating media in current use include the dry baffle system, the dry filter system, and the water wash system. In the dry baffle system, the air is circulated in a tortuous path over solid baffle surfaces disposed between the working area and the exhaust chamber, which causes the paint residue to be deposited thereon. The dry filter system employs filters of a variety of types through which the air is circulated. Both of these dry systems involve frequent cleaning and maintenance problems due to paint accumulation, and also the problem of disposal of waste matter and spent filters as well as presenting a fire hazard.
In the water wash booth, such as that described in the Pearson U.S. Pat. No. 2,545,672, water is caused to flow downward over an imperforate wall at the back of the working area and across an open gap between the bottom of said wall and the liquid level in an underlying water reservoir in the form more or less of a water fall, thereby to form a curtain of descending water against and through which the paint laden air is drawn at high velocity, and whereby the paint is entrained in the water and collected in the reservoir. Principal drawbacks of the water system are that the water must be treated with chemicals to prevent growth of algae and to control the paint collected in the reservoir, and that the waste water is a pollutant. Also, since the area for passage of air into the exhaust chamber is relatively small in comparison with the booth size, and located solely at the bottom regions of the booth, the air flow rate is not uniform within the booth, and a high horsepower fan must be used to maintain the minimum prescribed air flow rate in all areas at the face of the booth. Moreover, the accumulated paint solids cannot be reclaimed and reused and tend to clog the system. Rusting of the booth interior is also a problem, and a severe loss of efficiency in paint removal is experienced if the water curtain is interrupted.
In a development entirely separate from the paint spray booth art, proposals were made during the 1930's to remove dust particles from air by drawing the air at low velocity in a tortuous path through an oil coated baffle system. Representative patents relating to this development include Hines U.S. Pat. No. 1,751,999; Adams et al, U.S. Pat. No. 1,807,950; Gagen U.S. Pat. No. 1,895,619; Dauphinee U.S. Pat. No. 1,899,017; and Weisgerber U.S. Pat. No. 1,083,764. Hines U.S. Pat. No. 1,751,999, for example, discloses a low velocity air filter having a plurality of closely spaced, angularly disposed baffles, together with means to circulate oil over the baffles and through a filter.
Notwithstanding general similarities between the arts of dust particle air filters and spray booths, and a high degree of further development in the art of spray booths since the above development, the use of oil or other viscous liquid as an eliminating medium in a spray booth of the structure hereinafter described has not been developed in the prior art, and the art of air filters has developed separately and independently from the art of spray booths. One fair supposition for this divergence is that the use of oil in a conventional water wash booth would cause contamination of the external atmosphere with oil, due to the high velocity air flow. Conversely, the requirement of a high velocity air flow in a spray booth would be incompatible with the aforesaid air filter devices because large amounts of oil would be stripped off the baffle surfaces, causing such devices to become inoperable.
SUMMARY OF THE INVENTION
In accordance with the present invention, a supported moving film of oil is used as the paint collecting medium in a specially designed paint spray booth. The booth comprises an enclosure having an inlet opening therein through which air is drawn at a high velocity, or in excess of 60 cfm per square foot of opening. Spaced inward from said opening are a plurality of rows of baffles arranged substantially perpendicular to the air flow. The front row of baffles are substantially planar with wide frontal faces, and are closely spaced to define narrow vertical spaces therebetween through which air may pass. A film of oil is continuously flowed over the front surfaces of the baffles in order to entrain therein paint mist carried by the air stream, and the oil is circulated through a reservoir wherein the paint settles and may be removed and reclaimed. Means downstream of the baffles are also provided to remove oil droplets from the high velocity air before it is exhausted into the atmosphere.
The use of mineral oil as a permanent paint collecting or eliminating medium provides unexpected and unique benefits not attainable by prior art methods. The paint is not chemically modified by the oil and may be easily separated and reclaimed. The oil is continuously recirculated through the system, which allows for self-cleaning of the booth interior and prevents adherence of paint on any exposed surface, and the self-contained oil circulation system eliminates pollution problems. The baffle arrangement provides for a uniform high velocity flow of air through the working area of the booth without stripping the oil from the baffles.
The benefits herein recited are unexpected because both oil and paint mist are combustible materials, and it would be expected that the combination of the two would be unacceptable because of the possible fire hazard.
Unexpectedly, for reasons explained in detail herein, the combination of mineral oil and paint mist in a spray booth does not result in a flammable mixture at normal or above normal operating temperatures. The high rate of air flow through the booth prevents absorption of the volatile and highly flammable paint components into the thin film of oil, whereas the paint solids are entrained in the oil in a highly efficient manner. The entrained paint solids are thus coated with non-flammable mineral oil and tend to collect in a harmless manner at the bottom of the oil reservoir.
THE DRAWINGS
FIG. 1 is a perspective view of a simplified form of spray booth, which incorporates features of the present invention;
FIG. 2 is a vertical sectional view taken substantially on line 2--2 of FIG. 1;
FIG. 3 is a sectional view taken along line 3--3 of FIG. 2; and
FIG. 4 is a sectional view taken along line 4--4 of FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIGS. 1 and 2 illustrate a spray booth 10 having a forwardly extending sheet metal enclosure defining a spray painting or working area 11 and an air intake opening 12 at one side thereof, and a rearwardly disposed exhaust outlet 14 at the top. Objects to be spray painted, such as indicated at 16, are supported in the working area 11 inwardly of the opening 12, and a spray of paint or coating material is directed toward the objects by use of a spray device, such as shown schematically at 18. The paint may comprise any number of the known coating materials, including but not limited to water and solvent based materials, such as alkyds, nitrocellulose laquers, water base enamels, polyurethanes and epoxy resins.
Means are provided for forcibly drawing air horizontally through the inlet opening 12 and vertically up and out through the exhaust outlet 14 in substantially an L-pattern, such as a power driven fan 20 located in the exhaust outlet. Excess paint mist and paint overspray at the inlet is thus drawn into the interior of the spray booth by a high velocity air flow.
The working area leads rearwardly to the solids eliminator portion of the spray booth or baffle section and is surrounded by a top wall 22 and side walls 24. Spaced rearwardly from the working area are a plurality of rows of baffle plates 26, 28 and 30, the first row of plates 26 in effect constituting the rear wall of the working area. In general, the rows of baffle plates are arranged in a parallel relationship, and each row comprises a plurality of spaced, generally vertical members rigidly supported by their ends in a fixed position.
The baffle plates 26 comprising the outermost row, as shown in FIGS. 2 and 3 are substantially flat and are arranged substantially in a common plane which is substantially perpendicular to the direction of air flow at the inlet, as indicated schematically by the arrows. Adjacent plates are spaced from one another to define narrow open vertical slots 32 therebetween. The baffles are from about four to about seven times wider than the width of the slots, and the side edges thereof are bent rearwardly on an obtuse angle for reasons hereinafter more fully described.
The second set of baffle plates 28 are similar to the first set in terms of width and spacing from each other, except said plates are slightly V-shaped or concave relative to the direction of air flow, with the side edges being bent rearward on an obtuse angle. The longitudinal centerline of the second set of plates 28 coincides with the transverse centerlines of the slots 32 whereby the first and second rows of baffles are arranged in a staggered relationship.
The third row of plates 30 are relatively narrower than the plates of the first two rows and are located behind and are coextensive with the vertical slots 34 between the plates of the second row. The side edges of the plates are bent forwardly, and the space between the third and second rows is less than the space between the first and second rows. The described spacing causes a progressive increase in velocity of air passing through successive rows of baffles.
It will be noted that the respecitve second and third rows of baffles 28 and 30 are not entirely vertically coextensive with the first row 26; instead, the former are shorter than the first row and are suspended in a spaced relationship from a solid or non-permeable web 36 extending downward and supported from the top of the enclosure in parallel with the first row of baffles. Preferably, the length of the web 36 is about one-third of the length of the first row of baffle plates 26. The web 36 serves to alter the normal rate of air flow from the top to bottom of the first two rows of baffle plates, such that the flow is equalized or uniform from top to bottom of the plates and no area of the plates will be subjected to an excessively high flow that would strip the oil therefrom.
The rows of baffle plates are arranged in a spaced staggered relationship to provide for successive positive and at least right angle deflection of any paint and oil particles which emerge through the first group of vertical slots 32, and the final row of baffle plates 30 serve as collectors of oil and solids particles which may be carried through the downstream passages by the high velocity air flow. The air velocity is also rapidly increased up to the final row of baffles in order to increase the straight line momentum of any oil particles, which would otherwise tend to move in a tortuous path with the air flow around the baffles instead of collecting on the final row of baffles as desired.
Means are provided for establishing a continuous and uniform flow of oil down from the front surfaces of the first and second rows of baffle plates, 26 and 28 respectively. A reservoir 38 of mineral oil is provided in the bottom of the enclosure, and is connected, via a suitable pump 40 and line 42, to the top of the enclosure. The line 42 is connected to a bifurcated branch 44 leading into respective troughs 46 and 48 located respectively over and coextensive with the first and second rows of baffle plates 26 and 28. The troughs 46 and 48 have lowered forward edges which allow the oil to spill over and down the front surfaces of the first row of baffle plates 26 and web 36.
As shown in FIG. 4, the lower edge portion of the web 36 is provided with a spaced series of V-shaped channels 50 located above respective individual baffle plates of the second row 28. The channels 50 serve to funnel or concentrate the oil moving downward on the web into the central portion of the front surfaces of baffles 28, which has been found to minimize stripping and loss of oil by the air flow as the oil moves down the baffles. The third row of baffle plates 28 are not directly supplied with oil and are supported by a bracket 51 secured to the rear side of the web 36.
The lower ends of the front baffles 26 are connected to a substantially horizontal drain board 52 spaced slightly above the oil level in the reservoir 38, such that the paint laden oil falls a short distance into the reservoir, which has been found to minimize splashing and build-up of paint scum on the surface of the oil reservoir. The mere draining of oil onto the surface of the reservoir may allow the paint solids to float and cling together, whereas a slight drop allows for penetration of the surface. The lower edges of the rear baffles 28 and 30 are spaced above the reservoir oil level to provide the same effect.
It will be noted that the baffles 26, 28 and 30 are preferably inclined downward and outward on a slight vertical angle, preferably in the order of 3° to 4° and no greater than 5°, in order to enhance the continuity of oil flow thereon. An angle greater than 5° from vertical is not desirable due to the tendency of the baffle edges to lose their oil coating.
Important features of the baffle system include the substantial width or frontal surface area of the baffles in comparison to the width of the air passage slots therebetween, and the arrangement of the baffles in a plane which is substantially perpendicular to the path of air flow through the booth. These features allow for a maximum exposure of the moving films of oil to the contaminated air. Also, the planar or slightly concave quality of the baffles, together with the uniform spacing of the air slots therebetween, permits a very high air flow thereover without the oil being wiped from the surface, which would allow the undesirable accumulation of paint on the bare surfaces. The baffles are free from sharp corners, or corners which are less than 90°, because sharp corners would be wiped clean of oil by the high velocity air, especially in the vicinity of the slots. Hence, the baffle design described herein is particularly adapted to present large and efficient oil coated surfaces which retain their oil coating under conditions of high velocity air flow, which, at the first set of baffles may be 125 linear feet per minute and at the second set of baffles, in the order of 2300 linear feet per minute.
Another important feature in the design of the baffle system is the existance of a substantially uniform air flow from top to bottom and from side to side in the inlet opening. In contrast with a water wash booth having a relatively small waterfall area and high resistance to air flow, the present baffle system offers relatively low resistance to air flow due to the length of the slit openings and spacing of the baffle rows, thus allowing the use of a relatively low horsepower motor.
As shown in FIG. 2, located rearwardly or downstream of the first baffle system is a second baffle system, the primary purpose of which is to collect and remove oil particles which escape from the first baffle system. Whereas the first baffle system is arranged in substantially a vertical plane, the second system is arranged horizontally in a vertical exhaust chamber 54 upstream from the exhaust outlet 14. The chamber 54 comprises a forward vertical wall 56 spaced rearwardly from the first baffle system, which extends downward from the top of the enclosure and terminates at a location above a forwardly sloping base 58 and below the tops of the rear baffles 28 and 30, preferably at a point approximately at the horizontal center line of said baffles. As shown by the arrows indicating air flow, air entering at the top of the first set of baffles is swept downward around the wall 56 and then upward into the vertical chamber 54.
As shown, the second baffle system comprises, at the lower entrance of the chamber 54, a first pair of upwardly converging baffles 60 connected to opposite chamber walls by respective horizontal portions 62 having covered openings 64 therein to collect and drain away accumulated oil. The respective end edges of the baffles 60 are supported upon rods 66, said edges having a relatively wide space therebetween to channel and concentrate air flowing therethrough.
A deflecting baffle 68 supported on rods is provided upstream from and in the outlet path of the converging baffles 60. The baffle 68 comprises a horizontal portion which is wider than the outlet of baffles 60 and is connected to opposite legs 70, which are disposed in a downward obtuse angle from the horizontal portion, the ends of said legs being spaced outward from and about on the same level as the ends of the baffles 60. The legs 70 are spaced from the sides of the chamber 54, and air is caused to flow in a tortuous path around the legs, causing oil to accumulate thereon and fall downward onto horizontal portions 62.
A pair of downwardly angled baffles 72 are connected from the chamber walls above the legs 70 of the deflecting baffle 68. The baffles 72 are substantially planar and have terminal edges which extend over the juncture between the legs 70 and the horizontal portion of baffle 68. Thus, the baffles 72 are disposed in the path of the air which emerges around the baffle 68 and serve to further deflect the air flow toward the top of the underlying baffle 68.
Disposed above baffles 72 are a pair of permeable air filters 74 arranged in an inverted V-configuration. The filters 74 may be composed of a mesh material composed of metal, glass fibers, or the like, supported in a frame. The filters 74 serve to remove the final finite traces of the oil before the air reaches the exhaust outlet 14.
The type of oil employed is preferably a mineral oil without detergents or other additives, and having a viscosity to easily flow down the baffles at room temperature without undue vaporization. A mineral oil having a viscosity of 660 Standard Saybolt Units at 100°F have been found to be suitable, although other viscosities may be employed. A suitable flow rate is approximately 8 gallons per minute for each foot of width of baffles, and the reservoir preferably contains at least about 25 gallons per foot of baffle width, to provide sufficient volume for settling of the paint solids.
Mineral oil offers several advantages, including a high flash point and burning point, and is incompatible and chemically unreactive with paint solids in current use. Because the oil has a lower density than the paint solids, the solids tend to settle to the bottom of the reservoir where they may be removed. Moreover, the flammable volatile solvent components of the paint are not absorbed by the oil and do not lower the flash point or burning point thereof. The presence of paint solids which may remain entrained in the circulating oil do not substantially affect the efficiency of the eliminator baffles.
In operation, the fan 20 and oil pump 40 are activated, such that oil is pumped from the reservoir 38 upward through the line 42 into the troughs 46 and 48. A continuous supply of oil flows down over the first and second rows of baffles, 26 and 28, and air is drawn through the inlet opening 12 at a rate of at least 60 linear feet per minute and preferably in excess of 100 linear feet per minute.
With the booth in readiness, objects, such as inidicated at 16, are disposed in or near the opening 12, and the paint spray device 18 is located upstream of the object and is aimed at the object.
Atomized paint which does not adhere to the object 16 is carried by the high air flow into contact with the first baffles 26, which are entirely covered with a continuously moving film of oil. As a result, the solid paint particles are entrained in the oil and flow downward into the reservoir 38, where the paint solids are allowed to settle. Paint particles which avoid the first baffles 26 and pass through the air slots 32 increase in momentum and are deposited on the second set of baffles 28, and any particles passing the baffles 28 through the slots 34 are collected by the baffles 30, which are normally wetted by oil removed from the first two rows of baffles.
After the air has passed through the eliminator baffles, it passes under the barrier wall 56 and moves upwardly in the chamber 54, thereby encouraging elimination of oil mist by gravity forces. Also, the chamber 54 presents a relatively larger volume than the volume near the eliminator baffles, which causes a reduction in air velocity and decreases the ability of the air to carry any residual oil.
The air is deflected off the successive baffles 60, 68 and 72 such that virtually all residual oil is removed from the air and is returned to the reservoir. The filters 74 serve as a final precaution to the escape of the minute particles into the air.
After the booth has been used over a period of time, the paint solids which have collected in the bottom of the reservoir may be removed and reclaimed.
In comparison to other known spray booths, the spray booth offers the following advantages: very low emission of particulates into the atmosphere since the booth will normally operate at 99 or 100% efficiency; easy collection and reclaimation of coating material solids and ability to accommodate a greater variety of coatings; easier cleaning of booth and no corrosion of booth materials; quieter operation and uniform air velocity at face; less electrical power required; and various other advantages mentioned hereinbefore. | A paint spray booth for removing excess atomized paint from the air in the vicinity of a spray painting operation comprises a spray booth structure having a working or spray painting area, an exhaust chamber and an exhaust stack, which together define an air passage having an inlet at the spray painting area and an outlet at the stack, within which a fan is mounted for drawing air through the inlet and out the outlet at high velocity. A plurality of generally vertical baffles are disposed in the passage between the spray painting area and the exhaust chamber for the purpose of removing overspray or excess atomized paint from the air before it is exhausted out the stack. Mineral oil is continuously flowed over the front surface of the baffles so as to entrain therein paint solids in the air stream, and the oil is received in a reservoir or holding tank wherein the paint solids are allowed to settle, and from which the oil is recirculated for downward flow over the baffles. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to a sheet, especially for use in the building sector, with a planar sheet body.
[0003] 2. Description of Related Art
[0004] Sheeting and film products in the most varied applications must be fastened to undersurfaces. In the building sector, this relates, for example, to sheets which are used for sealing (airtightness and watertightness) of a building shell (for example, sealing sheets, facade sheets, air and vapor barriers, underlay sheets). If there is wood or wood material in the undersurface, fastening is generally performed mechanically, for example, by tacking, nailing, screwing and/or shooting. The latter three methods are also used in undersurfaces of plasterboard, concrete, plaster and rock. Here, the sheets are perforated such that the sealing function at the perforation site is no longer maintained.
[0005] At present, the sealing function is manually restored in a complex manner by subsequent sealing by means of sealing masses, sealing strips or adhesive tapes. One special case is the sealing of nails through counter laths. This is achieved by interposed foam strips (nail sealing strips).
[0006] The aforementioned known methods constitute a major additional effort and moreover entail the risk that undetected perforations and damage will continue to cause leaks.
SUMMARY OF THE INVENTION
[0007] Therefore, the object of this invention is to avoid the disadvantages of the prior art.
[0008] In one embodiment of this invention, it is provided that the sheet body has at least one elastic layer as a sealing layer. Here, the material of the layer has an elasticity and a restoring force such that, when the elastic layer is penetrated by a fastener, the material of the elastic layer surrounding the fastener encompasses the fastener and seals in the region of the fastener.
[0009] To achieve the aforementioned object, in one alternative embodiment, it is provided in accordance with the invention that the sheet body contains a material which, in the case of a perforation of the sheet body, emerges or swells automatically out of the sheet body to close and/or seal the perforation opening.
[0010] Ultimately, this invention is a self-sealing or self-healing sheet which automatically recloses perforations or perforation openings. Here, the term “perforation” means openings of any type which arise when the sheet is fastened to the undersurface or which are due to damage. This includes perforation openings which arise during fastening, such as unintentional tears or other damage to the sheet.
[0011] Otherwise, this invention relates fundamentally to sheeting of any type as well as film products, where the sheet body is made of plastic.
[0012] The basic idea of an embodiment of the invention lies in that the elasticity and restoring properties of the material of at least one elastic layer of the sheet body is used in order either to eliminate or close minor damage of the sheet body itself or to seal on the fastener which is penetrating the sheet by corresponding elastic contact itself. In another embodiment, the approach involves the body of the sheet contains a closing or sealing material which in the unperforated state of the sheet remains in the sheet body and is inactive. When the sheet body is perforated/damaged and especially when water and/or air enters, automatic activity of the material arises causing the material to emerge from the sheet body at the perforation site, i.e., runs out and/or swells out, and then, contributes to closing the perforation opening, and in the best case, closes it completely.
[0013] In all alternatives, a perforation opening can mean a complete opening or also an annular opening when there is, for example, a nail or fastener in the perforation.
[0014] The effect in accordance with the invention can be achieved by the following different principles:
1. Use of Adhesive-Containing Microcapsules in the Sheet.
[0015] When a fastener penetrates into the sheet, the capsules are destroyed, the adhesive emerges and seals the site. In this case, different alternatives are possible:
[0016] a) The microcapsules contain a single-component adhesive. It sets physically or chemically. Preferably, reaction partners in chemical setting are (penetrating) water, oxygen and/or reactive groups of the surrounding matrix material.
[0017] b) The microcapsules contain a binary adhesive. The reaction partners react with one another only after release.
[0018] c) The contents of the microcapsules react with the material (for example, steel) of the fastener (for example, nails) and form a sealing mass.
[0019] d) Two different types of microcapsules are used which contain different reaction partners (for example, resin and curing agent). When the fastener is inserted both types of capsules are destroyed, the reaction partners emerge, react with one another and seal.
[0020] e) Use of split microcapsules, for example, a core with a first material (resin) and a shell with a second material (curing agent).
2. Use of Flowing Sealants in Microcapsules.
[0021] When the fasteners are inserted, the capsules are destroyed, the sealant flows out and seals the site. Depending on the sealant the following processes can arise:
[0022] a) The solvent evaporates, the sealing mass becomes hard.
[0023] b) A dispersion is present, the liquid evaporating. Then, the viscosity of the sealing mass rises.
[0024] c) There is a swollen and thus easily flowable rubber. The swelling agent evaporates or is taken up and drawn off by the underlay sheet material.
3. Swelling Material in the Microcapsules.
[0025] When water enters, the material emerging from the capsules swells up and seals. In doing so, the diameter of the original perforation opening is narrowed, and in the best case, completely closed.
4. Incorporation of at Least One Flowing (Intermediate) Layer.
[0026] When the sheet is perforated/damaged the flowing resin emerges from the inner intermediate layer and flows together at the corresponding site and seals.
5. Incorporation of at Least One Swelling (Intermediate) Layer.
[0027] When the sheet is perforated/damaged, water enters and leads to swelling of the inner intermediate layer, and thus, to sealing. In doing so, the effect is the same as in alternative number 3.
6. Use of an Elastic Layer as Sealing Layer.
[0028] When a fastener (for example, a nail) is inserted, a layer of an elastic layer material surrounds the fastener, presses radially against it and seals in the region of the fastener. In conjunction with the elastic layer as the sealing layer, there are, among others, the following possibilities:
[0029] a) The sheet is formed of a multilayer composite of individual function layers. The sealing layer is made preferably of an elastomer. In this connection, both conventional and also thermoplastic elastomers are possible for use as the layer material. During elongation or under pressure, elastomers briefly change their shape, and after stress, return to their original shape. This effect is used for permanent sealing between the sealing layer and the perforation medium.
[0030] b) The sheet as the sealing layer has at least one layer of a closed-cell elastic foam. Here, the restoring force of the elastic material is also used. It is even possible to combine several function layers in only one single layer.
[0031] c) A layer of a viscoelastic gel is used as the sealing layer.
[0032] It is pointed out, first of all, that the aforementioned alternatives can each be used by itself or also in any combination with one another. Thus, for example, microcapsules according to alternative 1 can be provided in conjunction with a flowing intermediate layer according to alternative 4 and/or a supplementary elastic layer according to alternative 6. However, this is only one example of the possible layer structures.
[0033] In conjunction with the alternatives of an elastic layer as a sealing layer in accordance with the invention as mentioned under 6a) the following features by themselves or in any combination acquire importance:
There is a multilayer composite of the sealing layer and at least one other layer, especially of at least one membrane and/or at least one mechanical protective layer. The membrane has the function of a water vapor-permeable film or foam film, made preferably of thermoplastic elastomers such as thermoplastic polyurethanes (TPE-U) or thermoplastic polyester elastomer (TPE-E), thermoplastic polymers, such as, for example, polypropylene (PP), cellophane (cellulose film) or a water vapor-permeable coating, for example, based on polyurethane or acrylate or another water vapor-permeable layer of another type. The layer thickness of the membrane is between 10 μm and 1000 μm, any individual value and any intermediate interval being fundamentally possible even if this is not specifically mentioned. The layer composite, i.e., the sheet, as such, ensures watertightness and is made such that it withstands a hydrostatic water pressure of greater than 100 mm, preferably greater than 200 mm, furthermore preferably, greater than 1000 mm and even more preferably greater than 1500 mm. Here, any individual value within the indicated ranges is also possible. The sealing layer is designed for sealing to the perforation medium which is, for example, a nail. The sealing layer made preferably of elastic materials, such a films, foams, nonwovens, knits or woven fabrics. The material of the sealing layer is especially conventional and thermoplastic elastomers.
[0041] Among conventional elastomers are all types of synthetic and natural rubbers which can be irreversibly chemically crosslinked. The crosslinking takes place, for example, by vulcanization with sulfur, by means of peroxides or metal oxides. Examples for conventional elastomers are natural rubber (NR), acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR) and ethylene-propylene-diene rubber (EPDM).
[0042] Thermoplastic elastomers (TPE) are elastomers which are reversibly chemically crosslinked. At room temperature they show behavior similar to conventional elastomers. At elevated temperatures the physical crosslinking is cancelled so that these elastomers show a typical processing behavior of thermoplastics. Thermoplastic elastomers include elastomer alloys/polymer blends having polyolefins and uncrosslinked or partially crosslinked types of rubber (TPE-V, TPE-O) and also multiblock polymers (TPE-E, TPE-A, TPE-U, TPE-S).
Materials of the sealing layer are especially thermoplastic polymers such as PE, PP, PET, EVA, PA in crosslinked or uncrosslinked form, thermoplastic elastomers (TPE) such as for example, TPE-U, TPE-S, TPE-A, TPE-O or TPE-E, elastomers such as EPDM or natural rubber. The weight per unit of area of the sealing layer is between 10 and 3000 g/m 2 , preferably between 50 and 500 g/m 2 , any individual value and any intermediate interval within the indicated range boundaries being possible. The layer thickness of the sealing layer is between 10 μm and 3000 μm, any individual value and any intermediate interval within the range boundaries being possible. The layer thickness is conventionally greater than 50 μm, preferably greater than 150 μm, and more preferably is between 250 to 800 μm. The modulus of elasticity of the material of the sealing layer is between 0.001 and 20 kN/mm 2 , preferably between 0.005 and 1 kN/mm 2 , in this case, any individual value and any intermediate interval within the range boundaries also being possible. The restoring force of the material of the sealing layer is in the range between 1 and 2000 N/5 cm, preferably, between 20 and 500 N/5 cm, here, any individual value within the range boundaries being possible. Depending on the material and layer thickness, the elastomer layer can, fundamentally be open to diffusion or closed to diffusion. Thermoplastic elastomers such as representatives of the elastomer types TPE-E, TPE-A and TPE-U are already open to diffusion in films of a certain thickness, i.e., they have a watertight but water-vapor permeable nature. In other elastomer types such as conventional elastomers and some representatives of thermoplastic elastomers (TPE-O, TPE-V and TPE-S) or in the case of insufficient vapor diffusion, for example, due to the layer thickness, the diffusion-open property can be ensured by an additional planar perforation. This can take place in particular by mechanical or electrostatic perforation, by heat perforation, laser perforation and/or water jet perforation and/or punching of the film. The mechanical perforation or punching takes place for example, by needle materials, roll materials, plate or sheet materials and can thus have different hole shapes. The sealing layer or the material of the sealing layer has a water vapor permeability (WDD) between 10 and 10,000 g/m 2 d. Here, any individual value and any intermediate interval within the range boundaries are also possible. The material of the sealing layer can by nature have an open-pore character (intrinsic) and can be made, for example, as a nonwoven, woven fabric or knit. Alternatively, an open surface portion can be generated by punching or needle perforation. The portion of the open surface in the total area can be between 2% and 85%, preferably, between 10% and 60%. In this case, any individual value and any intermediate interval within the range boundaries are also possible. It is decisive that the diameter of the hole of the perforation or the mesh width of the woven fabric/knit/nonwoven be below the diameter of the perforation medium. The diameter of the hole of the perforation or the mesh width should be between 10 mm and 4 mm, preferably, less than 2 mm, and especially, in the range from 0.1 to 2.0 mm, here also, any individual value and any intermediate interval within the range boundaries being possible. In order to achieve an optimum sealing effect, the diameter of the holes of the perforations should, preferably, be less than 90% of the diameter of the fastener, preferably less than 75%, and more preferably, in the range less than 50%. In order to guarantee watertightness in an elastic layer with a large-pore perforation, additional backing/coating with a diffusion-open layer can be done. Other backings or coatings, for example, with layers of nonwovens, can contribute to planar stability of shape of the film. Furthermore, there is at least one mechanical protective layer which is designed mainly to protect the membrane against mechanical damage, such as for example, by wood splinters during perforation by nailing or screwing. Preferably, there are two protective layers which are located on the outer side, and thus, also the elastic sealing layer is protected against unnecessary mechanical damage. The mechanical protective layer can be made of nonwoven fabrics, woven fabrics, knits, films and/or open-cell or closed-cell foamed films. Materials for the mechanical protective layer can be thermoplastic polymers such as, for example, PE, PP, PET, EVA, PA in crosslinked or uncrosslinked form, thermoplastic elastomers such as for example, TPE-U, TPE-S, TPE-A, TPE-O or TPE-E, elastomers such as ethylene propylene diene monomer (EPDM) or natural rubber, but also natural or semi-synthetic materials, such as, for example, cotton, hemp, jute or viscose. Materials as blends of the aforementioned materials are also possible. The density of the material of the protective layer is between 1 and 2200 kg/m 3 , preferably between 5 and 500 kg/m 3 , any individual value and any intermediate interval within the range boundaries also being possible here. The layer thickness of the mechanical protective layer is between 30 μm and 3000 μm, any individual value and any intermediate interval within the range boundaries also being possible here. The weight per unit of area of the mechanical protective layer is between 10 and 1000 g/m 2 , preferably between 50 and 500 g/m 2 , with any individual value and any intermediate interval within the range boundaries also being possible here. It goes without saying that the protective layer must be water vapor-permeable when the sheet, therefore the composite, is used as a water vapor-permeable underlay sheet. In this case, the water vapor permeability (WDD) should be between 10 and 3000 g/m 2 d, preferably, between 100 to 1500 g/m 2 d, with any individual value and any intermediate interval within the range boundaries being possible. The individual layers of the multilayer composite, which is preferably provided in the sequence protective layer-membrane-sealing layer-protective layer, are joined by bonding, cement backing, extrusion coating or dispersion coating. Combinations of the methods are also easily possible. Thus, for example, adjacent layers can first be connected to one another by a certain method, and then, other layers can be connected to the pertinent prelaminate via another method. The technique of joining the layers must be matched to the application. If the sheet is being used as a water vapor-permeable composite, the joining of the layers should not, at least largely should not, adversely affect the water vapor permeability. The water vapor permeability of the multilayer composite should be between 10 and 3000 g/m 2 d, preferably, between 100 to 1500 g/m 2 d, with any individual value and any intermediate interval within the range boundaries being possible.
[0065] In the alternative named under 6b), the sealing layer is made in the form of a foam layer of a closed-cell elastic foam. The following features by themselves or in combination can also be implemented in conjunction with other aforementioned features:
The foam layer can be part of a multilayer composite, as has been described above. Reference is made expressly hereto. However, it is also fundamentally possible for several function layers to be combined in the foam layer. Thus, for example, a foamed TPE-U or TPE-E or even other layers can at the same time assume the function of the mechanical protective layer and/or the membrane and/or one or even several sealing layers. The material of the sealing layer is preferably a polymer foam layer which forms the seal to the fastener or the perforation means when the sheet is perforated/damaged. The polymer foam can consist of thermoplastic elastomers or blends, preferably of water vapor-permeable TPE-U or TPE-E which are foamed with chemical or physical propellants or by gases such as air, nitrogen, and/or carbon dioxide. The density of the material of the foam layer is between 1 and 2200 kg/m 3 , preferably between 5 and 500 kg/m 3 , with any individual value and any intermediate interval within the range boundaries being possible. The layer thickness of the material of the sealing layer is between 30 μm and 5000 μm, any individual value and any intermediate interval within the range boundaries being possible. The weight per unit of area of the foam layer is between 10 and 1000 g/m 2 , preferably between 50 and 500 g/m 2 , with any individual value and any intermediate interval within the range boundaries being possible. The water vapor permeability (WDD) is between 10 and 3000 g/m 2 d, preferably between 100 to 1500 g/m 2 d, with any individual value within the range boundaries being possible. The modulus of elasticity of the material of the sealing layer is between 0.01 and 20 kN/mm 2 , preferably between 0.05 and 1 kN/mm 2 , here any individual value and any intermediate interval within the range boundaries also being possible. In the implementation of a foamed elastomer layer, a perforation as mentioned above is otherwise possible. Here, the cell or pore diameter of the foam material should be smaller than the expected hole diameter due to the fastener. Preferably, alternatively, open-pore elastomer foam can be used, and thus, an additional perforation can be omitted.
[0076] In the embodiment described under 6c) the use of a viscoelastic gel as an elastic layer or sealing layer is provided. When the sheet is perforated or damaged, the flexible and highly elastic gel is displaced into the surface. In contrast to purely viscous media as described in the embodiment according to number 2, or a purely elastic layer, i.e., the use of an ideal elastomer, viscoelastic materials cover the transition region in which the properties of the two materials apply.
[0077] Even if an intermediate layer of a viscoelastic gel is not an ideal elastomer, it is still subsumed under the term “elastic layer”.
[0078] Due to their stability of shape, viscoelastic materials, such as gels, try to return to the initial shape and compared to pure elastomers thus provide for an additional flowing seal to the fastener or the perforation means. In this way, the viscoelastic gel has self-adhesive properties, and thus, provides for a further bond to the fastener/perforation means.
[0079] In conjunction with the use of a sealing layer of a viscoelastic material, the following features for themselves or in any combination with the aforementioned features of the other alternatives can also be used with one another:
Fundamentally, the sealing layer of a viscoelastic gel can be integrated in a multilayer composite according to alternative 6a), the layer of elastic material, as such, then being replaced by the gel layer. Reference is made expressly to the above described features. The viscoelastic gel for the sealing layer can also be binary or single-component polyurethane systems, silicone gels or PMMA-based gels. Instead of the aforementioned layer composites, the viscoelastic intermediate layer can also be combined with one or more (carrier) layers in order to increase stability. The carrier layers can be films, nonwovens, woven fabric, knits of materials such as thermoplastic polymers, for example, PE, PP, PES, EVA or the like. The gel film can be applied to a carrier, for example, by spraying, doctoring or rolling. The degree of hardness of the viscoelastic gel is in the range of Shore A 15 to Shore A 30, any individual value and any intermediate interval within the range boundaries being possible. The application weight of viscoelastic gel in the sealing layer is between 50 and 1000 g/m 2 , preferably, in the range between 100 and 400 g/m 2 , with any individual value and any intermediate interval within the interval limits being possible. To reduce the weight of the gel layer, fillers whose weight is less than that of the gel, such as, for example, hollow microspheres, can be used, or loading with air or other gases can be performed. The water vapor permeability of the gel layer, when the layer composite is to be completely permeable to water vapor, is between 10 and 3000 g/m 2 d, preferably, between 100 and 1500 g/m 2 d, any individual value and any intermediate interval within the range boundaries being possible. Fundamentally, the self-adhesive nature of the gel can also be used to cement the film sheets among other another. Thus, in the region of the edge of the sheet above the gel layer, the outer protective/carrier layer can be shortened on the side of the longitudinal edge so that a longitudinally running outer edge strip of the gel layer arises which is preferably covered by means of a protective film, for example, in the form of a polyurethane film or a polyurethane-enamel system. The protective film is removed for installation so that, on the edge side, the self-adhesive surface appears over which the following sheet can be cemented.
[0090] In this connection, it is fundamentally possible, on the opposing longitudinal edge, on the same or the other side of the sheet, to provide a corresponding formation in which the gel layer except for the protective film is likewise exposed on the edge side.
[0091] In all embodiments of the alternatives according to number 6, preferably, the following is provided by itself or in combination with one another or other of the aforementioned features:
The characteristic for the amount of sealing (MDA) of the sealing layer computed from the product of the restoring force F r [N/5 cm] and the thickness of the sealing layer d [μm] according to the following formula
[0000]
MDA=F
r
×D
[0000] is between 3 N/5 cm×μm and 10000 kN/5 cm×μm, and preferably, between 10 N/5 cm×μm and 5000 kN/5 cm×μm and especially between 50 N/5 cm×μm to 2000 N/5 cm×μm, with any individual value within the indicated value range being possible.
Preferably, the restoring force of the sealing layer should be in the range between 0.1 and 2000 N/5 cm, preferably, between 20 and 500 N/5 cm, with any individual value and any intermediate interval within the range boundaries being possible.
[0094] Furthermore, it is pointed out that, especially for alternatives 1 to 3, it is also possible to use corresponding unencapsulated material particles instead of microcapsules. In this connection, it should then be provided that these particles are embedded into the matrix of the sheet body, therefore are not freely accessible on the outside. Accessibility, and thus, the possibility of a reaction arise only in the case of a perforation. In this case, then, the reaction partners can be air or water. Therefore, it is also important that the microparticles, which preferably are made of a solid material in the unperforated state of the sheet, are completely incorporated into the sheet matrix and are not accessible on the outside.
[0095] In conjunction with the layers according to alternatives 4 and 5, it is pointed out that it is fundamentally possible, according to the execution of the microcapsules with different reaction partners, to provide two inner reaction layers which are then separated from one another via a separating layer. In the case of a perforation or damage to the sheet, the reaction partners of the individual layers, which have been separated beforehand via the separating layer, become joined to one another so that the above described reaction can occur.
[0096] Otherwise, it goes without saying that the above described sealing function layers, regardless of whether they are made as an intermediate layer or contain microcapsules or microparticles, can be combined with any other layers. The sheet body can therefore be easily built up from a multilayer material.
[0097] The chemical basis of the microencapsulated adhesives (core materials) is, for example, acrylates, polyesters, epoxy resins or polyurethanes.
[0098] A dedicated choice of the wall material, the core material and the method for microencapsulation can influence the desired properties of the microcapsules, such as the capsule diameter and wall thickness. Wall material and wall thickness are important characteristics for the mechanical, thermal and chemical stability. They also determine whether the core material is continuously or preferably suddenly released and dictate the storage stability of the material.
[0099] Thus, depending on the encapsulation technique which has been used, capsule diameters between 0.1 and 300 μm, preferably between 1 to 100 μm and especially between 10 and 50 μm can be used. Fundamentally, typical wall materials, such as, for example, amino resins, polyamides, polyurethanes, polyureas, polyacrylonitrile or gelatins are available.
[0100] The method used for producing sheets, such as extrusion, casting, coating or fiber spinning must be matched to the size and the stability of the microcapsules or particles, so that a premature release of the core material by excess mechanical, thermal or chemical stress in the sheet production process is avoided.
[0101] Furthermore, it must be considered that the concentration of the capsules (average number of capsules per unit of area) is chosen such that, in the case of diffusion-open sheets, the diffusion capacity of the sheet in the required magnitude is maintained.
[0102] Ageing of the sheet under the conditions which correspond to the application should not lead to damaging of the wall material of the capsules, and thus, to a planar distribution of the adhesive and to an associated general adverse effect on the diffusion capacity of the sheet.
[0103] Locally destroying the capsules and achieving the accessibility of the embedded parts or layers should only take place by relatively high mechanical pressure, for example, by perforation and damage as a result of nailing-through.
[0104] The adhesive which is released from the damaged capsules after the curing process establishes a water-impermeable bond to the perforation medium.
[0105] Swellable materials are preferably polymers of acrylic acid/acrylic salts (superabsorbers) and/or bentonites. However, polyurethanes, polyether esters, polyether block amides, polyacrylic acid esters, ionomers and/or polyamides with corresponding water absorption are also suitable.
[0106] The water absorption of the swellable materials at 23° C. in water when using superabsorbers and bentonites is between 10-1000 times. The water absorption for other polymers, especially for intermediate layers, is between 1 and 30%, preferably, between 3 and 15%, and more preferably, between 5 and 10%.
[0107] In one special case, the microcapsules are worked into a polymer (homopolymers or copolymers of polyethylene, polypropylene or polyester), this mixture is extruded and then stretched. In doing so, a microporous, diffusion-open membrane (breathable film) with self-sealing properties is formed. Some of the microcapsules can be replaced by conventional fillers such as chalk, talc, marble, limestone, titanium oxide or quartz powder.
[0108] The weights per unit of area of the sealing function layers or of the microcapsules/particles for an at least essentially uniform distribution over the surface of the sheet or in the diffusion-open case are between 5 to 150 g/m 2 , preferably, 10 to 100 g/m 2 , and more preferably, 20 to 80 g/m 2 . The respective weight per unit of area can depend especially on the respective application. Conversely the total weight per unit of area, i.e., the weight of the matrix material of the sheet body including the weight per unit of area of the sealing function layer/microcapsules/particles in the diffusion-closed case is between 30 to 1000 g/m 2 , preferably, 50 to 500 g/m 2 and more preferably 100 to 300 g/m 2 .
[0109] The concentration of the capsules/particles is between 5 to 70%, preferably, 10 to 50% and furthermore 20 to 30%. The aforementioned percentages can relate especially to the volume (% by volume) and also the weight (% by weight).
[0110] The sheet in accordance with the invention can be both open to diffusion and also closed to diffusion. For sheets open to diffusion, the sd value is in the range between 0.01 to 0.5 m, preferably, between 0.01 to 0.3 m, and furthermore, 0.02 to 0.15 m. In the diffusion-closed version, the sd value is between 0.5 to 1000 m, preferably, between 2 to 200 m.
[0111] In conjunction with this invention, it has otherwise been ascertained that the watertightness of the sheet in accordance with the invention after perforation with a nail or a screw is such that there is a tightness for a static water column>200 mm, preferably >500 mm, especially preferably >1000 mm, and furthermore, preferably, >1500 mm. Depending on the type and amount of the function material, the ratio of the watertightness of the sheet in accordance with the invention after perforation to the undamaged sheet is greater than 50%, preferably, greater than 70% and more preferably, greater than 90%. Ultimately, the invention can ensure almost a watertightness as in an undamaged sheet.
[0112] The sheets or strips of all alternatives outfitted, in this way, preferably, are used in the sealing of buildings, especially in the diffusion-open version, as an underlay sheet or as a facade sheet.
[0113] The diffusion-closed sheets are used as vapor brakes, vapor barriers, gas barriers (for example, against radon, methane), masonry barriers and vertical (walls) and horizontal seals (floors, flat roofs).
[0114] It is expressly pointed out that all of the aforementioned range data comprise all individual values and all intermediate vales within the indicated range limits, even if they are not given in particular. All unnamed individual values and intermediate ranges are regarded as critical to the invention.
[0115] Exemplary embodiments of the invention are described below. All described and/or illustrated features by themselves or in any combination form the subject matter of this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0116] FIG. 1 is a schematic depiction of a first embodiment of a sheet in accordance with the invention,
[0117] FIG. 2 is a schematic depiction of a second embodiment of a sheet in accordance with the invention,
[0118] FIG. 3 is a schematic depiction of a microcapsule,
[0119] FIG. 4 is a schematic depiction of a third embodiment of a sheet in accordance with the invention,
[0120] FIG. 5 is a schematic depiction of a fourth embodiment of a sheet in accordance with the invention,
[0121] FIG. 6 is a schematic depiction of a fifth embodiment of a sheet in accordance with the invention,
[0122] FIG. 7 is a schematic depiction of a sixth embodiment of a sheet in accordance with the invention,
[0123] FIG. 8 is a schematic depiction of the sheet from FIG. 1 in the perforated state,
[0124] FIG. 9 is a schematic depiction of the sheet from FIG. 1 with a counter lath in place in the perforated state,
[0125] FIG. 10 is a schematic depiction of the sheet from FIG. 6 in the perforated state,
[0126] FIG. 11 is a schematic depiction of a seventh embodiment of a sheet in accordance with the invention without fasteners,
[0127] FIG. 12 is a schematic depiction of the sheet from FIG. 11 with fasteners,
[0128] FIG. 13 is a schematic depiction of an eighth embodiment of a sheet in accordance with the invention,
[0129] FIG. 14 is a top view of the sheet from FIG. 13 , with the uppermost layer removed,
[0130] FIG. 15 is a schematic cross sectional view of another embodiment of a sheet in accordance with the invention and
[0131] FIG. 16 is a perspective partial view of another embodiment of a sheet in accordance with the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0132] FIGS. 1 & 2 as well as FIGS. 4 to 10 each show a respective embodiment of sheets 1 which are intended for use in the building sector. The sheets 1 can be, for example, sealing or facade sheets, air barriers and vapor barriers. Depending on the application, the sheets 1 can be open to diffusion or closed to diffusion. Here, the term “sheet” also includes strips or film products. In any case, the sheet 1 has a planar sheet body 2 which has an extrudable or castable plastic as a matrix material. Conventionally, the sheet body 2 has an elongated shape and is wound up when not in use for handling purposes. The length of the sheet body 2 , the width and the thickness are dependent on the application. Conventional thicknesses of the sheet body 2 are between 100 and 300 μm, and the thickness range can vary fundamentally between 50 μm and 2000 μm, any individual values between the aforementioned range limits being fundamentally possible.
[0133] In all embodiments, it is such that the sheet body 2 contains a material which is inactivate when not in use and which can be activated, and which, in the case of a perforation of the sheet body 2 , emerges from the sheet body 2 , and in doing so, is intended for closing or for sealing the perforation opening.
[0134] FIGS. 1 & 2 as well as FIGS. 4 to 7 show different embodiments of sheets 1 . In the embodiment as shown in FIG. 1 , in the matrix material of the sheet body 2 there are microcapsules 3 which contain a single-component adhesive. When the sheet body 2 is perforated by a fastener 4 , for example, in the form of a nail, the microcapsules 3 , which are located in the region of the perforation, are destroyed. In doing so, the adhesive emerges from the capsules 3 . Then, the adhesive can set physically or chemically. Reaction partners can be, for example, water which is penetrating from the outside, oxygen and/or reactive groups of the surrounding matrix material. Ultimately, a seal 5 ( FIGS. 8-10 ) is formed by the adhesive being released in the region of the perforation opening between the fastener 4 and the matrix material of the sheet body 2 ; the seal 5 seals the annular perforation opening between the fastener 4 and the surrounding matrix material of the sheet body 2 . In doing so, it can also be otherwise provided that the adhesive of the microcapsules 3 reacts with the material of the fastener 4 so that seal 5 occurs in that way.
[0135] In the embodiment according to FIG. 2 , there are two different types of microcapsules 3 which are identified here as light and dark. The two types of microcapsules 3 contain different reaction partners. When a fastener 4 is inserted, the microcapsules 3 are destroyed and the reaction partners emerge. In doing so, then, there is a reaction forming corresponding seal 5 , as is shown in FIG. 8 .
[0136] FIG. 3 schematically shows a microcapsule 3 . It has a core 6 of a first material and a shell 7 of a second material. The first material can be a resin, the second material a curing agent.
[0137] FIG. 4 shows an embodiment in which, instead of using microcapsules, solid particles 8 are embedded into the matrix material of the sheet body 2 . The particles 8 are a comparatively solid or grainy material. Since the particles 8 react when air and/or water enters, they are not located on the outside of the sheet body 2 , but in the middle region so that an unintentional reaction is precluded. A reaction takes place only when the sheet 1 is perforated.
[0138] FIG. 5 shows an alternative embodiment in which there are different particles 8 which are, likewise, embedded in the middle region of the matrix material of the sheet body 2 . The different particles are identified as light and dark. A reaction of the particles 8 of the different materials takes place only when air and/or water enters; this occurs only when the sheet 1 is perforated.
[0139] FIG. 6 shows an embodiment in which the sheet body 2 is built up in layers. Here, there are three layers, specifically an upper layer 9 , an intermediate layer 10 and a lower layer 11 . The sealing/swelling material is located in the inner intermediate layer 10 . The intermediate layer 10 can have a layer thickness between 0.1 to 300 μm, preferably between 1 to 100 μm and especially between 10 and 50 μm. When the sheet 1 is perforated by a fastener 4 , as is shown in FIG. 10 , the material of the intermediate layer 10 emerges in the region of the perforation opening, and in doing so, fills the region between the fastener 4 and the surrounding matrix material of the sheet body 2 so that a seal 5 is formed there, as is shown in FIG. 10 .
[0140] FIG. 7 shows an embodiment in which the sheet body 2 is made with five layers. Here the reactive intermediate layer 10 is composed of two reaction layers 12 , 13 and one separating layer 14 which is provided between the reaction layers 12 , 13 and which separates them. When the sheet body 2 is perforated the separating layer 14 is also perforated so that the materials of the reaction layers 12 , 13 react with one another and can assume their self-sealing or self-healing function in the region of the perforation opening.
[0141] FIG. 9 shows a situation as often occurs in the roof region. Wood 15 , for example, a counter lath which is connected to the undersurface via a fastener 4 , is placed on the sheet 1 . The fastener 4 goes through the wood 15 and the sheet 1 . In doing so, then, the effect of seal 5 shown in FIG. 8 arises via the material of the microcapsules 3 which has been destroyed during the perforation, the sealing 5 taking place between the fastener 4 and the surrounding matrix material of the sheet body 2 and in the region of the wood 15 .
[0142] In all embodiments, it is otherwise such that the microcapsules 3 /microparticles are distributed at least essentially uniformly over the base surface of the sheet body 2 . On the edge side, there should be no access to the capsules 3 /particles or exposure.
[0143] FIG. 11 shows one embodiment of a sheet 1 which has an intermediate layer 10 of a swelling material. The sheet body 2 is perforated, therefore has a perforation 16 . Air and/or water travels through the perforation 16 to the swelling material of the intermediate layer 10 so that this material swells into the perforation 16 and reduces the free diameter of the perforation relative to the diameter in the upper layer 9 or the lower layer 11 . The swelling of the material therefore provides for a narrowing of the cross section of the perforation which can even proceed so far that the perforation 16 in the region of the intermediate layer 10 is completely closed.
[0144] FIG. 12 shows an exemplary embodiment in which the fastener 4 is located in the perforation 16 . The material of the intermediate layer 10 has expanded in the region of the perforation opening or of the fastener 4 and presses against the fastener 4 which penetrates the sheet body 2 . In the region of the perforation 16 , the intermediate layer 10 thickens due to the swelling of the material in the intermediate layer 10 .
[0145] FIGS. 13 and 14 show another embodiment of the sheet 1 in accordance with the invention. The sheet body 2 here has an elastic layer as the sealing layer 17 which is provided with a plurality of through openings 18 . The diameter of the through openings 18 is smaller than the diameter of the fastener 4 . Since the through openings 18 have relatively large pores, the sheet body 2 has an upper layer 9 which is open to diffusion but which can also be closed to diffusion. Moreover, there is a lower layer 11 which can be, for example, a nonwoven layer which contributes to the planar stability of shape of the sheet body 2 .
[0146] If the sheet 1 is penetrated by the fastener 4 , due to the elastic properties of the elastic layer material and the use of through openings 18 whose diameter is smaller than the diameter of the fastener 4 , there is sealing contact of the elastic material with the fastener 4 .
[0147] It goes without saying that, for certain applications, it is fundamentally possible for the sheet body 2 , when using an elastic or sealing layer 17 , to be made only with one layer, so that it has only the sealing layer 17 . Fundamentally, the through openings 18 can also be omitted. For diffusion-open applications, the embodiment shown in FIG. 13 should be chosen, the lower layer 11 not being unconditionally necessary as a stability or support layer.
[0148] FIG. 15 shows an embodiment of a sheet 1 in which the sheet body 2 is made as a multilayer composite. There are an upper layer 9 and a lower layer 11 each of which forms a mechanical protective layer. Between the two protective layers 9 , 11 , there are a sealing layer 17 and a membrane layer 19 .
[0149] Otherwise, sheets are also possible in which the structure of the film composite is different.
[0150] Thus, the following exemplary embodiments of sheets and their respective production which are also possible.
Film Composite 1
[0151] A silicone gel of 50 μm is applied by means of a doctor blade to a calendared PP nonwoven material with a weight per unit of area of 150 g/m 2 and is laminated with a TPE-E film 90 μm thick.
Film Composite 2
[0152] A TPE-U film of 119 μm is extruded between two viscose nonwoven materials of 120 g/m 2 weight per unit of area each.
Film Composite 3
[0153] An EPDM film which has been perforated with holes (hole diameter 2 mm, open area 70%) is extrusion-coated with a TPE-E membrane of 134 g/m 2 . Then, cement lamination onto the membrane side is done with a heat-calendered PET nonwoven material.
Film Composite 4
[0154] A perforated PP foam film 200 μm thick with an open area of 47% is extrusion coated with a TPE-E membrane of 91 μm. This composite is cement-laminated on both sides with PP nonwovens of 120 g/m 2 each.
Film Composite 5
[0155] A mixture of an adhesive and superabsorber-filled microcapsules is applied to a PP nonwoven material that is 89 μm thick and then cemented by means of a second PP nonwoven material that 67 μm thick.
[0156] FIG. 16 shows an embodiment in which the sealing layer 17 is located between an upper layer 9 and a lower layer 11 which each form carrier layers. The three-ply layer composite of the sheet 1 is shortened on at least one longitudinal edge in the region of the upper layer 9 . In the same way, the lower layer can be shortened on the opposite longitudinal edge. The sealing layer 17 is made of a viscoelastic gel which has self-adhesive properties. On the exposed edge region of the gel layer, there is a covering protective film 20 which is pulled off for installation of the sheet. The self-adhesive properties of the gel layer 17 easily enable cementing of the sheet to an adjacent sheet in the edge region. In this embodiment, the sealing layer 17 has a dual function, specifically, on the one hand, the sealing action in the case of damage/perforation, and on the other hand, the function of joining to the next sheet which is to be installed. | A sheet ( 1 ), preferably for use in the building sector, and in particular, for sealing the shell of a building, comprising a planar sheet body ( 2 ) that has at least one elastic layer as a sealing layer ( 17 ) made of a material of such elasticity and such restoring force that, when the sealing layer ( 17 ) is penetrated by a fastener ( 4 ), the material of the sealing layer ( 17 ) surrounding the fastening means ( 4 ) encloses the fastener ( 4 ) and provides sealing in the region of the fastener ( 4 ). Alternatively, the sheet body contains a sealing material which, upon perforation of the sheet body, is able to automatically emerge or swell to an extent sufficient to close or seal the perforation. | 4 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The world's coal and shale reserves often pose difficulty in harvesting the fuel components. Extraction by mining is becoming increasingly dangerous because the easy to get coals have been mined and the shales have continued to be difficult to pull organics from with any degree of economic and procedural ease. Peat and landfill seam extraction of hydrocarbons should be handled in the same manner, though their deposits are more recent than coal and shale seams. The method here proposed should make the hard to access coals and in-ground shale safe and relatively easy and economical to extract the organics contained therein. The peat and landfill, because of their softness, may pose sinking problems which can be handled post extraction making them dry landfill.
[0003] Thermally, petroleum fractions have melting points from fuel gas at between minus 162° C. and plus 30° C. to lubricating oils melting over 300° C. Paraffin and asphalt melt at higher temperatures and may not be extracted in this method. To prevent heating flash in the extraction, pure Nitrogen gas is inserted in the extraction drilling and will be the carrier for the evaporated organics.
[0004] Economically, extraction is done with all personnel at ground level and the heat and tone causing the breakdown and evaporation of the light and medium weight organics. The method requires drilling, powering the heating element, and available Liquid Nitrogen to provide cold cracking cooling and pure Nitrogen gas for extraction.
[0005] Physiologically, the coal/shale field workers will have little exposure to the coal or shale gases since they are captured at the lower segment of the drilling and pulled out via pipes leading directly to the on-site cold cracking system that separates the organics into common condensation point materials. Full containers are replaced with empties, sealed and trucked away for the heavy molecule substances and the gaseous components can be compressed into gas tanks drawing the contents from the drums. Tonal vibrations are used to unsettle the buried sediments and release the trapped organics enhancing the harvest of petroleum chemicals from both coal and shale structures.
[0006] Convection at the coal or shale levels is created by inserting narrow drillings in ring patterns around the extraction drilling where the outer ring uses the coal mine fire equipment to insert pure Nitrogen gas into the layers being extracted. The first ring provides the external Nitrogen to push the evaporated petroleum into the extraction drilling. To expand the range of the extraction, a second ring of narrow drillings is made and the pure Nitrogen is inserted there while the inner ring holes are refitted with heating units comprise of, for instance, tube boilers with heating units inside them. To concentrate the pure Nitrogen gas input the upper portion of the drilling is fitted with an air sealing sleeve to reduce soil and rock layer absorption of the Nitrogen gas. To concentrate the heat in the inner narrow drillings, the narrow drilling is insulated to retain the heat emitted in the coal or shale layers of the earth at seam depths.
[0007] The present invention relates to cryo-technology providing pure Nitrogen gas cooling for the cold cracking process and providing the wind power to activate the vibro-tonals to shake the volatile organics from their point of formation and storage to the drill location for drawing up to the surface, separating by cold cracking and collection. This will make inaccessible fuel resources available for present extraction increasing the overall active oil reserves to include previously “useless” territories. The peripheral insertion of the Nitrogen provides the inert carrier gas to transport the evaporated organics and provides fire protection preventing flash fire in the coal or shale layers.
[0008] 2. Discussion of the Related Art
[0009] Patent application Ser. No. of Denyse DuBrucq, Liquid Nitrogen Enabler, 11/706,723 section for coal mine fire control and condenser methods and Liquid Nitrogen Enabler Apparatus, Ser. No. 11/750,149 for the related apparatus. Similar methods are employed here for fire prevention, for the separator or cold cracking system, and for providing the Nitrogen carrier gas for the evaporated organics in coal, shale, peat and landfill layers.
SUMMARY OF THE INVENTION
[0010] In accordance with one aspect of the invention, the method of drilling into the coal and shale fields for extraction of fuel gas and liquid petroleum fractions. Extraction from one drilling should pull organics from an acre or hectare or more.
[0011] In another aspect of the present invention, the method includes shaking the substrate to loosen the organics from their long term entrapment allowing them to seep toward the heat source of the drilling.
[0012] In another aspect of the present invention, the method applies a contained heat source to the coal or shale layers heating them to evaporate the organic gases trapped in the underground. To safely carry these organic gases to the surface, the pure Nitrogen gas used in blowing the organ pipes mixes with and carries the organics from the depth of the drilling to the ground surface
[0013] In accordance with another aspect of the present invention, the method of using pure Nitrogen gas as the carrier prevents fires because it lowers Oxygen levels in the gas mixture as it is heated to evaporation temperatures and brought to the surface.
[0014] In accordance with another aspect of the present invention, the method carries the hot gas mixture to a cold cracking system that slowly cools the gas as it moves through a tube with traps to remove the organic material that condensed in that section of the tube. Monitored temperatures and a means to move the divisions between condensation temperatures results in quite pure distillates to be carried from the mine site to market. As the remaining gases have boiling points at room temperature and below, the cold of the condenser for Liquid Nitrogen pulls them down as liquids and, once through the trap, they evaporate and are collected in gas drums. The remaining Nitrogen and Rare Gas mixture allows vertical passage of Hydrogen, Helium and Neon and capture in Mylar balloons for separation later. The Nitrogen release location has a mixing fan to insure the Nitrogen does not remain pure in clouds, rather mixes it to near 78% of atmospheric gases which is the portion of air it occupies.
[0015] In accordance with another aspect of the present invention, the fractions of the extracted petroleum materials are separately collected and marketed as partially refined organics increasing the price levels of the unrefined extractions.
[0016] In accordance with another aspect of the present invention, this method expands the field of extraction by drilling narrow peripheral holes to apply Liquid Nitrogen as used in putting out coal mine fires. This provides pressure to fill the porous coal and shale layers with Nitrogen gas which carries the evaporants to the extraction drilling. The Nitrogen flooding also reduces the opportunity for fires or flashes during extraction.
[0017] In accordance with another aspect of the present invention, once the extraction is exhausted in the space served by the first ring of narrow drillings, another ring of narrow drillings away from the extraction hole are made and these holes provide the Liquid Nitrogen application as did the first narrow holes drilled. The first narrow holes are then converted to supplemental heating locations having narrow boilers inserted in the holes at the coal and shale depths and the top of the holes sealed with thermal insulation.
[0018] In accordance with another aspect of the present invention, the field of extraction is expanded by drilling another ring of narrow drillings where Liquid Nitrogen is inserted and converting the inner ring holes to auxiliary heating locations to keep the evaporants gaseous and able to be carried to the extraction drilling by the outer ring insertion of Nitrogen. This convection carriage of the desired organic material in gaseous form through the porous coal and shale is what allows this method of extraction to pull material from a large field of coal, shale, peat and landfill substrates under the ground.
[0019] In accordance with another aspect of the present invention, this method will be ecologically an improvement over current mining methods because it does not disturb the underground structure and is carried out with a small surface footprint over the coal and shale reserves and subsequent narrow drillings to expand the field of extraction.
[0020] In accordance with another aspect of the present invention, this method will allow selection of the carbon content of the extraction by the primary heat and the auxiliary heat temperature level. To extract petroleum to include fuel gas through gasoline substrates, the thermal temperature should be at 200° C. To include Kerosene as used in diesel and jet fuels, the thermal temperature must be 275° C. and heating oil, 375° C.
[0021] In accordance with another aspect of the present invention, this method will allow capture of the rare gases, helium, neon and hydrogen for later separation; provides means to separate water from the gasoline segment of the Cold Cracker processing ridding the hydrocarbons of the contamination and pulling forth clear water and purifying it by freezing the water slowly allowing it to rid itself of contaminants. Regulating the evaporation of Liquid Nitrogen between the primary output into the Cold Cracker and a secondary output into the Nitrogen pipes after the Cold Cracker keeps both the Cold Cracker segment outputs in the same range of temperatures on a continuous basis and allows the Nitrogen flow through the shaft via the organ pipes to maintain the working vibrational levels and sufficient Nitrogen carrier gas available for extracting the evaporated hydrocarbons.
[0022] These and other advantages and features of the invention will become apparent to those skilled in the art from the detailed description and the accompanying drawings. It should be understood, however, that the detailed description and accompanying drawings, while indicating preferred embodiments of the present invention, are given by way of illustration and not of limitation. Many changes and modifications may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Preferred exemplary embodiments of the invention are illustrated in the accompanying drawings in which like reference numerals represent like parts throughout, and in which:
[0024] FIG. 1 is a drawing showing the overall drill hole from the surface of the ground to the coal, shale, peat or landfill seams below with components of the heater, tonal input, Nitrogen and the extraction tube shown complete vertically, and partially above the ground surface.
[0025] FIG. 2 is a drawing showing the lower part of the drilling gauging better the distance at the bottom of the drilling where the heating of the reserve occurs making volatile organics evaporate and escape to the drilling location. The funnel catches the pressured Nitrogen and evaporants, which are drawn into a well-insulated vertical pipe, which once at the surface bends horizontally to enter the Cold Cracking system.
[0026] FIG. 3 is a drawing showing the surface equipment with a power source for the heating unit, a lever to tune one of the organ pipes. Nitrogen sourcing from a condenser which is fed with Liquid Nitrogen from a large dewar.
[0027] FIG. 4 is a drawing better defining the extraction tube Cold Cracking of the extracted organics where the segments of the evaporant condenses as the temperature lowers and the Nitrogen warms up while condensing the evaporants. The major fractions of Petroleum are drawn out of the Cracking tube with drain type trapped piping.
[0028] FIG. 5 is a drawing showing the containment of the fractions of the extracted petroleum for collection and taking to market. Also shown is the Liquid Nitrogen storage and feeding into the condenser which cools the cracking pipe and eventually supplies the organ pipes with pure Nitrogen gas.
[0029] FIG. 6 is a drawing showing the cross-sections of the condensing tube with the cold Nitrogen gas cooling the extraction tube so as to condense the organic evaporants on a thermal gradient into increasingly larger carbon chain molecules.
[0030] FIG. 7 is a drawing showing means of driving evaporants with Nitrogen gas placed in narrow drillings and instilling safety in the process by displacing Oxygen.
[0031] FIG. 8 is a drawing showing the second use of the narrow drillings, heating the extraction layer while being thermally insulated from the soil and rock over the extraction layer and the air above the drilling.
[0032] FIG. 9 is a diagram showing the first ring of narrow drillings surrounding the extraction drilling, which feed the Nitrogen gas into the system to carry the evaporated organics to the central drilling for extraction.
[0033] FIG. 10 is a diagram showing the expanded extraction field with several rings surrounding the extraction drilling where the outer ring of narrow drillings insert the Nitrogen gas into the systems and the inner rings of narrow drillings provide auxiliary heat to the coal, shale, peat or landfill layers being extracted of their selected organics based on the residual temperatures maintained during the extraction.
[0034] FIG. 11 is a drawing showing the final Cold Cracking step, capturing the rare gases by allowing these light molecular weight gases to rise into an inverted cylinder, which becomes lighter weigh as the rare gases fill the cylinder lifting it up. It is then lowered as these gases fill a mylar balloon, or other such reservoir, preserving this segment of the evaporated hydrocarbon mix from the coal, shale and peat seams.
[0035] FIG. 12 is a drawing showing the separation of water from the gasoline segment of the evaporated hydrocarbons in the Cold Cracker where the density of water is greater than that of hydrocarbons and thus settles to the bottom of an undisturbed vessel. The light gasoline is drained into a container and the water segment is siphoned out and then processed through freezing the water to gain purity from dissolved material.
[0036] FIG. 13 is a drawing showing the details of Nitrogen insertion in the system having a regulator that balances the output of Liquid Nitrogen between the condenser feeding the Nitrogen pipes going through the Cold Cracker and the auxiliary condenser feeding the Nitrogen pipes after the Cold Cracker and before entering the Shaft. This keeps both the Cold Cracker thermal segments stable and the needed flow of Nitrogen in the shaft to both produce the vibrations by passing through the organ pipes and appropriate levels to handle the carrier function for emerging evaporated hydrocarbons.
[0037] FIG. 14 details the tuning of the thermal segments of the Cold Cracker whereby one method is to have thermodetectors planted in the insulation monitoring the temperature of the extraction pipe. A partial block is placed at the desired break between the condensation temperatures that is adjustable, as a bag of iron spheres movable with external magnets to the desired location. The extraction pipe is expanded downward to drain the liquid contents of that segment of the pipe into the drain trap and container.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0038] Turning now to the drawings and initially to FIGS. 1-3 , showing the center, lower section and top of the drill hole for extracting fuel hydrocarbons from coal, shale or peat. In FIG. 1 , the coal, shale, peat or landfill seam 1 is vibrated with sound at both the frequency of the standard organ pipe 30 and the frequency difference beats created by the adjustable frequency organ pipe 31 that can vary widely with the tuning of the adjustable pipe. The purpose of this ground stimulation is to get motion throughout the seam 1 such that the heat evaporated hydrocarbons can escape the structure of the seam. The pipes 30 , 31 are blown with pure Nitrogen gas 3 which is carried into the extraction drilling 10 by Nitrogen pipes 32 , one for each organ pipe. The Nitrogen gas is sealed in the shaft 10 by seal 37 so it can act as the carrier gas for the evaporated hydrocarbons. The funnel 11 below the organ pipes catches the hydrocarbon enriched Nitrogen and draws it out of the shaft 10 enclosed in a thermally insulated pipe 12 carrying the hydrocarbon enriched Nitrogen 15 .
[0039] FIG. 2 shows the lower portion of the shaft 10 with the heat energy source 20 passing down through the funnel 11 and the heating element 2 heats the coal, shale, peat, or landfill seams 1 . The middle section of the shaft is the cool zone 44 and the lower is the hot zone 45 . Convection in the shaft 10 forces the pressure imposed Nitrogen 3 activating the organ pipes and allows it to flow to the hot zone 45 around the gaps between the funnel 11 and the walls of the shaft. Evaporants 15 from the seams 1 enter the hot zone and are taken out of the shaft via the gaseous escape pipe 12 which pulls the hot gases rising with the heat out of the shaft. The evaporants 15 in the seams 1 escape the seam as the tonal output of the organ pipes cause the seam structure to vibrate.
[0040] FIG. 3 presents the top of the shaft 10 showing the around level 4 and a spacing 42 indicating the workings of the shaft contents can be well below the surface of the around. The power source for the heater 22 is on the ground powering the heat energy source 20 which passes down to the bottom of the shaft. The tonal adjustment 36 for the adjustable tone organ pipe 31 sticks up so it can be controlled from the top of the shaft. The Nitrogen pipes 32 , one for each organ pipe 30 , 31 get their Nitrogen 3 from the condenser 33 where Liquid Nitrogen 35 is evaporated into Nitrogen gas and passes through the Cold Cracker 13 which heats the Nitrogen before entering the shaft. The gaseous escape pipe 12 comes up the shaft and passes under the Nitrogen pipes 32 .
[0041] FIG. 4 elaborates on the Cold Cracker 13 showing the gaseous escape pipe 12 coming from the shaft. The tank of Liquid Nitrogen 39 feeds Liquid Nitrogen 35 down the Liquid Nitrogen pipe 34 and into the condenser 33 which is insulated 23 throughout the Cold Cracker 13 providing cooling for the evaporated hydrocarbon/Nitrogen mix 15 coming through the gaseous escape pipe 12 . The coldest Nitrogen cools the last, low carbon chain hydrocarbons left in the gaseous escape pipe 12 . As the Nitrogen gas warms, it condenses the longer carbon chain hydrocarbons to where the longest as collected in the Cold Cracker 13 closest to the shaft 10 . To separate the Kerosene from the gasoline and petroleum ethers and fuel gases segment output pipes 14 draw the condensed hydrocarbons in sections of the pipe 12 . These liquids pass through the trap 17 and go to storage shown in FIG. 5 . The final output of the gaseous escape pipe 12 is the Nitrogen gas 3 left in the pipe which is dispersed being mixed with air by a fan 38 .
[0042] For safety and to prevent clouding of pure Nitrogen 3 , a tan 38 is employed to mix the Nitrogen with the residual air so there is no opportunity for people or animals to develop Nitrogen Asphyxiation or Nitrogen Coma, a reflex of the lungs when Oxygen is not available and Carbon dioxide cannot be exchanged in the lungs. Breathing stops, but the heart keeps pumping and one loses consciousness. There are about six minutes from when one is so stricken until he or she or an animal would die. With these Nitrogen employing methods, one should be aware of the possibility of this condition and, if finding a person down, one should think first to apply artificial respiration with a good mix of air present and, if the person recovers, all is well. If he or she does not recover, then call 911 and do the CPR-type work to recover a person from a heart attack. And if that fails, check for stroke or other difficulties. Shortly the medics will arrive.
[0043] FIG. 5 completes the Cold Cracking apparatus by having the segment output 14 and trap 17 allow the condensed liquids to flow into containers 18 if the hydrocarbon is liquid at ambient temperatures or gas drums 19 if the hydrocarbon fraction is a gas. The gas drums 19 are fed with an outsource pipeline 16 . The final separation 60 in the sequence is collection of the rare gas segment—Hydrogen, Helium and Neon—light weight gases 6 collected in an inverted container 61 and drawn off through the extraction tube 63 into a mylar balloon 64 held to the ground with a tether line 65 . It also shows the remaining gas in the gaseous escape pipe 12 . Also defined is the cold source for condensing the hydrocarbons with the tank of Liquid Nitrogen 39 feeding through a pipe 34 Liquid Nitrogen 35 into the condenser 33 which feeds its cold Nitrogen gas 3 into the Nitrogen pipes 32 that cool the gaseous escape pipe 12 as it enters the Cold Cracker 13 .
[0044] FIG. 6 defines the Cold Cracking System 13 structure with the insulated cover 23 enclosing the Nitrogen pipes 32 carrying the warming Nitrogen gas 3 to the shaft. Radiator tabs 24 transfer the cold from the Nitrogen pipes 32 to the gaseous escape pipe 12 carrying the Hydrocarbon/Nitrogen mix 15 . As the mix is cooled, first the high number carbon molecules condense and the liquid runs into the segment output 14 and through the trap 17 and into the container 18 . Viewing the containers 18 in FIG. 6A , the patterns indicate lighter and lighter condensation coming into the containers at each segment output 14 . The gas contents of the pipes defined in FIG. 6B are included but not shown in FIG. 6A . This method of separation of output at the drilling site brings high prices for the extraction process because the chemicals emerging are defined in melting point ranges. The major fractions of petroleum assumed to be included in the extractions from the drilling include from heaviest to lightest: Heating oil with boiling (condensing) points between 275-375° C.; Kerosene between 175-275° C.; Gasoline between 40-200° C.; Petroleum ether between 30-60° C.; and Fuel gas at −162-+30° C. Fortunately, Liquid Nitrogen evaporates at −195.8° C. so even the Methane Gas can be captured which condenses at −162° C.
[0045] FIG. 7 shows a method of inserting Nitrogen in the periphery of the coal, shale or peat seam 1 . One drills narrower holes, 10 centimeter diameter, maximum, around the periphery of the drill site. These allow one to add Nitrogen 3 to the mix by putting in the Liquid Nitrogen Enabler coal mine fire fighting equipment 5 including a four liter dewar 50 with an apparatus for slow flow from the dewar 51 which fills a dump bucket 52 with Liquid Nitrogen which, when full, dumps the Liquid Nitrogen 35 into the sieve with spaced small holes 53 which separates the Liquid Nitrogen drop into tiny droplets that evaporate rapidly as they fall from the sieve. The cold Nitrogen gas 3 flows to the bottom of the drilling and seeps into seam 1 so it carries the evaporated hydrocarbons 15 into the evacuation drilling or shaft 10 shown in FIGS. 1-3 . When the dewars 50 are taken for filling, the drilling hole top is sealed with a bowling ball. A plastic sleeve 37 is inserted down the drilling covering the walls above the coal, shale, or peat seams. When the dewars are in place, they seal the top of the hole as well preventing the Nitrogen from flowing out of the narrow drill hole and insuring that it seeps into the porous seam structure to carry the evaporated hydrocarbons to the shaft. This operation does two things. First, it reduces the amount of Oxygen available in the hydrocarbons lowering, and hopefully eliminating, the chance of starting a coal mine fire, shale fire or peat fire. Second, it helps carry the evaporated hydrocarbons to the collection and extraction site.
[0046] FIG. 8 shows an auxiliary heating of the coal, shale or peat seam 1 . As the draw of hydrocarbons into the shaft 10 continues, the periphery of the extraction range grows. The holes that held the coal mine fire apparatus 5 can next be equipped with an auxiliary heating unit 2 . The heating unit is powered by the energy source and the wiring to the heaters 26 are shown. The hole heating unit 2 consists of the heat energy source 20 which extends the depth of the hole with its heating element 28 in a boiling can 27 that has a fluid in it 21 which boils at the temperature desired to heat the seam 1 , as, if one wanted to extract all hydrocarbons from fuel gas to heating oil, one would heat it to 275° C. and to include heating oil extraction, 375° C. The whole apparatus is lowered down the narrow drilled hole 25 and insulation 23 is placed in the hole to insure no heat loss to the surface occurs. This will help heat a larger region of the seam 1 to increase the area or space underground from which the evaporated hydrocarbons emerge. To keep the Nitrogen flow going from the peripheral regions, new holes are drilled for the coal mine fire units 5 further from the shaft 10 . As that area is exhausted, the heating units can occupy two circles of holes and a third circle of narrow drills is made for another placement of the coal mine fire units. This can continue with many circles of heating units rimmed by one circle of Nitrogen inserting coal mine fire units.
[0047] FIG. 9 shows the initial circle of coal mine fire units 5 around the shaft 10 shown from the ground surface 40 . The shaft heating unit is heating the coal, shale or peat seam 1 so close to the shaft 10 is the hot zone 45 . The Liquid Nitrogen flowing from the coal mine fire units 5 are cool so the periphery is the cool zone 44 . This schematic does not represent the true distance of sourcing the Nitrogen 3 as shown by the distance spacer 42 . The vector arrow shows the flow direction of the Nitrogen gas from the narrow drillings 25 to the shaft 10 .
[0048] FIG. 10 illustrates the expanded periphery of the draw of hydrocarbon extraction with distances larger than shown as indicated by spacers 42 where the shaft 10 is surrounded by narrow drillings 25 containing heating units 28 closest to the shaft 10 and the furthest ring containing the coal mine fire units 5 supplying Nitrogen 3 to the seams carrying the evaporated hydrocarbons to the shaft 10 for extraction. The hot zone 45 is expanded to include all the rings of heaters 28 and the cold zone 44 includes the final ring of coal mine fire units 5 . Nitrogen 3 flow is indicated by the vector arrow from the coal mine fire units 5 to the shaft 10 . This schematic also is showing the layout from the ground surface 40 .
[0049] FIG. 11 shows in FIG. 11 a a means to preserve for marketing the rare gases that emerge from the coal, shale and peat seams as the last component of the Cold Cracker 13 . The rare gas extractor 61 is comprised of an inserted elbow pipe insertion 66 placed in the Cold Cracker piping 13 which has a vertical pipe 63 to release the rare gases 6 into the inverted rare gas container 60 . As the rare gas 6 fills the inverted container 60 , it becomes lighter weight and rises on the vertical pipe 63 as shown in FIG. 11 b . Brushes 62 on the outer wall of the vertical pipe 63 keep the inverted container 60 properly vertical. To save these light gases, the rare gas extractor 61 opens and allows the rare gas 6 to flood the mylar balloon 64 , which lowers the inverted container 60 on the rare gas release tube 63 as shown in FIG. 11 c . The trigger to open the valve on the rare gas extractor 61 is the tether line 67 attaching to the inside top of the rare gas container 60 and the inner wall of the vertical pipe 63 . When the tether line 67 is tight because the rare gases have lifted the container 60 so high the line is tight, the valve opens on the extractor 61 and the rare gases enter the mylar balloon 64 . As it does the container lowers, loosening the tether line, the valve has a time delay to allow the rare gases to enter the balloon. When the top of the container 60 strikes the vertical tube 63 , the valve shuts allowing rare gases to accumulate again in the rare gas container 60 . When the balloon is filled it is held to the ground with the tether line 65 . Once the mylar balloon 64 is filled, it will be removed from the rare gas extractor, and its opening folded and sealed as is common practice in use of these balloons. The balloon 64 is kept on the tether line 65 as it is stored and carried to market. Rare gases 6 contained are hydrogen, helium and neon. Argon, another noble gas, may be captured as the final part of the Cold Cracker final gas drum since its condensing temperature is higher than that of the Liquid Nitrogen and Nitrogen gas just after evaporation will liquefy Argon so it runs through the trap and evaporates in the gas drum as shown in FIG. 5 .
[0050] FIG. 12 shows the manner the Cold Cracker separates water, boiling and condensing at 100° C., from the gasoline fraction of the hydrocarbons, condensing at between 40 and 200° C. This segment is split into two components, heavy gasoline between 200° C. and 120° C. and light gasoline between 119° C. and 40° C. which includes the water condensation. The container 18 collecting the light gasoline segment is shown with the segment output 14 attached to the gaseous escape pipe 12 in the Cold Cracker 13 with its trap 17 and container 18 is illustrated in FIG. 12 a . Details of this particular container 18 are shown in FIG. 12 b . These include a float lighter than water 71 which has spaced holes and rides between the liquid of the light gasoline 9 and the water 7 keeping the interface calm and undisturbed as the added condensed materials enter the vessel. This water/gasoline separator 70 has the float 71 defined by rounded shape with a pattern of holes 75 shown in FIG. 12 c in the vessel 18 and a siphon tube 72 draining the water 7 from the vessel into a water container 73 . When the volume of the cylinder is close to full, the light gasoline extractor 91 allows the gasoline fraction 9 to empty into the light gasoline container 93 . Not shown here are: the trigger floats noting the height of the gasoline 9 and the float 71 which properly high and spaced opens the light gasoline extractor 91 to drain some of the gasoline, and the float height that triggers the water siphon tube 72 to drain emptying some water into the water container 73 ; and the final water purifying process of slowly freezing the water in cubes and lower its temperature well below freezing such that the contaminants are eliminated from the water crystal of the ice. Surface contaminants can be removed by wiping or lifting the ice cube from its container where the rejected contaminates remain or a quick pure water rinse. This purifying process is common. In the oceans, when ice bergs form, the salt and organics in the water are eliminated from the ice crystals and left in the ocean water. Tasting ice from an ice berg and sea water just beside the ice berg will allow one to experience the difference of contamination, the ice berg being more like fresh water and the sea water, salty. FIG. 12 c defines the float 71 between the light gasoline 9 and water 7 segments which has spaced holes 75 holding the liquid relatively calm so the gasoline/water separation 76 easily reforms after condensation pours into the container 18 .
[0051] FIG. 13 shows the physical features of the regulated Liquid Nitrogen 3 flow with the regulator 8 on the tank of Liquid Nitrogen 39 feeding two Liquid Nitrogen pipes 34 , one feeding the Cold Cracker 13 condenser 33 and the other feeding the secondary Nitrogen input 80 with condenser 83 feeding Nitrogen gas into the one-way valves 82 allowing Nitrogen gas 3 to enter the Nitrogen insertion elbows 81 inserting the Nitrogen into the Nitrogen pipes 32 which, of course, drive the organ pipes and carry the evaporated hydrocarbons out of the shaft. This system keeps the thermal levels of the segments of the Cold Cracker constant because the thermostats imbedded in the Cold Cracker 13 at the segments drive the regulator to determine if any or how much Nitrogen gas should be fed into the Nitrogen pipes to keep shaft functions at needed levels when the Cold Cracker segment temperatures are kept at the determined levels to get appropriate fractions of the hydrocarbons extracted from the coal, shale or peat seam at the location of the shaft and zone surrounding which is enabled by the rings of auxiliary heaters and the outer ring forcing Nitrogen gas into the coal, shale, peat or landfill seam.
[0052] And, finally, FIG. 14 shows further definition of the condensing tube and its cooling from the Nitrogen gas lines shown in FIG. 6 where the condensing tube is expanded downward 84 to implement draining into drain tube 14 with the radiator plates 24 elongated to accommodate this expansion and keep the thermal conditions constant. FIG. 14 a shows the side view of a length of the piping and FIG. 14 b defines this drain accommodation. A vertical line shows where the cross section is taken. A second vertical line leading to FIG. 14 c shows the thermal tuning of the condensing system where the constantly round condensing pipe sections have thermodetectors 86 along the distance allowing one to tune the system at desired temperatures to define the condensing material at that interval by placing a sack of iron balls 87 at the division temperature between two condensing drains. A magnet 85 is used to move the sack of iron balls 87 to that location where the temperature in the condensation tube 12 matches the junction temperature between the two hydrocarbon groups being collected. A cutaway 88 in FIG. 14 a condensation tube 12 shows the side view of this divider 87 between drains. This method is used between the collection zones of all the hydrocarbon and noble gas groups collected by condensation. The magnets can be driven manually or by an automated process. When the manual method is used, the instrument tracking the thermodetectors can signal the thermal change in any of the junctions so the supervisor on duty can adjust the location of the sack of iron balls with the magnet. Once these dividers are placed, the thermodetectors in one section will have a common temperature among the detectors more so than without the divider. Automated, the electromagnet in that pipe segment can go on so the change of location of the sack of iron balls is made and the condensation progresses. It can be expected that there may be changes in hydrocarbon contents over time in the extracting process which will necessitate adjustments at various times, even varying as to when one segment junction needs adjusting from when another segment junction needs adjusting.
[0053] FIG. 15 is included to show where each of the extracted components from the coal, shale, peat and landfill seams are collected including: Rare Gases as Hydrogen, Helium, and Neon; Argon; Methane; Ethane; Fuel Gas; Light Gasoline and Water (separated in second stage); Heavy Gasoline. Jet Fuel; Diesel Fuel; and two sections of Heating Oil. This array of components isolated will probably be a maximum sized group of isolated elements, molecules and molecule mixtures.
[0054] This clean method of hydrocarbon extraction should allow the readily burnable parts of coal, shale and peat be extracted from underground with minimal disturbance of the site and with little chance of sinking surface structure after the extraction. It may replace surface mining as we know it, eliminate underground coal mining as we know it, and bring hydrocarbons from some situations where mining would not be practical or economical because of the difficulty of extraction of the material, as is the case presently with shale deposits.
[0055] This completes the statement of invention. | A method of extraction of fuels and elements from coal, shale, peat and landfill seams is described which cuts the earth with only a main shaft which could measure half a meter diameter and with auxiliary narrow drillings of, say 10 centimeter diameter, widely spaced from the shaft. The coal, shale or peat seam is heated to the highest temperature of the hydrocarbon fraction desired to be extracted and the evaporated hydrocarbons are carried out of the shaft by Nitrogen gas. To enhance the extraction rate of the evaporated hydrocarbons, tonal input from two or more organ pipes vibrates the seam structure freeing the evaporated hydrocarbons allowing their escape into the shaft. As the extraction continues requiring inclusion of a greater area of the seam structure, narrow drillings are made and Liquid Nitrogen is inserted in the drillings reaching seam levels as Nitrogen gas which seeps into the seam. A gas-impenetrable sleeve prevents the Nitrogen gas from seeping into the soil or substrate between the ground level and the seams. Further expansion of the field moves the Nitrogen sourcing to the outer circle and inserts auxiliary heaters in the narrow drillings between the outer ring and main shaft bringing more of the seam to the desired extraction temperature. Extracted evaporated hydrocarbons are cold cracked allowing the fractionation of hydrocarbons into fuel types as heating oil, kerosene, gasoline, ethers, and fuel gas, methane, argon and rare gas segments. The thermal gradient of the extraction pipe is implemented by sourcing the Nitrogen from Liquid Nitrogen and running the pipes bundled with the extraction pipe condensing its contents by hydrocarbon fractions in vessels and gas drums depending on boiling points of fractions. Water is separated from the gasoline segment and purified by separation and freezing. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the fields of optical and magnetooptical recording. More particularly, it relates to improvements in moving coil linear motors of the type commonly used in optical and magnetooptical recording/playback apparatus to control the focus and tracking position of an objective lens used to direct a read/write beam onto a moving recording medium, such as an optical or magnetooptical disk.
2. Discussion of the Prior Art
In the fields of optical and magneto-optical recording, as illustrated in FIG. 1, a beam of radiation B, as emitted by a diode laser L or the like, is focused on the recording layer RL of an optical or magneto-optical disk D by a lens L1. The disk is supported by a spindle S which, in turn, is rotated about its axis A by a motor M. In a data recording mode, the laser output is intensity-modulated by a controller C which responds to a signal representing data to be recorded. In a playback mode, the data recorded on the disk serves to intensity modulate the reflected laser beam. In an optical recording system, the laser output is transmitted to the disk through the combination of a polarizing beam-splitter PBS and quarter wave plate QWP. These elements cooperate in a well known manner to optically isolate the laser cavity from radiation reflected from the disk. Upon being reflected from the disk, the laser beam is divided by a beam splitter BS. One portion of the beam is focused by a lens L2 onto either of a pair of spaced photodetectors, PD1 and PD2. A mask M' blocks half of the aperture of lens L2, and the focal distance between lens L1 and the disk determines which of the two photodetectors receives the more reflected light. The respective outputs of PD1 and PD2 are processed by a focus control circuit FCC which, in turn, produces a focus error signal FES. A focus actuator or transducer T responds to the focus error signal to adjust the position of lens L1 toward or away from the disk in order to maintain proper focus. Similarly, the other portion of the beam divided by the beam splitter is focused onto a pair of photodetectord PD3 and PD4. The respective outputs of PD3 and PD4 are summed to provide the data signal RF, and the respective outputs of PD3 and PD4 are differenced by a tracking control circuit TCC to produce a tracking error signal TES representing the displacement of the beam focused on the disk relative to a desired data track. A tracking actuator or transducer T' responds to the tracking error signal to adjust the position of lens L1 in a plane parallel to the disk, thereby moving the focused beam in a radial direction on the disk in order to maintain the focused spot centered on a desired track. Optical arrangements of the type shown in FIG. 1 are well known and can be seen, for example, in the disclosure of the commonly assigned U.S. Pat. No. 4,967,404.
Moving coil linear motors are widely used today in optical and magnetooptical disk drives to control both the focus and radial (tracking) position of the objective lens L1 as described above and shown in FIG. 1. Usually, such motors are relatively tiny in order to fit into those "tight" spaces of the disk drive where "real estate" is always limited. Small as they are, these motors must develop a significant amount of force so that adequate acceleration of the moving parts or payload can be achieved. The required acceleration determines the amount of electrical power, both average and peak, which must be provided without overheating the coils. Additionaly, the design of linear motors for disk drives must be correlated with the overall structure of the mechanism so that the motor's dynamic performance does not result in resonances within the required range of operating frequencies, a requirement related to the necessity to successfully control motion of the moving parts.
In designing linear motors, specified requirements are fulfilled by choosing proper geometric parameters. Among them, most attention must be paid to coil sizing and defining the motor's magnetic structure. These two factors are especially important since their optimization results in minimization of the amount of required power which, in turn, minimizes the temperature rise of motor coils. In radial acces mechanisms of optical and magnetooptical disk drives, the position of the read/write head need only be controlled in one direction, that being along the radial direction of the disk. With a singular motor being utilized, the design optimization is carried out by solving the motor/load matching problem. For drives with symmetrical velocity profiles, an optimized motor design requires that the coil mass to be equal to the payload mass. Coil masses of motors with unsymmetrical velocity profiles must be defined depending upon the so-called normalized cycle time of the disk drive. In general terms, the same relationship between coil and payload masses can be maintained in designing lens actuators for optical disk drives. In such cases, however, the objective lens requires motions in two mutually perpendicular directions, one motion being towards and away from the disk (for focus), and the other motion being in a plane parallel to the disk (for fine tracking). The need for these two motions necessitates the use of two discrete motors. Usually, separate coils for these two motors, as being located in the same air gap, are penetrated by the magnetic flux of a common permanent magnet. Such a design is illustrated in FIG. 2 where a four-bar focus/tracking actuator is illustrated. An exploded view of the same actuator is shown in FIG. 3. As shown, an objective lens 1 is located in a lens holder 2 which is suspended by four flexible bars 3A-3D. Lens motion in either the focus (along the Z axis) or tracking (along the Y axis) directions is achieved by employing two linear motors. Both linear motors are of the moving coil type, the motor which controls the focus position of the lens comprising focus coil 4, and the motor which controls the tracking position of the lens comprising tracking coils 5 and 6. These coils are located within air gaps defined by the spaced magnetic structures 7 and 8. The four-bar focus/tracking actuator shown in FIGS. 2 and 3 is better described in the commonly assigned U.S. pat. application Ser. No. 108,031 filed on Aug. 17, 1993 in the name of Boris A. Shtipelman, the subject matter of which is hereby incorporated herein by reference.
The Technical Problem
The requirement for dual motion of the objective lens in optical and magnetooptical disk drives creates a situation in which the tracking coil mass becomes an integral part of the total payload mass of the focusing motor in providing a focussing motion of the lens. Similarly, the focus coil mass is an integral part of the total payload mass of the tracking motor in providing a tracking motion of the lens. This situation neccessitates a different approach to optimizing the two motors of a two-axis optical actuators. Such optimization of motor characteristics, when the respective masses of the focus and tracking coils are required to minimize the amount of electrical power consumed, represents the technical problem addressed by this invention.
SUMMARY OF THE INVENTION
In view of the foregoing discussion, a primary object of this invention is to provide an improved focus/tracking actuator of the type described, an actuator in which the respective masses of the moving coils are optimized in order to maximize the actuator's effectiveness (i.e. speed of response) in controlling the focus and tracking position of a lens.
Like the prior art, the focus/tracking actuator of the invention comprises a pair of moving coil type linear motors, one motor being adapted to control the focus position of a lens assembly used to focus a beam of radiation on a desired data track on a moving recording element, and the other motor being adapted to control the tracking position of such lens, and each of the linear motors comprises a coil of wire disposed in a magnetic air gap and adapted to move therein in response to an applied current flow in the coils. Unlike the prior art actuators, each of the coils of the focus/tracking actuator of the invention has a mass substantially defined by the equations:
m.sub.ocf =m.sub.l /[(1+(1/k.sup.2)·C.sub.mt /C.sub.mf)]
m.sub.oct =m.sub.l /[(1+k.sup.2 ·(C.sub.mf /C.sub.mt)]
where m ocf is the mass of the focus motor coil; m oct is the mass of the tracking motor coil; m l is the mass of the moving payload (i.e., the lens assembly and all that moves therewith, including, for example, the lens itself, the lens holder and at least a portion of the suspension used to support the lens holder for movement along two perpendicular axes); k is the ratio of the focus motor efficiency to the tracking motor efficiency; and C mf and C mt are the respective motor design parameters of the focus and tracking motors, each of said design parameters being defined by the expression, γρ/(βB) 2 , where γ is the density (kg/m 3 ) of the wire material of the coil; ρ is the resistivity of the wire material (ohm-meters); and β is the ratio between the effective and the total length of the coil wire. Preferably, the combined masses of the focus and tracking coils equals the payload mass, and the ratio of these masses is defined as
m.sub.ocf /m.sub.oct =k.sup.2 ·(C.sub.mf /C.sub.mt)
The invention and its advantages will be better understood from the ensuing detailed description of a preferred embodiment, reference being made to the accompanying drawings in which like reference characters denote like parts.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of a conventional focus/tracking actuator;
FIGS. 2 and 3 are perspective and exploded illustrations of a conventional focus/tracking actuator;
FIGS. 4-7 are a series of graphs illustrating various relationships between coil masses and motor efficiency parameters.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Apart from a number of physical characteristics such as overall sizes, structural integrity, and dynamic behavior, the most critical parameter of a focus or tracking actuator is the amount of force developed by its motor. Usually, this force is characterized by the force constant K f , which is defined as
K.sub.f =l.sub.e ·B (1)
where l e is the effective length (in meters) of wire coil located in the motor air gap, and B is the magnetic flux density (in Tesla) crossing the coil in the air gap. It should be noted that for any practical application, the magnetic flux density is not uniform throughout the air gap due to a certain amount of flux leakage. Therefore, in equation (1), it is advisable to replace B by its average value of B av .
Force constant K f is measured in Newtons per ampere and represents the motor force when 1.0 ampere of current is passing through the coil. In terms of coil mass m c and resistance R c , the force constant can be defined as ##EQU1## where C m represents a motor design parameter which characterizes the effectiveness of the magnetic structure, as well as the coil and magnet materials. This parameter has a time dimension, and it can be expressed as
C.sub.m =γ·ρ/(β·B).sup.2 (3)
where γ is the density (kg/m 3 ) of the wire material of the coil; ρ is the resistivity of the wire material (ohm-meters); and β is the ratio between the effective l e and the total l w length of the coil wire. Such a ratio may be defined as
β=l.sub.e /l.sub.w (4)
It is known that the force constant K f represents an incomplete measure of a motor's performance since, for a motor coil with the established mass and overall dimensions, the value of K f (from equations (1) and (2)) can be easily boosted when the wire length, both effective l e and total l w , is increased by choosing a wire with smaller cross section dimensions that subsequently increases coil resistance R c . A more fundamental performance measure of the motor is provided by the effectiveness parameter K ef which is not a function of wire diameter or its resistance. This parameter is measured in N/√w and can be determined in the following form:
K.sub.ef =F/√P=√m.sub.c /C.sub.m (5)
where F is motor force (in Newtons) and P is the power dissipated in the coil (in watts). Here, motor force F is a function of the current I passing through the coil, or
F=K.sub.f ·I (6)
The motor force F must be sufficient to overcome gravity and spring resistance of the suspension, and then to move the payload with a desired amount of acceleration. In other words, the value of F must exceed, or at least be equal to a combined acceleration force
F.sub.a =m·a+F.sub.s (7)
where m is the total moving mass (kg); a is the combined acceleration of the moving mass (meters/sec 2 ); and F s is the force required to overcome spring resistance of the suspension (in Newtons).
In equation (7), mass m and acceleration a can be presented by the following two expressions, respectively:
m=m.sub.l +m.sub.cf +m.sub.ct (8)
a=a.sub.g +a.sub.m (9)
where
m l =payload mass (kg),
m cf =focus coil mass (kg),
m ct =tracking coil mass (kg),
a g =gravitational acceleration equal to 9.81 meters/sec 2 ,
a m =desired acceleration of mass (meters/sec 2 ).
Additionally, for a maximum stroke δ and desired natural frequency f n , force F s can be expressed as
F.sub.s =m·δ(2πf.sub.n).sup.2 (10)
If value F in equation (5) is substituted by the force F a from equation (7), the motor effectiveness parameter K ef can be transformed to a similar parameter
K.sub.af =a/√P=(1/m)√m.sub.c /C.sub.m (11)
which represents the effectiveness of the motor in terms of load acceleration per square root of power. Parameter K af is measured in (meters/sec 2 )/√watts, or, if expressed in grams/√watts, ##EQU2## The structure of the above two equations indicates that the amount of power required to operate the actuator can be minimized when the efficiency parameter K af is maximized.
Since focus and tracking motions of the objective lens 1 in the FIG. 2 aparatus are executed by separate motors, each of them will be characterized by its own effectiveness parameter. Such values, if combined with equation (8), will have the following expressions: ##EQU3## for the focus motor, and ##EQU4## for the tracking motor.
In the above equations, the design parameter C mf of the focus motor may differ from the design parameter C mt of the tracking motor when different wire materials (with their own density γ and resistivity ρ) are used for the focus and tracking coils. Additionally, the effective to total wire length ratio β may not be the same for each coil.
If the effectiveness parameters K aff and K aft for the focus and tracking motors, respectively are specified by the drive application, the required coil mass for both focus and tracking motors can be defined by combining equations (13) and (14) and solving them together. In such a case, preliminary values of the design parameters C mf and C mt have to be established in advance based upon the initial design layouts of the optical head. After simplification, the final solution results in the following focus and tracking coil masses, respectively: ##EQU5## Analysis of the expressions for m cf and m ct allows us to make the following important statements:
1. For the required values of motor efficiencies K aff and K aft and expected design parameters C mf and C mt , the respective masses of the focus and tracking coils have a real solution only when the expression under the radical in equation (17) is positive.
2. Both masses, m cf and m ct , have a pair of solutions due to the plus and minus signs in front of the radical in equation (17). Therefore, it is appropriate to conclude that for a given ratio between the focus and tracking motor efficiencies there are certain values of m cf and m ct when each of the parameters K aff and K aft will be at its maximum.
3. The ratio between masses of focus and tracking coils is directly proportional to the product of ratios between squared values of motor efficiencies K af and design parameters C m . In other words, from equations (15) and (16),
m.sub.cf /m.sub.ct =(K.sub.aff /K.sub.aft).sup.2 ·(C.sub.mf /C.sub.mt) (18)
or
m.sub.cf /m.sub.ct =k.sup.2 (C.sub.mf /C.sub.mt) (19)
where
k=K.sub.aff /K.sub.aft (20)
is the ratio between the focus and tracking motor efficiencies. In a special case, when C mf =C mt ,
m.sub.cf /m.sub.ct =k.sup.2 (21)
As stated in the first statement above, for masses m cf and m ct to have a solution, the following condition must be fulfilled:
1-4m.sub.l [(K.sub.aff).sup.2 C.sub.mf +(K.sub.aft).sup.2 C.sub.mt ]≧0
Therefore, with the expected design parameters C mf and C mt , the required values of focus and tracking motor efficiencies are attainable only for an actuator having a payload m l which cannot be larger than
m.sub.l(max) =0.25/[(K.sub.aff).sup.2 C.sub.mf +(K.sub.aft)C.sub.mt ](22)
If the actual payload mass m l is larger than m l (max) and no appropriate changes can be implemented to decrease the value of m l , the motor efficiency requirements must be lowered. To avoid an efficiency decrease, steps may be taken to enlarge the allowable maximum value of the payload mass. This can be done by forcing design parameters C mf and C mt to become smaller. As equation (3) indicates, such a change in values of C mf and C mt may be achieved by choosing materials for coil wire with smaller density and resistivity, for instance, by using aluminum instead of copper wire. For the same reason, both flux density B and the effective to total wire length ratio β must be increased.
When the expected design parameters C mf and C mt are defined by the preliminary optical head layout and the required motor efficiencies are established by the actuator application, the focus and tracking coil masses can be optimized to maximize values of K aff and K aft . This optimization assumes that the specified efficiency ratio k from equation (20) is kept constant, and the payload mass m l does not exceed its maximum allowable value m l (max) from equation (22).
Optimization of coil masses can be carried out by presenting motor efficiencies as two separate functions of either m cf for m ct , and then solving expressions for partial derivatives of K aff and K aft with respect to each mass. In such a case, with the ratio between masses m cf and m ct from equation (19), equations (13) and (14) can be rewritten as ##EQU6## Therefore, when simplified and solved for values of focus and tracking masses, the following two equations
∂K.sub.aff /∂m.sub.cf =0
∂K.sub.aft /∂m.sub.ct =0
will result in mass values equal to
m.sub.ocf =m.sub.l /[1+(1/k.sup.2)·(C.sub.mt /C.sub.mf)](25)
m.sub.oct =m.sub.l /[1+k.sup.2 ·(C.sub.mf /C.sub.mt)](26)
In the special case where C mf =C mt ,
m.sub.ocf =m.sub.l /(1+1/k.sup.2) (27)
m.sub.oct =m.sub.l /(1+k.sup.2) (28)
In the equations above, the obtained values of focus and tracking coil masses are denoted by a new subscript "oc" to indicate that both coils are optimized to maximize efficiency parameters of each motor. The latter can be easily demonstrated by differentiating equations (23) and (24) twice and showing that the resulting values are negative. The fact that motor efficiencies have maximum values can also be illustrated graphically by plotting K aff and K aft as a function of the coil mass. In FIG. 4, such graphs are presented for an actuator with the following design parameters:
m l =0.8 gm
k=1.5
C mf =4.5 ms
C mt =9.5 ms
As seen in FIG. 4, when the ratio between focus and tracking coil masses is specified by equation (19), maximum values of efficiency parameters are equal to 19.29 and 12.86 grams per square-root of power (watts) for the focus and tracking motors, respectively. For such a case, these parameters can be achieved with coils in each motor having respective masses of 0.413 and 0.387 gm.
In FIG. 4, it is apparent that the graph slopes in the area of maximum motor efficiencies are gentle enough to provide a wide tolerance in determining masses of focus and tracking coils due to certain manufacturing deviations in coil sizes, number of turns, wire diameter, etc. For instance, for an optimized focus coil mass but with a tracking coil mass different from its optimized value, motor efficiency parameters will be computed by equations (13) and (14) as ##EQU7## For m ocf =0.413 gm, values K' aff and K' aft are plotted in FIG. 5 as a function of m cf . These graphs, combined with graphs from FIG. 4, are presented in FIG. 6. A fragment of this figure, illustrated in a larger scale and taken in the area of maximum motor efficiencies, is shown in FIG. 7. The latter indicates that, for an optimized tracking coil with a mass of m ct =0.387 gm, a ±25% change in this value from 0.3 to 0.5 gm will result in motor efficiency changes less than ±7%.
Although optimized masses m ocf and m oct from equations (25) and (26) are characterized by the same ratio as defined in equation (19), their individual values are different from the ones in equations (15) and (16). However, if m ocf and m oct are added together, the following simplified expression can be written:
m.sub.l =m.sub.ocf +m.sub.oct (29)
This equation is very significant since it points to a clear design direction, namely: for maximum efficiencies of both motors, the respective masses of the focus and tracking coils must be characterized by a ratio from equation (19) with their combined value equal to the mass of the payload.
With optimized coil masses, equations (13) and (14) for maximized values of motor efficiencies can be easily simplified to the following expressions: ##EQU8##
These parameters, if substituted for values K aff and K aft in equation (22), define the allowable value of m l (max) as being equal to m l . In other words, for focus and tracking motors with maximum efficiencies, the payload mass m l represents its maximum allowable value which guarantees the existence of the solution for coil masses in each motor.
For a given design application, it is logical to assume that the payload mass m l and ratio k between the desired efficiency parameters of the focus and tracking motors are specified. If the preliminary design parameters C m for each motor are also determined, in other words, when magnetic flux density B and coil material (γ and ρ) and sizes (such as β) are established, optimized coil masses in equations (30) and (31) can be easily excluded as variables in determining maximum values of motor efficiencies. To present these maximum values as a function of design characteristics only, optimized coil masses in equations (30) and (31) have to be substituted with their respective values from equtions (25) and (26). After simplification, this substitution results in ##EQU9## or, for the special case when C mf =C mt =C m , ##EQU10## Furthermore, if in this special case the focus and tracking motors have the same efficiencies, in other words, for a ratio k=1, the maximum efficiency parameters for each motor will have values equal to ##EQU11## or, combined with equations (8) and (9), ##EQU12## For such a special case, when C mf=C mt=C m and k=1.0, the total moving mass of the focus/tracking actuator is equal to m=2 m l =4 m c , where m c is the mass of either focus or tracking coils. With it, equation (37) can be easily transformed into the form expressed by equation (11).
In view of the foregoing analysis, the following conclusions can be drawn:
1. When motor efficiency parameters have maximum values defined by equations (32) and (33), the actuator lens acceleration in either focus or tracking direction will require the minimum amount of power. For a majority of applications, this represents the most desirable design optimization. Therefore, for an actuator with established values of m l , k, C mf and C mt , maximum motor efficiencies from equations (32) and (33) will be guaranteed with focus and tracking coil masses characterized by the optimized values m ocf and m oct from equations (25) and (26), respectively. In such a case, their combined mass will be equal to the payload mass m l .
2. If the achievable values of K aff (max) and K aft (max) are smaller than the required efficiency parameters, the overall design of the actuator has to be reviewed in order to lower the payload mass m l or steps must be taken to decrease design parameters C mf and C mt (e.g., by enlarging β and B, and choosing materials with smaller γ and ρ.
3. If maximum motor efficiencies K aff (max) and K aft (max) exceed the required values of K aff and K aft , the coil masses can be chosen within a range of values allowing one to trade off motor efficiencies for other factors, such as mass distribution, coil thicknesses, manufacturing cost, etc.
While the invention has been described with reference to a preferred embodiment, it will be appreciated that certain modifications may be made without departing from the spirit and scope of the invention. Such modifications are intended to fall within the scope of the appended claims. | A focus/tracking actuator for controlling the respective focus and tracking positions of a lens used to direct a focused beam of radiation onto a desired data track on a moving recording element comprises a pair of moving coil-type linear motors. Each of the motors comprises a coil of wire disposed in a magnetic air gap and adapted to move therein in response to an applied current flow. According to the invention, the respective masses of the motor coils are optimized to achieve maximum acceleration with minimum power comsumption. Preferably, the coils have a combined mass substantially equal to the mass of the moving payload, which includes the lens assembly and its movable support. | 6 |
This is a continuation of PCT application No. PCT/GB99/03452, filed Oct. 19, 1999, the entire content of which is hereby incorporated by reference in this application.
The present invention relates to a process for making n-butyl esters by reacting butadiene with a carboxylic acid in the presence of a Brønsted or Lewis acid catalyst to form the unsaturated ester which is subsequently hydrogenated to form the saturated ester.
BACKGROUND OF THE INVENTION
It is known that n-butyl esters such as n-butyl acetate can be produced by a number of routes. For instance, the hydroformylation of propylene in the presence of acetic acid is a method which gives a mixture of n-butyl acetate and iso-butyl acetate. This method however requires a source of syngas which increases capital costs. An alternative method is to react ethylene with vinyl acetate in the presence of an acid catalyst followed by the hydrogenation of the resultant unsaturated ester. A further method is the reaction of ethylene with ethanol in the presence of a base catalyst to form butanol and the reaction thereof with acetic acid to form butyl acetate. In addition, all these methods rely on the use of either relatively expensive feedstocks such as ethylene and n-butanol or involve multiple reaction stages or expensive catalysts and separation stages. The acid catalysed addition of butadiene to acetic acid using ion-exchange resin catalysts having bulky counterions to improve the reaction selectivity to two isomeric C 4 butenyl acetates is disclosed in several patents viz., U.S. Pat. No. 4,450,288 (alkyl pyridinium), U.S. Pat. No. 4,450,287 (quaternary ammonium), U.S. Pat. No. 4,450,289 (quaternary phosphonium). The main objective of these patents is stated to be the production of secondary butenyl acetate. However, there is no mention in these documents of the isolation of n-but-2-enyl acetate or the production of n-butyl acetate. Butadiene is a relatively inexpensive by-product of the refining process and is a potential feedstock for making butyl esters. It is commercially available either as a purified chemical or as a constituent of a hydrocarbon cut. For example, as a constituent of a mixed C 4 stream obtained from naphtha stream cracking. Typically such streams contain species such as butane, 1-butene, 2-butene, isobutane and isobutene in addition to butadiene. It is advantageous that a process utilising butadiene can use such streams. However, butadiene is also in equilibrium with 4-vinyl cyclohexene, a Diels Alder dimer of butadiene. This dimer can be thermally cracked back to butadiene:
So any process involving the use of butadiene as feedstock needs to take this reversible reaction into consideration.
EP-A-84133 describes a process for the production of unsaturated alcohols and/or esters of unsaturated alcohols. The reference describes the reaction between conjugated dienes and water or aqueous carboxylic acids. The resulting product, is a complex mixture of unsaturated isomeric alcohols and esters.
SUMMARY OF THE INVENTION
It has now been found that saturated n-butyl esters and secondary butyl esters can be synthesised without resort to either (a) the hydroformylation route from propylene or (b) the use of vinyl acetate or ethylene feedstocks in relatively simple stages.
According to a first aspect of the present invention, a process is provided for making a butyl ester from butadiene, this process comprising:
a. reacting butadiene with a saturated aliphatic monocarboxylic acid to form a mixture of n-butenyl and secondary butenyl esters, b. separating the n-butenyl ester from the secondary butenyl ester, and c. hydrogenating the n-butenyl ester separated in step b) in the presence of a catalyst to the corresponding n-butyl ester.
The butadiene employed in step a) may be employed in the form of a substantially pure butadiene. Alternatively, a hydrocarbon mixture comprising butadiene may be employed. In one embodiment a raw (e.g. crude or depleted) C 4 stream comprising butadiene, isobutene, 1 and 2-butenes and butane is employed. Such a stream may comprise up to 60% butadiene.
The secondary butenyl ester separated in step b) may be: i) recycled to step a), ii) hydrogenated in the presence of a catalyst to produce sec-butyl ester, iii) thermally cracked to produce the starting butadiene and a saturated aliphatic monocarboxylic acid; or iv) further reacted.
A preferred embodiment of the present invention is a process for making a butyl ester from butadiene, said process comprising:
a. reacting butadiene or a hydrocarbon fraction comprising butadiene with a saturated aliphatic monocarboxylic acid to form a mixture of n-butenyl and secondary butenyl esters, b. separating the n-butenyl ester from the secondary butenyl ester, c. recycling the secondary butenyl ester thus recovered to step a), and d. hydrogenating the n-butenyl ester in the presence of a catalyst to the corresponding n-butyl ester.
In the present process, the saturated, aliphatic carboxylic acid suitably has 1-6 carbon atoms and is preferably acetic acid. Thus, the present process can be readily adapted to the reaction of butadiene with acetic acid to form a mixture of n-butenyl acetate (also known as crotyl acetate) and secondary butenyl acetate, the latter being separated and preferably recycled to the initial stage and the n-butenyl acetate (crotyl acetate) being catalytically hydrogenated to form n-butyl acetate.
The reaction is suitably carried out in the liquid or mixed liquid/gas phase in the presence of a solvent. It is not essential that both reactants dissolve completely in the solvent. However, it is an advantage if the solvent chosen is such that it is suitably capable of dissolving both the reactants. Specific examples of such solvents include hydrocarbons such as decane and toluene and oxygenated solvents such as butyl acetate or excess carboxylic acid reactant and recycled higher esters such as C 8 acetates recycled sec-butenyl acetate. The use of excess carboxylic acid as a reactant can be advantageous when this chemistry is used to extract butadiene from an impure stream, as it facilitates reaction at high conversion of butadiene, or in process terms high efficiency of removal of butadiene. Currently the removal or recovery of butadiene from refinery streams requires a separate processing stage.
The reactions taking place in a preferred embodiment of the invention can be represented graphically by the following equation:
n-Butyl Carboxylate by the Addition of Carboxylic Acids to Butadiene
The reactions, and in particular, the addition reaction between butadiene and the carboxylic acid (step a), may be carried out using a homogeneous or heterogeneous catalyst. Heterogeneous catalysts may be advantageous in certain cases as they can facilitate the separation of the reaction product from the reaction mixture, and/or allow the catalyst to be conveniently separated from reaction by-products (mostly high boiling point butadiene oligomeric species). The preferred catalysts are based on strong acid ion-exchange resins (e.g. Amberlyst 15®, Amberlite IR120®) with a proportion of the acidic sites exchanged with bulky counterions such as tetra-phenylphosphonium counterions. Typically these counterions account for less than 10% of the available acidic sites.
The heterogeneous catalyst phase can be a partially or fully insoluble liquid phase (e.g. acidic ionic liquids, liquid acidic polymers and partially solvated polymers) or a solid (e.g. HY zeolite, strong acid macroreticular, macronet and gel ion-exchange resins and heteropolyacids of tungsten or molybdenum which have been ion-exchanged and/or supported on a carrier material). In addition to Amberlyst 15® mentioned above, other suitable examples of heterogeneous catalysts include fluorinated ion-exchange resins like Nafion®, phosphoric acid functionalised polymers, and acidic oxides such as HY zeolites.
In certain cases the activity of heterogeneous catalysts may decrease after prolonged periods of use. This may be due to blockage of active sites by butadiene oligo- and polymerisation products. In such cases, it may be advantageous to carry out the process of the present invention in homogeneous phase. Suitable homogeneous catalysts include sulphonic acids, triflic (trifluoromethanesulphonic) acid and its salts (triflates). Examples of such salts include lanthanide triflates, such as lanthanum trifluoromethanesulphonic acid salts. Suitable organic sulphonic acids include methane sulphonic acid, p-toluene sulphonic acid and sulphonated calixarenes. Heteropolyacids such as tungsten Keggin structure, strong acid ionic liquids such as those described in prior published EP-A-693088, WO 95/21872 and EP-A-558187 are also suitable.
The activity of the above mentioned heterogeneous catalysts can be modified by additives such as alkyl pyridinium, quaternary alkyl ammonium, quaternary arsonium and quaternary phosphonium compounds. These additives exchange with some of the acid sites on the support and to one skilled in the art can be introduced as a salt with a displaceable counterion e.g. halides, sulphates or carboxylates.
Levels of water may also play an important part in the activity of the catalyst. For example, water levels below 5% w/w are found to be preferable because at levels above 5% w/w the catalyst activity is significantly reduced. At levels below 0.01% w/w, however, the activity has also been found to be reduced. Consequently the water level in the reaction zone is suitably in the range from 0.01 to 5% w/w based on the carboxylic acid, preferably from 0.05 to 1% w/w.
The presence of water as a reaction adjuvant can also beneficially affect the selectivity of the catalyst. For example, when Amberlyst 15® is employed as a catalyst for the reaction between butadiene and acetic acid, the rate of reaction increases through a maximum as the concentration of water is increased. Thus, the reaction occurs at an optimum rate at a particular water concentration. Thus for the Amberlyst 15® catalysed reaction between butadiene and acetic acid, preferred water concentrations are about 0.2 to 0.5 w/w %, preferably 0.3 to 0.4 w/w %.
The reasons for this effect are not fully understood. However, without wishing to be bound by any theory, it is believed that water may have an effect on the accessibility of the active sites on the catalyst, the acidity of the catalyst and/or the hydrophilicity of the catalyst. It should be noted, however, that the effect of water on both the activity and selectivity of the catalyst may also be dependent on other factors, such as the nature of the catalyst and other reaction conditions employed.
In the process of the present invention it is also advantageous to use polymerisation inhibitors such as alkylated phenols (e.g. BHT butylated hydroxytoluene, also called 2,6-di-tert-butyl-p-cresol). Other members of this series include the Irganox® series of materials from Ciba Gigy, Lowinox® series of materials from Great Lakes Chemical Corporation, tropanol® series from ICI and t-butylcatechol, nitroxides and derivatives (e.g. di-t-butylnitroxide, and n,n-dimethyl-4-nitrosoaniline, nitric oxide), stable radicals (e.g. 2,2,6,6,-tetramethyl-piperidine-1-oxyl, 2,2,6,6,-tetramethyl-4-hydroxypiperidine-1-oxyl and 2,2,6,6,-tetramethylpyrrolidine-1-oxyl).
The relative mole ratios of butadiene to the carboxylic acid reactant in the addition reaction is suitably in the range from 5:1 to 1:50, preferably in the range from 1:1 to 1:10.
This addition reaction (step a)) is suitably carried out at a temperature in the range from 20 to 140° C., preferably from 20 to 130° C., more preferably, 30 to 120° C., and most preferably 40 to 90° C. The reaction is suitably carried out at the autogeneous reaction pressure which is determined by factors such as the reaction temperature, presence of absence of solvent, excess of reactants and impurities present in the butadiene stream. An additional pressure may be applied to the system if single fluid phase is preferred e.g. no butadiene gas phase in addition to the solvated liquid phase.
The addition reaction (step a)) may be suitably carried out in a plug flow reactor with the unused butadiene being flashed off and recycled to the reactor via a vapour liquid separator, but equally could be conducted in a slurry reactor. In the case of a plug flow reactor, the butadiene can be present partially as a separate gas phase as well as being dissolved and this would result in either a trickle bed operation or a bubble bed operation. A typical LHSV (liquid hourly space velocity=volume of liquid feed/catalyst bed volume) for the carboxylic acid is 0.1 to 20 more preferably 0.5 to 5. In the case of a slurry reactor, a continuous bleed of any deactivated catalyst can be taken. In this case it is economically advantageous to run with catalyst in a various stages of deactivation to improve the utilisation of catalyst. This may result in the total loading of catalyst (activated+deactivated) reaching high levels such as 50% w/w of the reaction charge.
Preferably, the butadiene may be added gradually to the saturated aliphatic monocarboxylic acid, for example, by multiple injection at constant pressure in a batch reactor. By adding the butadiene gradually in this manner, side reactions leading to, for example, the polymerisation of the butadiene can be minimised.
In the process, distillation is suitably used to allow separation of the reactants and products. A small amount of water azeotroping of reaction products may occur due to the low levels of water employed. However, this is minor and does not significantly effect the separation of the isomeric butenyl esters, i.e. the n-butenyl ester and secondary butenyl ester (step b)). The sec-butenyl ester can be recovered and recycled to the initial addition reaction between the butadiene and the carboxylic acid (step c)). It has been found that the sec-butenyl ester under reaction conditions interconverts with butadiene, free carboxylic acid and the crotyl ester. The conversion of the sec-butenyl ester to free carboxylic acid and butadiene can be achieved by treatment in the vapour phase with an acidic support such as silica-aluminas. The use of such a separate pretreatment prior to the return to the carboxylic acid and butadiene to the addition reactor may have a beneficial effect on productivity and selectivity.
The separated n-butenyl ester stream is then passed to the catalytic hydrogenation stage (step d)) to form the n-butyl ester. It is preferable to carry out the hydrogenation step under heterogeneous conditions so that it is easy to separate the catalyst from the reaction products. The catalytic hydrogenation step is suitably carried out using one or more of the following catalysts: transition metal catalysts, typically from the later groups such as ruthenium, platinum, nickel, palladium, preferably supported on a low acidity carrier such as carbon or coating a support so that little free acidity remains. Examples include Raney nickel, supported Raney nickels, 5% ruthenium on carbon.
The preferred hydrogenation catalysts are a Raney nickel catalyst supported on carbon and a ruthenium catalyst also supported on carbon.
This hydrogenation (step d)) is suitably carried out at a temperature in the range of from 80 to 250° C., preferably, in the range of from 120 to 200° C. This stage can be conducted at elevated, atmospheric or sub-atmospheric pressures. The hydrogenation reaction is suitably carried at a pressure in the range from 1 barg to 100 barg, preferably from 5 to 50 barg. The hydrogenation can be carried out in slurry and flow reactors. If some carboxylic acid from the previous process stages is present, this can have a detrimental effect on some catalysts e.g. nickel catalysts can dissolve to give nickel acetates. This can limit the selection of the catalyst. A solvent is not required for this reaction. The reaction can be carried out in an all gas/vapour phase or as a two phase mixture. In the latter case, a flow reactor would be operated in either a trickle bed or a bubble bed mode. The completion of the hydrogenation of the n-butenyl esters can be determined conveniently for batch reactions by cessation of hydrogen uptake and in the case of both flow and batch reactors by sampling and analysis by methods such as Gas Chromatography and UV.
The process of the present invention has the following advantages:
i. The addition of butadiene to carboxylic acids may provide an attractive alternative to hydroformylation as a source of n-butyl esters. There is a significant feedstock cost advantage to the new process. ii. The proposed C 4 butadiene based routes have an advantage over a propene-based routes when propene feedstock costs are high. ii. In this process, impure butadiene streams can be used and this could further reduce feedstock costs and aid in refinery integration.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is further illustrated with reference to the accompanying drawings, in which:
FIG. 1 is a schematic diagram of the apparatus suitable for carrying out a first embodiment of the present invention and
FIG. 2 is a schematic diagram of the apparatus suitable for carrying out a second embodiment of the present invention.
FIG. 3 is a graphical depiction of component concentrations with inhibitor and without inhibitor plotted against reaction time.
FIGS. 4a , 4 b, 5 a, 5 b and 6 summarize the results obtained by varying the w/w/ % of water in acetic acid charge.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference is first made to FIG. 1 , which depicts an apparatus 10 suitable for the production of n-butyl acetate from a substantially pure butadiene feedstock. The apparatus 10 comprises an addition reactor 12 , which is coupled to a hydrogenation unit 14 via a pair of distillation columns 16 , 18 and a guard bed 20 for the removal of acetic acid. The addition reactor 12 comprises three fixed beds (not shown).
In operation, butadiene and acetic acid are fed into the addition reactor 12 via lines 22 , 24 . The reactants react to produce a product stream 26 comprising sec-butenyl acetate and crotyl acetate. Unreacted materials, such as butadiene, acetic acid and water (as an azeotrope) are also present in the product stream 26 .
The product stream 26 is introduced into column 16 , which separates the water, unreacted butadiene, some unreacted acetic acid and some sec-butenyl acetate from the remainder of the product stream 26 . The water, unreacted butadiene, some unreacted acetic acid and some sec-butenyl acetate are recovered from the top of the distillation column 16 as an overhead stream, and recycled to the addition reactor 12 via line 28 . In an alternative embodiment (not shown), the overhead stream is decanted to adjust the amount of water recycled. In a further alternative (not shown), the overhead stream is cracked, so as to convert the secondary butenyl acetate back to butadiene and acetic acid.
A stream consisting essentially of crotyl acetate, sec-butenyl acetate and acetic acid is recovered from the base of the column 16 and introduced into the second distillation column 18 . The column 18 separates the remainder of the secondary butenyl acetate and acetic acid from the crotyl acetate. The secondary butenyl acetate and acetic acid are recycled back to the addition reactor 12 via the top of the column 18 , whilst the crotyl acetate is removed from the base of the column 18 and introduced into the guard bed 20 . The bed 20 removes any traces acetic acid that may still be present in the crotyl acetate stream.
The crotyl acetate, substantially free of acetic acid, is then introduced into the hydrogenation unit 14 . Hydrogen is introduced into the unit 14 via line 30 , and the ensuing reaction produces a product stream 32 comprising impure n-butyl acetate.
The stream 32 is recovered from the hydrogenation unit 14 and introduced into a third distillation column 34 for purification. The column 34 removes C 8 and C 12 acetate that may be produced as by-products. The C 8 and C 12 by-products may be separated from one another using a further distillation column 38 .
Reference is now made to FIG. 2 , which depicts an apparatus suitable for carrying out a second embodiment of the present invention. The apparatus 110 is similar to the apparatus 10 depicted in FIG. 1 . However, whereas the apparatus 10 of FIG. 1 is adapted for use with a substantially pure butadiene feedstock, the apparatus 110 of FIG. 2 is adapted for use with a mixed C 4 feedstock comprising butadiene, butane, isomeric butenes and isobutane.
The apparatus 110 comprises an addition reactor 112 which is coupled to a hydrogenation unit 114 , via a flash drum 116 , a series of distillation columns 118 , 120 , 122 , and a guard bed 124 .
In operation, acetic acid and a mixed C 4 stream are introduced into the addition reactor 112 . The ensuing reaction produces a product stream 126 which comprises unreacted starting materials and a mixture of addition products including n-butenyl acetate, sec-butenyl acetate, and t-butyl acetate.
The product stream 126 is removed from the addition reactor 112 and introduced into the flash drum 116 , which separates the most volatile components from the remainder of the product stream 126 . These volatile components include a mixture of butane, isomeric butenes, butadiene, isobutene and butadiene. By hydrogenating this mixture under mild conditions in reactor 128 , the traces of butadiene present are hydrogenated to butene. The resulting product 130 is suitable for sale.
The less volatile remainder of the product stream 126 is then introduced into the first of the distillation columns 118 , which further purifies the stream by removing the traces of butane, isomeric butenes, butadiene, isobutene and butadiene, not previously removed by the flash drum 116 .
Thus purified, the stream 126 is introduced into the second distillation column 120 , which separates the t-butyl acetate 127 from remainder of the stream 126 . The t-butyl acetate 127 is removed from the top of the distillation column 120 , and introduced into a thermal cracker 132 , which cracks the t-butyl acetate into iso-butene and acetic acid. These compounds are separated and recovered using a distillation column 133 . The isobutene recovered 134 is substantially pure, and is suitable for direct use or further processing. The acetic acid recovered is recycled back to the addition reactor 112 .
The stream recovered from the base of the distillation column 120 is introduced into a third distillation column 122 . This distillation column 122 separates the acetic acid and sec butenyl acetate from the crotyl acetate. The acetic acid and sec-butenyl acetate are recovered from the top of the column 122 , and recycled back to the addition reactor 112 . The impure crotyl acetate is removed from the base of the column 122 , and introduced into the guard bed 124 , which purifies the crotyl acetate by removing any traces of acetic acid that may be present.
The acid-free crotyl acetate is then hydrogenated in the hydrogenation unit 114 to produce a product stream comprising impure n-butyl acetate. The stream is purified in distillation column 136 , which removes any C 8 acetates and other by-products that may be present. These by-products may be removed from the base of column 136 and separated using a further distillation column 138 .
EXAMPLES
Examples of Stage (A) Reaction of Butadiene with Acetic Acid General Method for Preparation of Feeds and Autoclave Reaction
The following apparatus was used in batch mode to conduct the addition reaction of acetic acid to butadiene. A 10 L stainless steel autoclave equipped with a high efficiency impeller type stirrer and LPG handling facility was used for these experiments. The autoclave had mounted within it a fine mesh stainless steel bag in the form of a stationary annulus around the stirrer. This was used to contain the catalyst and prevent attrition during stirring. It also served to facilitate multiple reactions involving the same catalyst. The autoclave was also equipped with a sampling valve arrangement which allowed retrieval of samples during the course of the reaction.
The following general method was used for the reactions. The ion-exchange resin was pre-cleaned of extractable materials by use of a Soxhlet extraction apparatus. A range of solvents were used depending upon the nature of the resin. For example, with gel type strong acid resins, acetic acid or methanol were used and the resin was charged to the autoclave in the wet form. For macroreticular type resins, methanol was used as the solvent and the cleaned resin was then dried in a stream of nitrogen prior to use. In the case of cation exchanged resin samples, the resin was pre-treated as described above by a Soxhlet extraction and then the resin was used wet (pre-swelled) to exchange with an acetic acid solution of the target cation salt. This was achieved by stirring the solution with the resin in glassware for 16 hrs before replacing the resin in the Soxhlet extractor and repeating the extraction with methanol or another suitable solvent. The cleaned exchanged resin was then dried in a nitrogen stream prior to use. The resin to be tested was then weighed and charged to the stainless steel bag mentioned previously.
The autoclave was then sealed, pressure tested with a nitrogen pressure and pressure-purged of any residual oxygen. The acetic acid feed was subjected to a Karl Fischer water analysis (water level of 0.2% w/w±0.05 except where specified otherwise). The water level in this feed was modified to the experimental target level either by pre-treatment with acetic anhydride (strong acid ion-exchange resin used as a catalyst removable by filtration prior to use) or by adding water. The acetic acid was also purged with nitrogen prior to use to remove dissolved oxygen. The acetic acid charge to the autoclave was used also to solubilise and add any di-tert-butyl hydroxy toluene inhibitor or other trial additive.
The acetic acid charge was added to the autoclave via a funnel, the autoclave was then pressure-purged with nitrogen and heated to the reaction temperature with stirring, at which point the butadiene charge was added to the autoclave as a liquid by forcing the material in from a weighed storage vessel with a nitrogen pressure. The point of this addition was taken as t=0 and the stirred autoclave contents were sampled at regular intervals and analysed by flame ionisation detector (FED) Gas chromatography (GC). Due to problems associated with loss of volatile butadiene from the autoclave samples it was found to be advantageous to add 0.1-1% w/w on the acetic acid charge of decane as an internal standard. Control experiments with and without this added decane demonstrated that there was no significant effect on the progress of the reaction. The identity of the GC peaks was established by the synthesis of model compounds and GC/MS. The GC was calibrated by means of the purchase and synthesis of pure compounds, i.e. acetic acid, butenyl acetate, sec-butenyl acetate, and 4-vinyl cyclohexene. The higher boiling by-products from the reaction were assigned the same response factor determined for butenyl acetate and thereby roughly quantified. All these higher boiling point material peaks were combined together—designated “highers”—and the calculated % w/w used to calculate the reaction selectivity.
Example 1
Use of Amberlyst® 15H Resin without Pre-treatment
The general method described above was used except that the Amberlyst 15H® resin was used without any purification.
Charge to autoclave Amberlyst 15H® (unwashed)—85 g Acetic acid—3600 g 1,3-butadiene—1400 g Reaction conditions: 60° C. with stirring at 1200 rpm
Example 1
sec-Butenyl
n-Butenyl
Runtime
acetate
acetate
4-Vinyl cyclohexene
Highers
(Hours)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.3
0
5
7.7
7.59
1.3
2.85
6
8.95
9.37
1.28
3.91
7
9.49
10.24
1.25
4.34
8
10.49
11.72
1.26
5.07
24
10.98
14.21
0.77
6.55
These results illustrate that the reaction proceeds to give predominantly the isomeric C 4 acetates and that some loss of selectivity occurs to higher boiling point materials particularly at high reaction times. The reaction product was pale yellow which darkened on standing.
Example 2
Use of Amberlyst 15H® Resin with Pre-conditioning
The general method was used and the resin washed with ethyl acetate and dried prior to use. The following components were charged to the autoclave:
Amberlyst 15H®—85 g Acetic acid—3600 g 1,3-Butadiene—700 g Reaction conditions: 50° C., with stirring at 1200 rpm
Example 2
sec-Butenyl
n-Butenyl
Runtime
acetate
acetate
4-Vinyl cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.39
0
30
1.08
0.72
1.31
0.21
60
1.97
1.37
1.34
0.45
90
2.83
2.02
1.35
0.71
150
4.01
3.1
1.31
1.2
210
5.3
4.37
1.26
1.75
270
6.2
5.43
1.19
2.26
330
6.96
6.36
1.19
2.71
390
7.92
7.58
1.2
3.09
These results reaffirm the previous results and demonstrate that the sec-butenyl acetate is the kinetic reaction product and that the n-butenyl acetate is the thermodynamic product. The reaction product was initially colourless but darkened on standing to a pale yellow. This illustrates that pre-treatment of the Amberlyst 15H® resin served to reduce the colour of the product.
Examples 3 and 4
Effect of Temperature on Reaction Rate
Two sequential reactions were carried out on the charge of 85 g of Amberlyst 15H® used in example 2 (ethyl acetate pre-washed), the catalyst between runs was washed with acetic acid in situ to remove residual material from the previous run in the sequential reactions. The charge of butadiene was 700 g and acetic acid was 3600 g for all three experiments.
Example 3 at 40° C.
sec-Butenyl
n-Butenyl
Runtime
acetate
acetate
4-Vinyl cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.39
0
60
0.77
0.64
1.44
0.16
90
1.01
0.77
1.44
0.25
150
1.55
1.15
1.4
0.36
210
2.24
1.62
1.37
0.53
270
2.63
1.91
1.36
0.64
330
3.32
2.44
1.36
0.86
390
3.89
2.89
1.39
1.04
Example 4 at 60° C.
sec-Butenyl
n-Butenyl
acetate
acetate
4-Vinyl cyclohexene
Highers
Runtime
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.39
0
60
3.19
2.62
1.3
0.9
90
4.13
3.55
1.26
1.32
150
6.16
6.02
1.18
2.63
210
7.44
7.89
1.14
3.77
270
7.92
8.71
1.13
4.25
330
8.39
9.56
1.1
4.96
390
8.63
10.18
1.07
5.43
Examples 2, 3 and 4 illustrate that an optimum balance exists between activity and selectivity, i.e. at higher temperatures the activity is increased at the expense of the reaction selectivity. The process optimum will vary with factors such as catalyst employed and feedstock costs.
Examples 5 and 6
Illustration of Catalyst Deactivation without Addition of Inhibitor
The Amberlyst 15H® resin charge used in example 4 was re-used as described for examples 3 and 4 by washing in situ with acetic acid in between runs. The butadiene and acetic acid charge were kept substantially identical to that employed in example 2. Example 6 re-used the charge used in example 5.
Example 5 at 50° C.
sec-Butenyl
n-Butenyl
Runtime
acetate
acetate
4-Vinyl cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.39
0
60
0.96
0.84
1.41
0.31
90
1.34
1.1
1.51
0.4
150
1.98
1.55
1.51
0.55
210
2.44
1.89
1.44
0.71
270
3.22
2.5
1.47
0.94
330
3.72
2.91
1.44
1.14
390
4.53
3.6
1.52
1.34
Example 6 at 50° C.
sec-Butenyl
n-Butenyl
Runtime
acetate
acetate
4-Vinyl cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.39
0
150
1.57
1.05
1.56
0.33
270
2.87
2.01
1.49
0.74
330
3.22
2.3
1.46
1.86
Comparison of examples 2, 5 and 6 shows that catalyst deactivation occurred. The rate of deactivation is such that the conclusions drawn from examples 2, 3 and 4 are still valid.
Examples 7, 8, 9, 10 and 11
To Show that the Presence of an Inhibitor Reduces the Rate of Catalyst Deactivation
The autoclave was charged with a fresh ethyl acetate-washed sample of Amberlyst 15H® resin (85 g) for example 7 and this was re-used in the subsequent examples (7 then 8 then 9 and then 10) by washing with acetic acid in situ as previously described. The inhibitor BHT (2.5 g) was dissolved in the acetic acid charge 3600 g prior to charging the autoclave. 700 g of butadiene was used in each example.
Example 7 at 50° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.44
0
155
3.15
2.44
1.1
0.68
275
4.7
3.97
1.03
1.2
395
5.24
4.57
1.02
1.4
Example 8 at 50° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.44
0
155
2.86
2.16
1.66
0.67
275
4.74
3.88
1.57
1.33
395
6.04
5.26
1.53
1.93
Example 9 at 50° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.44
0
155
2.02
1.45
1.46
0.43
275
3.25
2.42
1.44
1.77
395
4.33
3.4
1.42
1.03
Example 10 at 50° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.44
0
155
1.96
1.37
1.47
0.41
275
3.11
2.27
1.43
0.72
395
4.23
3.26
1.41
1.00
Example 11 at 50° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.44
0
155
1.68
1.16
1.45
0.1
275
2.72
1.95
1.42
0.61
395
4.22
3.24
1.42
1.00
Comparison of examples 2 to 6 and 7 to 11 illustrates that the presence of inhibitor both decreases the rate of catalyst deactivation and also increases the reaction selectivity. A slight decrease in initial activity of catalyst is also observed.
Examples 12-14
To Illustrate the Effect of Water
Example 12
The general method was followed. The following charge was used:
Amberlyst 15H® (ethyl acetate washed)—85 g Acetic acid—3600 g Water—72 g Butadiene—700 g Reaction temperature 60° C. with stirring at 1200 rpm. No conversion to the butenyl acetates was observed over 5 hrs.
Example 13
The catalyst from example 12 was reused, by pre-washing in situ with acetic acid. The same reaction conditions and charge were used except that the amount of added water was reduced to 36 g.
Example 13 at 60° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.56
0
150
1.62
1.38
1.51
0.15
270
2.44
2.13
1.51
0.28
Example 14
The catalyst from example 13 was reused, by pre-washing in situ with acetic acid. The same reaction conditions and charge were used except that the amount of added water was reduced to 14 g.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.37
0
150
3.7
3.01
1.32
0.78
270
5.62
5.02
1.24
1.52
390
7.52
7.25
1.24
2.3
Comparison of examples 12-14 illustrate that water is a reversible poison for the catalyst.
Examples 15,16,17 and 18
To Show the Effect of Low Levels of Water on Catalyst Deactivation
Fresh Amberlyst 15H® resin (ethyl acetate washed, 85 g) was charged to the stainless steel bag. The catalyst was re-used in these examples (using an acetic acid wash in situ in between examples). The following charge was used:
Acetic acid (3600 g, pre-treated with acetic anhydride-content <0.01% w/w) water (0.052% w/w based on acetic acid) BHT (3 g) Butadiene (700 g) Reaction temperature 50° C. with stirring at 1200 rpm.
Example 15 at 50° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
0.507
0
150
2.64
2.068
0.478
0.487
270
3.729
3.174
0.468
0.788
390
4.675
4.34
0.465
1.139
Example 16 at 50° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
0.424
0
170
1.972
1.499
0.43
0.354
270
3.229
2.634
0.43
0.69
390
4.193
3.685
0.43
1.017
Example 17 at 50° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
0.41
0
150
1.76
1.252
0.542
0.31
285
2.776
2.144
0.416
0.577
390
3.487
2.87
0.42
0.8
Example 18 at 50° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
0.43
0
150
1.298
0.851
0.43
0.204
270
2.107
1.478
0.43
0.377
390
2.836
2.131
0.43
0.580
Comparison of this set of examples with previous examples demonstrates that lower levels of water lead to an increased loss of reaction selectivity (selectivity to the isomeric C 4 acetates) and also an increased rate of deactivation of the catalyst.
Example 19
Use of Co-solvents and Counterions in the Reaction
4.5% of the acid sites on a sample of ethyl acetate-washed Amberlyst 15H® resin were exchanged with tetraphenyl phosphonium bromide by the method described previously. This material was charged to the autoclave with acetic acid (1700 g, 0.2% w/w water), ethyl acetate (900 g) and butadiene (700 g). The reaction was conducted in the usual manner at 50° C. with stirring at 1200 rpm.
Example 19 at 50° C.
sec-
n-
4-Vinyl
Runtime
Butenyl acetate
Butenyl acetate
cyclohexene
Highers
(Minutes)
(% w/w)
(% w/w)
(% w/w)
(% w/w)
0
0
0
1.35
0
155
3.53
3.11
1.28
1.06
275
4.89
4.62
1.24
1.63
395
6.43
6.55
1.28
2.46
Example of Step (b)—Isolation of Crotyl Acetate from the Reaction Mixture
Example 20
The butadiene and excess acetic acid recovery stage was modelled. The crude recovery was modelled using a rotary evaporator (80% of reaction mixture taken overhead, ˜500 mmHg pressure). The initial composition of the reaction mixture is shown below:
sec-Butenyl n-Butenyl acetate acetate 4-Vinyl cyclohexene Highers Example (% w/w) (% w/w) (% w/w) (% w/w) 20 6.43 6.55 1.28 2.46
Analysis of the overheads product (80%) by GC showed that it consisted of mainly acetic acid and sec-butenyl acetate with traces of other species such as 4-vinyl cyclohexene and water.
The remaining concentrate in the flask (20%) was transferred to a distillation apparatus equipped with a reflux splitter and 1.5 m long, 30 mm wide packed column. The apparatus was operated in batch mode with the following main fractions being collected in the following order:
Mixed fraction of sec-butenyl acetate and acetic acid with a trace amount of water (at 106-117° C.); and crotyl acetate (at 120-125° C.)
Examples of Step (c)—Recycle of Sec-butenyl Acetate
Example 21-25
To demonstrate the inter-conversion of the isomeric C 4 butenyl acetates, a Quickfit® glass apparatus was assembled consisting of a heated three-necked round-bottomed flask equipped with a condenser, an overhead stirrer, a sampling valve and a nitrogen top cover. The examples were carried out as follows:
The reaction flask was charged with Amberlyst15®, acetic acid and an internal standard (decane). This was allowed to equilibrate at the reaction temperature for 20 minutes. The C 4 butenyl acetates were added through a syringe in 6×10 ml doses over 3 minutes.
Samples from the reaction vessel were taken by syringe at regular intervals. Conversion of both crotyl acetate to sec-butenyl acetate and the corresponding reverse reaction of sec-butenyl acetate to crotyl acetate was monitored. An equilibrium between crotyl acetate and butenyl acetate was found, the reaction mixture tending to a 1:1.5 mixture of sec-butenyl:crotyl acetate under the reaction conditions. An acid catalyst was required to promote this reaction: no reaction was observed in the absence of a catalyst. Free butadiene was also observed in the GC trace. The presence of inhibitor was found to improve the selectivity of the inter-conversion.
Crotyl 2-Butenyl Ex. Acetate Acetate Acetic Amberlyst Atmo- Temp. No. (g) (g) Acid (g) 15 ® (g) sphere (° C.) 21 59.4 0.0 180.2 15.8 Static N 2 50 22 0.0 60.8 183.3 15.8 Static N 2 50 23 29.1 29.3 183.3 15.8 Static N 2 50 24 60.0 0.0 183.3 15.8 Static N 2 50 25 0.0 60.0 183.3 15.8 Static N 2 50
Examples 24 and 25 contained the inhibitor 2,6-Di-tert-butyl-4-methylphenol at 600 ppm FIG. 3 illustrates the re-equilibration of the two isomers (see below).
Step d) Hydrogenation of Crotyl Acetate to n-butyl Acetate
An initial charge of crotyl acetate (60.0 g), toluene (240.0 g), decane (3 g) and Raney nickel catalyst supported on carbon (ex Harshaw, ground to >60 mesh, 6.0 g) was charged to a stirred batch autoclave (500 ml, zirconium metal body), pressurised at 30 barg with hydrogen and heated to 100° C. for 5.5 hrs. During this period the autoclave was maintained at 30 barg with hydrogen from a gas ballast vessel. The reactants were allowed to stand overnight with the heating and stirring turned off. The following day, the autoclave was de-pressurised, sampled and then purged with nitrogen. The reactor was then charged with hydrogen and the heating and stirring recommenced. The heating was stopped after a further 6.5 hrs (bringing the total of the heating time to 12 hrsat 100° C.) and the contents of the autoclave sampled again after cooling.
The samples were analyzed by gas chromatography which showed that the hydrogenation of crotyl acetate had been driven to completion. This analysis also showed that the reaction was more than 85% selective to n-butyl acetate. The loss of reaction selectivity is believed to be due to the reversal of the butenyl acetate back to butadiene and acetic acid under the hydrogenation conditions which was catalysed by the presence of the acid. In spite of the closeness of the boiling points of crotyl acetate and n-butyl acetate, it was found that the hydrogenation products contained no detectable amounts of crotyl acetate. This is important since the odours of n-butyl acetate and crotyl acetate are very different and any significant amounts of crotyl acetate impurity in the product n-butyl acetate would be unacceptable.
Example 26
In this example, the effect of water on the reaction of butadiene and acetic acid in the presence of the Amberlyst 15® catalyst is investigated.
Experimental
The reactions described in this example were carried out in a 10 liter stainless steel autoclave. The ion-exchange resin Amberlyst 15® (85 g) was in this particular case washed with methanol (Soxhlet extraction), dried in vacuo at ca. 70° C. for six hours prior to use. The following were charged to the autoclave: acetic acid (3600 g), BHT (2,6-di-t-butyl-4-methylphenol, 3.0 g) and internal standard (n-decane, ca. 18 g). The desired amount of deionised water was then added to the acetic acid. The autoclave was then pressurised with N 2 and vented (three times). The reaction mixture was stirred (at ca. 1200 rpm), heated to the desired temperature (50° C.) and finally butadiene (700 g) was added. The progress of the reaction was monitored by GC analysis.
FIGS. 4-6 (see below) summarise the results obtained by varying the w/w % of water in acetic acid charge. The experiments described above show that the rate of reaction, the conversion of the starting materials and the selectivity towards the two product C 4 -isomers, crotyl acetate and sec-butenyl acetate, was heavily affected by the water concentration during the individual autoclave reaction runs. The effect of water upon the reaction was explored ranging from 0.14% to 1.68% of w/w of water (based on the starting material acetic acid) and is illustrated in FIGS. 4 and 5 .
The rate of C 4 -isomer formation was estimated by linear regression ( FIG. 4 ) and this analysis clearly identified 0.35% w/w water as the concentration which resulted in the fastest formation of both sec-butenyl acetate and crotyl acetate. This particular water concentration also led in the highest production of C 4 -isomers at a total C 4 selectivity which was not significantly lower than those of the other water concentrations tested, especially when the much higher conversion of the starting materials was taken into consideration (see FIGS. 4 and 5 ).
Example 27
These examples investigated the use of triflic acid (trifluoromethanesulphonic acid) and triflate salts as catalysts for the addition reaction between butadiene and the saturated aliphatic carboxylic acid (step a)).
The experiments in this example were carried out in a 10 L stainless steel autoclave. The catalyst to be investigated was introduced into the autoclave as a solution in acetic acid. The reaction mixture was heated to the desired temperature. At the same time, a feed vessel was filled with the amount of 1,3-butadiene required and slightly pressurised with nitrogen. As soon as the autoclave reached the required temperature, 1,3-butadiene was added to the autoclave in one aliquot.
a) Triflic acid
The autoclave charge used is shown below:
Catalyst:—trifluoromethanesulphonic acid (triflic acid) 50 g.
Temp.:—50° C. Charge: acetic acid 3668 g.
BHT (inhibitor) 3.0 g. decane 72.1606 g.
Addition:—butadiene 705 g.
The table below shows the run results:
Triflic acid R6/1 1 2 3 4 5 6 7 8 Component Run time mins. % w/w 5 50 99 168 200 252 321 354 acetic acid 72.50 84.12 82.38 82.87 81.68 80.95 81.22 81.16 sec-butenyl 0.23 1.53 2.35 2.93 3.13 3.29 3.39 3.40 acetate C8 butadiene 0.18 0.07 0.13 0.20 0.23 0.22 0.31 0.32 dimers crotyl acetate 3.06 1.50 2.68 3.56 3.90 4.26 4.40 4.42 4-vinyl 0.10 0.10 0.09 0.09 0.08 0.08 0.08 0.07 cyclohexene C8 acetates 0.32 0.36 1.34 1.82 2.36 2.98 2.97 3.11 C12 butadienes <0.01 0.16 0.03 0.05 0.06 0.06 0.18 0.16 trimers
b) Lanthanide Triflates
Three trials were conducted, 1 2 and 3 (see below).
1) Catalyst:—ytterbium trifluoromethanesulphonate (ytterbium triflate) 60.2 g.
Temp.:—50° C. Charge:—acetic acid 3676 g.
bht (inhibitor) 3.0 g. decane 68.5285 g.
Addition:—butadiene 700 g.
2) Catalyst:—ytterbium trifluoromethanesulphonate (ytterbium triflate) 60.2 g.
Temp.:—135-145° C. (set 135° C.) Charge:—acetic acid 3676 g.
bht (inhibitor) 3.0 g. decane 68.5285 g.
Addition:—butadiene 700 g.+310 g.
3) Catalyst:—lanthanum trifluoromethanesulphonate (lanthanum triflate).
Temp:—102° C. Charge:—acetic acid 3852 g.
bht (inhibitor) 0 g. decane 0 g. lanthanum acetate 32.7 g. triflic acid 50 g.
Addition:—butadiene 703 g.
The method outlined for triflic acid was followed except in trial 2) the autoclave was re-charged with the material from trial a). A fresh charge of butadiene was added. In trial 3 the lanthanum triflate was prepared in situ by adding lanthanum acetate and triflic acid (2.8 eq./La) as separate components to the charge. The results of the three trials are tabulated below:
trial so.
1
2
3
Run time mins.
236
241
251
Component % w/w
acetic acid
80.65
83.65
77.24
secondary
0.04
1.81
2.67
C8 butadiene
0.01
0.11
0.16
dimers
Crotyl acetate
0.02
2.42
3.61
4-vinyl
0.14
0.07
0.07
cyclohexene
C8 acetate
0.01
1.07
1.93
C12 butadiene
<0.01
0.04
0.03
trimers | Process for making a butyl ester from butadiene, comprising (a) reacting butadiene with a saturated aliphatic monocarboxylic acid to form a mixture of n-butenyl and secondary butenyl esters, (b) separating the n-butenyl ester from the secondary butenyl ester, and (c) hydrogenating the n-butenyl ester separated in step (b) in the presence of a catalyst to the corresponding n-butyl ester. | 2 |
BACKGROUND OF THE INVENTION
The present invention refers to the extraction of parallelepiped shaped blocks of rock from a rock formation and to an extractor to be used for such purpose.
The extraction of ornamental blocks of rock from rock formations, especially of granite, began to show signs of advancement in recent years with the development of specific explosives. Such explosives are placed in drill holes aligned along one or more cutting planes and then detonated simultaneously so as to make extraction more rapid.
FIGS. 1 to 4 of the accompanying drawings illustrate the most common method presently used for the extraction of blocks of rock from solid rock formations. Fundamentally, it comprises the following steps:
Step 1: as shown in FIG. 1, a large block of rock having, for example, a volume of 100 to 400 cubic meters is freed from the rock formation. Slots or channels are opened along the sides of the block of rock to be removed so as to relieve internal stresses. The slots or channels are normally opened by means of jet flame burners or slot-drills forming secant perforations.
Rear, vertical and/or horizontal perforations are then drilled and the rock block is separated by the simultaneous detonation of explosives placed in such perforations.
One manner of carrying out this method is to take advantage of the natural separations found in many rock formations. In order to extract the block, it is sufficient to drill the spaced aligned perforations suitably arranged in a plane normal to the plane defined by the natural separation in the rock formation and then to detonate the explosives placed in such perforations.
Another manner is not to make the vertical perforations, but rather to open a rear slot or channel and to drill perforations in the plane of the natural separation, then simultaneously detonating the explosives placed in such perforations.
Stage 2: as shown in FIG. 2, in this step the block of rock is sub-divided along the planes of separation defined by corresponding aligned drillings, separation being obtained by means of explosives or metal plugs driven into the drillings so as to produce smaller blocks of rock of commercial size.
Stage 3: as shown in FIG. 3, this stage concerns the finishing of the block of rock by squaring it perfectly using closely spaced aligned drillings, the block being cut by means of plugs driven into the drillings or alternatively cutting is effected by means of manual tools. Only then will the block be in condition for being passed for final processing in rock slicing machines.
The following problems in the above method are to be noted:
low yield. When explosives are used, the block does not always separate from the rock formation in the manner intended, be it due to lack of precision in the calculations for the explosive, be it due to a misalignment of the rear perforations with respect to the cutting plane;
since the vertical and horizontal perforations are normally deep, it is necessary, as shown in FIG. 4, to provide for an angle greater than 90° between the planes formed therebetween so as to avoid jamming of the separated block. This makes it necessary to square the block of rock later which means loss of material and additional finishing work.
The purpose of the present invention is to overcome the majority of the above problems by means of a process that permits the extraction of effectively already finished blocks that do not have the cracks or microfissures that usually appear when conventional processes are used, thus ensuring an improved yield with less labour.
A further object of the present invention is to provide an extractor of blocks of rock for carrying out the process.
SUMMARY OF THE INVENTION
According to the present invention, a process for preparing the exposed surface of a rock formation to permit the extraction of parallelepiped shaped blocks of rock ready for final processing, comprises the steps of:
a) cutting into the surface of the rock formation a slot having a depth substantially equal to a width dimension of said blocks;
b) drilling into said surface of the rock formation a first series of parallel aligned perforations orthogonal to said slot, said perforations terminating along the bottom of said slot and defining a first cutting surface orthogonal to the plane of said slot;
c) drilling into said surface of the rock formation a plurality of parallel second series of parallel aligned perforations, said perforations of each of said second series defining a second cutting surface orthogonal to the plane of said slot and to said first cutting surface;
d) separating by the use of plugs applied in the perforations of said first and second series, the blocks defined by steps a) to c); and
e) carrying out steps a) to d) repeatedly so the slot of step a) is cut from the exposed surface of the rock formation, beginning along a line defined by the outer ends of the perforations of said first series of perforations, whereby the exposed surface of the rock formation, after extraction of the various blocks in steps d), acquires a stepped profile.
Further according to the invention, a process for extracting parallelepiped shaped blocks of rock ready for final processing, from a rock formation having an exposed surface with a stepped profile, comprises the steps of:
a) cutting orthogonally into a first surface of one step of said stepped profile a slot of a depth equal to that of the second surface of the same step, said slot being cut slightly above the plane of the second surface of the immediately previous step;
b) cutting orthogonally into the second surface of the same step a first series of parallel aligned perforations along the junction between said second surface of the same step and the first surface of the immediately following step, the perforations of the first series extending to the bottom of said slot;
c) cutting orthogonally into the second surface of the same step a plurality of parallel second series of parallel aligned perforations extending to said slot, said second series defining lines normal to said junction;
d) separating by the use of plugs applied in the perforations of said first, and second series, the blocks defined by steps a) to c); and
e) repeating steps a) to d) with respect to the following steps of the profile of said rock formation, extracting the respective blocks of rock.
Preferably, the slot is cut by means of secant perforations and the first, second and third series of perforations are effected by drilling hammers.
The present invention also provides an extractor for extracting blocks of rock from a rock formation, that comprises a structure formed by a front frame, a central frame and a rear frame, said front and rear frames being perpendicular to said central frame, each said frame being associated with at least one respective perforation system.
Each perforation system preferably includes at least one pair of rails and a support carriage mounted for displacement along said rails, the pairs of rails of the three perforation systems being orthogonal with respect to each other.
Moreover, the support carriage of each perforation system may include a pair of upright support guides perpendicular to its respective pair of rails, a perforation tool being displaceable along said support guides.
The perforation system associated with said front frame may be a slot-cutter whereas the perforation systems associated with the central and rear frames may comprise hammer drills.
The carriages of the extractor are preferably driven by electric motors and locking means may be provided for locking each carriage in predetermined positions along their respective pairs of rails, adjustable support jacks being arranged under said central and rear frames for the correct positioning of said extractor on a rock formation.
Auxiliary wheels on the central and rear frames may be included for the support and displacement of the extractor over the rock formation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 to 4 show the sequence of steps in a prior art method of extracting blocks of rock from solid rock formations;
FIG. 5 illustrates a slice of rock removed from a solid rock formation in a first step in preparing a stepped profile for a method according to the present invention;
FIG. 6 shows the same slice of rock after one face has been separated from the formation;
FIG. 6a shows the slice of rock after its second face has been severed from the formation;
FIG. 7 is a front view of the formation indicating a suitable position for the cuts to be made for separating the slice of rock;
FIG. 7a is a longitudinal section illustrating the manner of choosing the longitudinal axis of the slice;
FIG. 8 shows the slice of FIGS. 7 and 7a when a first face has been severed from the formation;
FIG. 9 illustrates the manner of selecting the position of the cuts to remove a slice of rock when the surface of the formation falls away to a lesser extent at one end than in the case of FIG. 7a;
FIG. 9a illustrates the manner of selecting the position of the cuts to remove a slice of rock when the surface of the formation falls away to a lesser extent at both ends than in the case of FIG. 7a;
FIG. 10 is a perspective view of a reentrance opened in the rock formation as a first stage for the removal of the initial slice of rock;
FIG. 11 is a perspective view of a typical block of rock to be removed according to the method of the present invention;
FIGS. 12 to 16 show the sequence of steps removing a series of slices of rock to prepare the stepped formation in the rock formation;
FIGS. 17 to 23 show the sequence of steps in which blocks of rock are removed in accordance with the invention and further slices of rock are removed as necessary;
FIG. 24 illustrates the minimum space possible for the cutting of the first face of a block;
FIG. 25 shows the cutting of the second face of a block;
FIG. 26 shows a slice of rock from which blocks are being produced;
FIGS. 27, 28, and 29 are perspective illustrations of the three steps of cutting and removing blocks of rock according to the method of this invention;
FIGS. 30 and 31 illustrate the use of a fork lift loader to remove a block of rock;
FIG. 32 is a simplified representation of a three frame extractor used in the method of the present invention;
FIG. 33 is a side view of the extractor;
FIG. 34 shows the front frame of the extractor;
FIG. 35 shows the rear frame of the extractor;
FIG. 36 shows the central frame of the extractor;
FIG. 37 shows a cable and winch system for displacing the extractor;
FIG. 38 is a detail showing the manner in which the extractor is supported during displacement;
FIG. 39 shows how the rear frame is supported during displacement; and
FIG. 40 is a detailed perspective view of the complete structure of the extractor during use.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A process according to the present invention will now be described, by way of example, with reference to FIGS. 5 to 30 of the accompanying drawings, in which:
FIG. 5 shows a slice of rock displaced from the rock formation and having a width and height equal to the thickness (e) and length (c) of the blocks of rock to be extracted.
After the slice of rock is freed, it is chopped into blocks of rock having the desired width L of the blocks so that they can be extracted without requiring finishing.
In this process the slot or channel is opened with a slot-drill using secant perforations. The slot is opened on or near the rising or levant plane of the rock formation and has a depth equal to the depth of the block of rock to be extracted.
In the conventional processes, the slot is opened vertically or perpendicularly to natural separations, when there are any in the rock formation, and is normally deeper than that used in the present process.
Since the depth of the slot is now limited to the thickness of the blocks, its opening is facilitated in a position where it is difficult to work, it being possible to make it horizontal or inclined to accompany the levant plane of the rock formation.
FIG. 6 shows the slice of rock with the bottom slot opened and still held to the rock formation by means of face B. When face B is cut by means of plugs, the weight of the block makes it displace itself by a few centimeters which assists in the freeing of the individual blocks at the time of their extraction. (See FIG. 6a.)
Since the height of the slice of rock is limited to the length of the blocks to be extracted, cutting face B, which is still part of the rock formation, by means of metal plugs is facilitated, there being no need for the use of explosives.
FIG. 7 is a front view of the rock formation and preliminarily defines the most suitable position for extraction of the blocks of rock, taking the following into consideration:
the cutting planes of the rock. The closer the perforations are situated to such planes, the more spaced they may be, which makes extraction more economical;
the designs on the rock formation in relation to the finished blocks; and
the equipment to be used for manoeuvering the blocks of rock during extraction.
Once the position of the slice of rock to be extracted from the rock formation has been defined, a slot A is first opened in the surface of the rock formation by means of continuous cut drilling to define a face A. Preferably, face A accompanies the levant plane of the formation and the corresponding slot A is opened using secant perforations.
Face B, perpendicular to face A, is cut using metal plugs, in a plane of perforations made with hammer drills, the spacing between perforations being determined by the type of rock formation.
As shown in FIG. 7a, axis YY'--which is the intersection of faces A and B--should be positioned in such a way that it passes out of the exposed surface of the rock formation at its two ends, it having an inclination (alpha) with respect to the horizontal that permits gravity assisted withdrawal of the blocks. As can be seen from FIG. 8, after cutting of face A, the material (slice of rock) to be initially extracted will be held to the formation only by face B.
It will be understood from FIGS. 9 and 9a that, if the rock formation does not fall away at the two ends of axis YY', it will be necessary to open a slot with the slot rill using secant perforations at one of the ends of axis YY', depending on the case.
FIG. 10 is a perspective view of the reentrance opened in the rock formation during the first stage of removal of the initial slice of rock.
The material extracted on forming faces A and B (see also FIG. 12) does not provide blocks of rock at this stage. It will be cut into sizes that may be removed with the handling equipment available at the site. Such cutting may be effected using explosives in split perforations.
Next, face A 1 , parallel to face A, is cut using the same method of cutting as used for face A. The distance between face A and face A 1 will be the length (c) of the extracted block plus an amount Z.
FIG. 13 shows the cutting of face B 1 parallel to face B, using the same method as for cutting face B. The distance between face B and face B 1 will be the same as the thickness (e) of the block of rock to be extracted.
The mass of rock between faces A 1 and B 1 will not produce a block and will be extracted precisely as was that between faces A and B.
FIG. 14 shows the sequential cutting of faces A 2 and B 2 . Face A 2 is parallel to face A 1 with a spacing Z. The mass of rock delimited by faces A 2 and B 2 will be extracted just as in the case of the mass between faces A and B.
As shown in FIG. 15, faces A 3 and B 3 are then cut. Face A 3 is parallel to face A 2 and their spacing is equal to the distance between faces A and A 1 . Face B 3 is parallel to face B 2 and their spacing is the same as the thickness (e) of the block of rock to be extracted. The mass of rock delimited by faces A 3 and B 3 is removed in the same manner as the mass between faces A and B, as shown in FIG. 15.
Whenever a new face An is cut, it will be separated from face A n-1 by (c+Z). If it does not attain this value, then the latter will be only Z.
FIG. 16 shows the cutting of faces A 4 and B 4 in the same manner as faces A 2 and B 2 and the mass of rock therebetween will be removed as in the case of the mass between faces A and B.
Faces A 1 ' are B 1 ' are cut, face A 1 ' being spaced by Z from face A and face B 1 ' following the direction of face B 1 at the point where the perforatons in face B 1 terminate.
FIGS. 17 to 23 show the sequence of the continuation of the cutting of slices from faces A n and B n .
As is shown in FIG. 24, Z is the smallest dimension in which the drill succeeds in cutting between two faces An and A n-1 , it being noted that, in order to cut a face B n of a slice, it has to has to have the continuity of face B n of the immediately following or upper block of rock.
FIG. 25 shows a plug F. In order to cut a face B n next to a step, one has to use a plug F having a body length K greater than Z.
FIG. 26 shows a slice of rock when blocks are being produced. The slice formed by faces A n and B n is sliced during block extraction along faces C, C 1 , C 2 . . . C n which are parallel to each other and perpendicular to axis YY', being spaced from each other by a distance equal to the width L of the blocks of rock to be extracted.
As shown in FIG. 27, the cutting of faces C n is effected using metal plugs in drilling planes made with hammer drills, the perforation interspacings being determined by the type of rock.
With reference to FIG. 28, cutting of faces C n with plugs is only effected after removing the block of rock originating from face C n-1 . After cutting face C n with plugs, a larger diameter plug G is used at the lower region of face C n to separate the block of rock at this point from the rest of the slice of rock by a further 1 or 2 centimeters, this avoiding jamming. After this procedure, a steel cable Q is tied to the top of the block of rock and hauled in the direction of axis YY'. As can be seen from FIG. 29, the block of rock which was at right angles to axis YY', turns about an axis formed by face An with face C n so as to lie along axis YY'. This rotation is relatively smooth since the block of rock is supported and therefore will be dragged over face B during the turn without damaging the block. Once it is lying in position, the block of rock will be further hauled until it leaves the rock formation. It will then be ready, without any need for squaring operations or other basic finishing.
It should be noted that, at this point, the first cuts C, C 1 , C 2 . . . made in triangular parts of the rock slices will not produce blocks of rock and the distances between such cuts are determined as a function of the masses of rock to be removed.
On removal of the last slice from faces A n and B n , a formation L-L 1 -L 2 will appear, representing the total volume f worked rock, as can be seen from FIG. 23.
It will be observed that the last blocks of rock supported on face B n at the end of the formation will have a smaller thickness (e) due to the impossibility of maintaining the same alignment during cutting of such last face.
When axis YY' perforates the rock at its lower end (FIG. 9), the block of rock may be hauled off the rock formation with steel cables, it being possible to adjust angle alpha so as to make better use of gravity assistance during this manoeuver.
Where there is no possibility of hauling along axis YY' (FIG. 9a), the blocks of rock may be removed by strategically placed cranes.
As shown in FIG. 30, when fork lift loaders are used to handle the blocks of rock, they will require platforms on which they can be driven. For this purpose, axis YY' will be made close to horizontal with a small inclination sufficient to ensure suitable drainage of rain water, as seen in FIG. 31. A layer of earth will then be spread over the tops of the blocks of rock (face A) so as to produce a platform having a regular surface where it is easy to operate the loaders. This earth will be removed as the lower platform advances.
The process of the present invention provides for the slots or channels of secant perforations to be opened in an inclined position varying from 45° to almost horizontal. Existing equipment for opening such slots have been designed to work vertically or nearly vertically and at depths of up to six meters, it being difficult to adapt them to surfaces with steep inclinations.
An extractor for blocks of rock according to the present invention will now be described in detail with respect to an exemplary embodiment shown in FIGS. 32 to 40.
FIGS. 32 and 33 show such an extractor which comprises a metallic structure formed from a front frame R, a central frame T and a rear frame S. Front frame R and rear frame S are perpendicular to central frame T, each having a respective perforation system.
As can be seen in FIG. 34, the front frame is comprised of a two-rail track 1 supported on three bars 2. On track 1 runs a carriage 3 which is the support for an upright support guide 4 that carries a slot drill P 1 that opens the slot or channel of secant perforations. Carriage 3 is displaceable by means of a chain 5 driven by electric motor M 1 . The upper portion of track 1 is provided with orifices 18 with spacings equal to the spacings between the perforations made in opening the continuous slot. Carriage 3 has an orifice 19 that coincides with orifices 18 so that it may be locked during opening of the perforations by drill P 1 (FIG. 34).
FIG. 35 shows that rear frame S is comprised of a two-rail track 6 supported on three supports 7. A carriage 8 runs on this track and mounts support guide 9 that carries a hammer drill P 2 which opens the face B perforations perpendicular to the continuous slot of face A. Carriage 8 is also moved by a chain 10 driven by an electric motor M 2 . The upper portion of track 6 is formed with orifices 20 with spacings equal to the spacing between the perforations made by hammer drill P 2 . Carriage 8 has an orifice 21 that will coincide with orifices 20, permitting locking during drilling by hammer drill P 2 .
FIG. 36 shows the central frame T that is comprised of three two-rail tracks 11 supported on parts 12 and 13. Part 12 serves as a base for the three bars 2 of front frame R. In their turn, tracks 11 support the three bars 7 of the rear frame S. On each track 11 runs a carriage 14 mounting a support guide 15 that carries a hammer drill P 3 for drilling the perforations parallel to the slot in the blocks of rock. Carriage 14 runs on a rack 16, being moved by a cooperating pinion driven by an electric motor M 3 . Each track 11 is provided with orifices 22 with spacings equal to the spacing between the perforations made by the corresponding hammer drill P 3 . Carriage 14 has an orifice 23 that coincides with orifices 22, permitting locking during drilling by hammer drill P 3 .
Frames R, S and T are reinforced with auxiliary beams 17 to increase the rigidity of the structure.
As shown in FIG. 37, in order to change the working position, the extractor may be displaced by a system of steel cables 24 operated by a winch 25.
FIG. 38 shows how the extractor is supported during displacement. This is effected by means of three guide wheels 26 positioned at the edge formed by faces A and B of the slice of rock that have already been cut, as well as of four auxiliary wheels 27.
During drilling, the extractor is supported on four support jacks 28 that permit the correct positioning of the extractor on the rock.
FIG. 39 shows how the rear frame S is displaced along tracks 11 so as to facilitate the initial phase of drilling. In this position, both the auxiliary wheels 27 and the support jacks 28 work in positions that are perpendicular to the rock. As shown in FIG. 38, such wheels and jacks are pivotally mounted on the extractor.
Finally, FIG. 40 is a perspective view of the complete metal structure formed by frames R, S and T. The auxiliary reinforcement beams and two of the perforation systems, however, are omitted for clarity of representation.
It is believed that the advantages of the present invention when compared with the conventional techniques described at the beginning of this specification will be abundantly clear to a person versed in the art. This, however, is further emphasized when one considers that, quite apart from the savings in labour costs and the convenience of not having to provide a site for the various finishing operations of the prior art, an enormous increase in yield of the reserve of rock in the formation may be obtained. This can to a certain extent be estimated in numerical terms. For example, in a given rock formation, as little as 20% of the rock removed may be used for commercialisation. Using the method and preferred embodiment of extractor of the present invention, on the other hand, this yield may be increased to values exceeding 60%.
It will also be appreciated that the method of this invention does not depend exclusively on the use of the specific extractor illustrated and described herein. Thus much of the benefit of the invention can still be obtained if the perforation and cutting of each face B n is terminated before the perforation and cutting of the individual faces C 1 to C n , this latter being done after the whole slice of rock has been separated from the rock formation. | The present invention refers to the extraction from rock formations of blocks of rock that are already of a paralellepiped shape and thus do not require final time consuming finishing operations. The process of the invention involves cutting a long slot in the formation beneath a slice of rock to be removed and then drilling various orthogonal series of parallel aligned perforations to define cutting surfaces that are separated using metal plugs applied to the perforations. In this manner parallelepiped shaped small blocks are obtained directly and can be removed from the formation in a stage virtually ready for commercialization. Equipment in the form of an extractor is also described which permits the simultaneous formation of the slot and the perforations. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to electrical connectors. Specifically, it relates to high speed, modular cable connectors.
2. Brief Description of Prior Developments
U.S. patent application Ser. No. 08/974536 filed Nov. 19, 1997 (owned by the assignee of the present application and incorporated by reference herein) discloses high speed cable connectors having terminal carriers mounted on circuit substrates. These connectors are modular and provide high performance. However, there is a desire to maintain such performance but reduce manufacturing costs.
SUMMARY OF THE INVENTION
This invention relates to connectors having frames for retaining electrical terminals and providing cable receipt and attachment facilities. Terminals can be mounted in the frame from relatively large open sides. Similarly, cable attachment can take place through such relatively large open sides. The sides can be closed by circuit substrates that provide for interconnection of terminals with cable attachment points and/or with shields that overlie one or both sides of the frame.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of a first embodiment of a cable connector in accordance with the invention;
FIG. 2 is an exploded view of the connector shown in FIG. 1;
FIG. 3 is a top view of the frame of the connector shown in FIGS. 1 and 2;
FIG. 4 is a side cross-sectional view taken along line 4--4 of FIG. 3;
FIG. 5 is a plan view of the opposite side of the frame shown in FIG. 3;
FIG. 6 is an end view taken from the left-hand side of FIG. 3;
FIG. 7 is an isometric view of a contact terminal used in the connector illustrated in FIG. 1;
FIG. 8 is a side elevational view, partially in cross-section, of the terminal shown in FIG. 7 mounted in a terminal cavity;
FIG. 9 is an isometric view of the opposite side of the connector shown in FIG. 1;
FIG. 10 is an isometric view of a partially assembled modular cable connector using a plurality of modules of the type shown in FIG. 1;
FIG. 11 is an isometric view of a second embodiment of cable connector frame;
FIG. 12 is an exploded isometric view showing an assembly of elements utilizing the frame of FIG. 11;
FIG. 13 is an isometric view showing the insertion of terminals into the frame of FIG. 11;
FIG. 14 is an isometric view of the assembly shown in FIG. 13 with terminals retained in the frame;
FIG. 15 is an isometric view of the opposite side of the frame shown in FIG. 11;
FIG. 16 is an exploded isometric view of a third embodiment of the invention;
FIG. 17 is an isometric view of the assembly formed from the parts shown in FIG. 16;
FIG. 18 is an exploded isometric view of the elements depicted in FIG. 16 and a shield plate;
FIG. 19 is an isometric view of a terminal used in the embodiment illustrated in FIGS. 16-18;
FIG. 20 is a side elevational view of the terminal shown in FIG. 19;
FIG. 21 is a top plan view of the terminal illustrated in FIGS. 19 and 20; and
FIGS. 22 and 23 are cross-sectional views illustrating attachment of wires to circuit substrates.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Several embodiments are explained in the following description. Similar elements in each embodiment are identified by the same reference numeral, differentiated between embodiments by the use of single or multiple prime designations.
FIG. 1 illustrates a cable connector module 20 embodying the invention. The module 20 is formed of an insulative or dielectric body 22 that has a generally frame-like configuration defined by two opposed major surfaces 24 and 26 (FIG. 4) that are joined by a front edge member 28, a back edge member 30 and a pair of side edge members 32a and 32b. The body 22 is preferably formed by molding a polymeric resin having appropriate strength and heat resistant characteristics. The front edge member 28 defines a mating interface for receiving terminals of a mating connector through a plurality of openings 34. For example, the module 20 could mate with one column of an array of terminal pins arranged in rows and columns in a pin header backplane connector, with such pins generally be inserted into the openings 34 in a direction parallel to the longitudinal axis of the module 20.
A circuit substrate 36, preferably a generally planar printed circuit board, is received on one of the major sides 24 of the frame 22. The circuit substrate 36 is retained and located with respect to the frame 22 by a securing/locating post 38 receivable in opening 39 (FIG. 2) and a pair of locating lugs 40 received in openings 41. The post 38 and lugs 40 can also function as stand-offs to achieve a desired terminal pitch distance between adjacent stacked modules 20, as later explained. The outer surface of the circuit substrate 36 is preferable coplanar with surrounding portions of the frame 22. If shielding is desirable, the substrate 36 may be of multi-layer construction, incorporating a ground plane.
Cables C, which may or may not be accompanied by an associated drain wire D are introduced into the interior of the frame 22 through the rear edge member 30. As shown, each of the cables C preferably comprises a two wire, differential pair conductor. Such cables may include shielding (not shown).
Referring to FIGS. 2-6, the frame 22 includes shoulder surfaces 42 along each of the side edge members 32a and 32b. The circuit substrate 36 rests on these shoulder surfaces as well as other surfaces within the frame that are coplanar with shoulder 42.
A plurality of terminal receiving cavities 44 are formed along the front edge of the frame for receiving terminals 58 that are described below in more detail. Each of the cavities 44 is aligned with one of the openings 34 along the front edge member 28. Each cavity includes a terminal retention section such as a recess 46. The back ends of the cavity 44 are partially closed off by pairs of wall members 47. As illustrated in FIG. 2, the terminals 58 are inserted in the cavities 44 generally in the direction of arrow F. That is, generally in a direction that is perpendicular to the plane formed by the major surface 24.
A plurality of wire receiving cavities 48 are formed adjacent the rear edge member 30 of the frame 22. Dividing walls 50 form two cavities 48, one for each wire W of cables C. The cavities 48 communicate with cable entry openings 52 formed through the end member 30. If a drain wire D is present, the frame 22 will also include a drain wire cavity 54. The drain wire D enters the cavity 54 through a drain wire slot 56 (FIG. 5). When the circuit substrate 36 is mounted on the frame 22, access to wires W can be obtained from major surface 26 to secure the wires W onto the circuit substrate 36, as by soldering, welding, conductive adhesives or other means commonly used for obtaining electrical continuity between wires W and appropriate contact pads of circuit substrate 36.
FIG. 7 is an enlarged view showing a typical receptacle terminal 58. The terminal preferable includes a generally U-shaped base/securing section 60 having a generally flat base member 62 and two opposed arms 64a and 64b extending from each end of the base 62. Each arm 64a and 64b includes a distal mounting portion 66. Each distal mounting portion is bounded by a rear edge 65 and a front edge 67. Preferably a retention element, such as a barb 68, is carried on one or both of the edge surfaces 65 and 67. The bottom surface 70 of the base 62 is preferably flat and is plated or prepared in a manner that is receptive to solder. A pair of cantilever beams 72 extends from the base section 66 and carry opposed contact surfaces 74 that are adapted to engage a mating pin. The terminal 58 is preferably formed as a one piece stamping of suitable electrical terminal material, such as beryllium copper alloys and phosphor bronze alloys.
FIG. 8 illustrates the manner in which a terminal 58 is secured into a terminal cavity 44. The back end of the cavity includes a pair of end walls 47 and an intermediate retaining wall 49. The distance between the front surface 47a of each wall 47 and the rear surface 49a of the retaining wall 49 is substantially equal to the length, in the longitudinal direction of cavity 44, of the distal portion 66 of each terminal arm so that the distal portion 66 is received in an interference fit relationship in the slot 46 formed between front surface 47a and rear surface 49a. The retention barbs 68 engage the surfaces 49a of the retaining walls 49 for additional securing of the terminal 58 in the cavity 44.
The terminal 58 is retained in the frame 22 in a manner such that the surface 70 of the terminal is either coplanar with or spaced slightly by a distance t (FIG. 8)from the support plane formed by the supporting surfaces 25, such surfaces generally comprising the shoulder surface 42 and the top surfaces of the walls between cavities 44 and cavities 48. Such positioning is desirable to accommodate the presence of an adequate amount of solder paste disposed between the surfaces 70 and the facing surface of the circuit substrate 36. A complete connected module 20 is made by inserting a plurality of terminals 58 into terminal cavities 44. A quantity of solder paste is applied to the circuit substrate 36 by conventional means, such as through a solder mask. Then, the circuit substrate 36 is pressed onto the frame 22 and is held into position by the peg 38 and lugs 40. Thereafter, the assembly comprising the frame 22, circuit substrate 36 and terminals 58 undergoes a re-flow operation to effect a solder connection between the terminals 58 and contact pads (not shown) at the front ends of circuit traces T (FIG. 9) of the circuit substrate 36. Such an assembly can then be affixed to cables to form a cable assembly by soldering the stripped portions R of wires W (FIG. 1) to contact pads (not shown) at the rear ends of tracks T.
Such a cable assembly is illustrated in FIG. 9. As shown, each of the conductors or wires W from one of the cables C is positioned in one of the wire cavities 48 by inserting the cable end through an opening 52 in the end member 30. Each of the wires W is arranged on one or the other side of wall 50. The stripped ends of wires R are positioned over appropriate contact pads formed at the ends of circuit traces T on the circuit substrate 36. By reason of the fact that the cavities 48 are open to the major surface 26, there is ready access to the wires W for purposes of soldering, welding or otherwise securing such conductors to the circuit traces T. If a drain wire D is present, in a similar fashion it is introduced into an appropriate cavity 54 through grove 56. The cavity 54 provides access for soldering or otherwise affixing the drain wire D to an appropriate trace on the circuit substrate 36. The surface 26 of the frame 22 is provided with locating features, such as the circular boss 75 (FIG. 9) and locating lugs 77. The boss 75 is sized and positioned to engage the peg 38 of an adjacent stacked module and the locating lugs 77 are sized and positioned to receive and locate the lugs 44 of an adjacent stacked module, thereby facilitating alignment of the modules 20. The module to module terminal pitch distance, for example 2 mm to match the 2 mm centerline pitch between adjacent columns of a pin header, be regulated by the axial length of post 38 and the height of lugs 40 and/or the height of boss 75 and lugs 77. As a result, these elements may create a stand-off distance or air gap between adjacent stacked modules, that can influence impedance of the connector.
Referring to FIG. 10, a multi-conductor shielded cable connector can be formed by stacking a plurality of modules 20 and enclosing the stack within mating halves 76 of a shield. Such mating shields of this type have previously been described in published PCT Patent Application W097/47058 filed in the name of the assignee of this application (the disclosure of which is incorporated herein by reference) and in co-pending U.S. patent application Ser. No. 08/941824 filed Oct. 1, 1997 and U.S. patent application 09/041917 filed Mar. 12, 1998, both of which are owned by the assignee of this application and both of which are incorporated herein by reference.
In FIGS. 11, 12, 13 and 14, a second embodiment of connector module 20' is illustrated. Referring to FIG. 11, the frame or body member 22' has many of the features of the frame 22 previously described. It differs primarily in the addition of locating/guidance bodies 78a, 78b and 78c formed on side member 32a' and locating/guidance members 78d, 78e and 78f formed on side member 32b' (FIG. 12). The members 78a-d primarily provide a means for locating the modules in correct orientation in a shield, such as shield 76, and provide guidance structures extending beyond the shield for guiding a cable connector into a mating header, as described in the patent applications identified in the previous paragraph.
The bodies 78a-78d are arranged so that the distance S (FIG. 12) is just slightly greater than the width of module 20. Thus module 20 as shown in the previous embodiment, can be located and aligned in stacked relation to a module 20' formed from the frame member 22'. Terminal pitch between modules can be controlled by the height of boss 75' and standoffs 41' (FIG. 12).
As illustrated in FIGS. 12 and 13, the terminals 58 are inserted into terminal cavities 44' and are retained therein by structure as illustrated in the previous embodiment. Once the assembly of the frame 22' and terminals 58 is completed, that assembly is associated with a circuit substrate 36. Under preferred manufacturing conditions, the individual circuit substrates 36 are formed in multiples from a larger sheet represented by the numeral 80. The individual substrates 36 are held in the larger sheet by narrow bridging elements 82 that are designed to be easily ruptured. Each of the substrates includes terminal contact pads 84 and wire contact pads 86 formed at each end of continuous circuit traces (not shown). Substrate 86 also includes a ground contact pad 88 that includes a generally width-wise extending portion 89. The ground pad 88 may have a ground wire, if present, soldered to it. Also, shields, if present in the cables C, can be soldered or otherwise electrically associated with the width-wise extending portion 89. The ground pad 88 may be connected to a ground plane (not shown) formed within the circuit substrate 36. A connector module is assembled in the manner previously described, using a preferred technique of applying solder paste through a mask to the terminal contact pads 84. The assembly comprising the frame 22' and terminals 58 is then pressed onto the circuit substrate and the resulting assembly thereafter undergoes a reflow operation to solder the terminals onto circuit substrate 36.
As in the previous embodiment, the frame 22' includes openings 52' and 56' for the cables and drain wire, as previously described. As shown in FIG. 14, the terminals 58 are assembled in the frame 22' with the solder receiving surfaces 70 of the terminals coplanar or slightly spaced from the plane formed by the surfaces 25'.
FIGS. 16-18 illustrate a third embodiment of connector module 20". This embodiment differs from the previous embodiments by eliminating the need for the circuit substrate 36, 36'. In this embodiment, the frame 22" includes a plurality of terminal receiving cavities 44' that communicate with pin receiving openings 34". The contact terminals 90 are inserted into the cavities 44" through the major surface 26" that is opposite to the major surface 24 and 24' of the previous embodiments. As in previous embodiments, the end member 30" includes cable receiving openings 52' for receiving cables in cable receiving cavities 48" that are formed on each side of separating walls 50". The cavities 44" differ from those previously described by having a pair of flanking terminal securing walls 91 formed in each cavity (FIG. 17). The walls 91 each have a forwardly disposed surface 92 and a rearwardly disposed surface 94. In addition, the cavities 44" extend rearwardly and have a floor section 96 extending to the wire receiving cavities 48". Referring to FIGS. 19, 20 and 21, each terminal 90 includes a U-shaped base section having a transverse base 62' and a pair of upstanding arms 64a' and 64b' as previously described. Cantilever beams 72' extend forwardly from the arms 64a', 64b' and carry contact sections 74' for engaging a pin. Each of the terminals 90 includes a rearwardly extending neck portion 98 and a securing plate 100 having laterally extending portions. The laterally extending portions include locking tabs 102 that preferably are lanced from plate 100. A terminal tail portion 104 extends from the plate 100. The base 62', neck 98 plate 100 and tail portion 104 preferably are substantially coplanar and colinear.
As illustrated in FIG. 17, the terminals 90 are pressed into the cavities 44'. The terminals 90 are retained by an interference fit formed between the surfaces 92 and 94 of the securing walls 91 and the rear edge surfaces 65 and forward surfaces of the locking tabs 102. As shown in FIG. 17, the two pairs of outer terminals 90 are each positioned with the securing base 100 and tail 104 resting on the floor 96 of the cavity. Wires are inserted into the wire cavities 48" with insulation stripped portions overlying the tail portions 104. Attachment of the wires to the tail portions by soldering, welding, conductive adhesives or other means, such as IDC connections, crimping etc. can readily be achieved through open major side 26'.
In this embodiment, the centrally disposed terminal 90' is meant to function as a ground terminal. In this case, the cavity 44" receiving the terminal 90' has a shorter floor section 99 so that the tail portion 104 extends beyond the floor for purposes as will be later described.
Referring to FIG. 18, this third embodiment can include a shield plate 106 disposed on one side of the module. The shield plate 106 includes a pair of upstanding, preferably barbed retaining tangs 108. The retaining tangs 108 are received in slots 112 (FIG. 17) and retained therein by an interference fit, thereby holding the shield onto the frame 22". As shown in FIG. 18 the shield 106 also includes a raised contact portion 110. When the shield is fixed onto the frame 22', the contact member 110 engages the underside of the tail section 104 of the ground terminal 90', thereby establishing an electrical connection between the ground terminal 90' and shield. As with previous embodiments, provision can also be made for ground wires and shielding braids to be attached to the shield 106.
As previously described and with reference to FIGS. 22 and 23, the stripped portions R of wires W are affixed to contact pads 114 of the traces by suitable means. One particular means that has been found particularly useful is to pre-tin the strands of the wires w and then solder them onto the pads 114 by means of an appropriately shaped tool 116, that essentially comprises a heated electrode. Of course, other means may be utilized for soldering, welding or otherwise electrically and mechanically fixing the wires W onto the contact pads 114.
While the present invention has been described in connection with the preferred embodiments of the various figures, it is to be understood that other similar embodiments may be used or modifications and additions may be made to the described embodiment for performing the same function of the present invention without deviating therefrom. Therefore, the present invention should not be limited to any single embodiment, but rather construed in breadth and scope in accordance with the recitation of the appended claims. | Connectors are formed from insulative, terminal-carrying frames that are open on at least one major surface. The open major surfaces allows rapid insertion of contact terminals and attachment of wires to contact surfaces within the frame. The frame includes wire receiving openings and cavities for positioning wires within the frame. Electrical continuity between the wires and the terminals may be achieved directly or by a circuit substrate that has circuit traces for electrically connecting an attached wire to a connector terminal. High speed cable connectors can be made in an industrially effective manner by such structures. | 8 |
RELATED APPLICATIONS
[0001] This application claims benefit of earlier filed Provisional Application Serial No. 60/253,918 filed on Nov. 29, 2000.
BACKGROUND OF THE INVENTION
[0002] This invention relates to computerized processes for financial planning for individuals and groups whose financial portfolio would be subject to tax on certain events. More, particularly, this invention is a method for transforming the usual pretax information for calculation of an efficient frontier, unique to an investor's portfolio, in such a manner that any portfolio on the calculated frontier is efficient after incorporating the effect of taxes on the risk and expected return of each asset class permitted in the investor's portfolio. In this context an “efficient frontier” is the set of all efficient portfolios. An after-tax efficient portfolio is one that provides the greatest expected after-tax total return for a given level of after-tax risk. In order to structure a portfolio for an individual investor, one must take the effects of taxes into account, since taxes levied on investment outcomes, typically on income and realized capital gains, may have an important impact on net portfolio results.
SUMMARY OF THE INVENTION
[0003] This invention addresses how this may be done and how certain facets of the process may be incorporated into a computer program or system so as to provide convenience to the potential user.
[0004] The invention achieves its purpose by transformation of pretax input data typically used in the current state-of-the-art optimization processes. It may be applied to any such process that seeks to minimize risk that may be calculated as a function of the standard deviations of each asset class and their covariances or correlations. The invention may most typically be applied to facilitate portfolio optimization under the widely-used paradigm derived from the work of Harry M. Markowitz (see for example “Portfolio Selection,” Journal of Finance (March 1952), and Portfolio Selection: Efficient Diversification of Investments (New York: John Wiley & Sons, 1959) which publications, to the extent it is consistent with our invention, is hereby incorporated by reference), commonly referred to as mean-variance efficiency. In such an approach the risk function is a quadratic form. Of course this invention could also, quite naturally, be applied to extensions of the Markowitz approach, such as described by Michaud and Michaud (Michaud, Efficient Asset Management, A Practical Guide to Stock Portfolio Optimization and Asset Allocation, 1998, which publication, to the extent it is consistent with our invention, is hereby incorporated by reference). Alternatively, it could be applied to any form of risk function which is based on the aforementioned statistical characteristics and which may be solved by algorithms for calculating a minimum, subject to linear constraints. The essential purpose of the invention is to establish a means and process by which i) both pre-tax and after-tax portfolio restrictions may be transformed into a set of consistent linear after-tax constraints, ii) the pre-tax characteristics of asset classes under consideration for the investor's portfolio may be transformed into after-tax characteristics, and iii) the prescribed efficient portfolios may be presented to the investor in pre-tax form, usually as hypothetical portfolios along the efficient frontier. It is also an object of this invention to provide a method of creating a derived asset class from the tax parameters, expected returns, and standard deviations of more than one, predefined asset class.
[0005] Presently no commercially-available process exists to achieve the objectives of the invention, which are detailed as follows:
BRIEF DESCRIPTION OF THE FIGURES
[0006] [0006]FIG. 1 is the flow chart showing an inventive process for defining and creating asset classes.
[0007] [0007]FIG. 2 shows the inventive process for determining after-tax, total return and standard deviation for an asset class.
[0008] [0008]FIG. 3 shows the inventive process for developing an optimal after-tax investment strategy.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0009] Creation of Derived Asset Classes
[0010] Commercially available computer programs that may be used to calculate an efficient frontier usually provide a standard set of potentially investable asset classes. They typically provide estimates of pre-tax expected total returns along with standard deviations and pair-wise correlations of such total returns for each of the several specified standard asset classes, or a means by which the user may specify how such expected returns, standard deviations, and pair-wise correlations may be determined (usually by analysis of an historical data base concerning the asset class). The user, however, may wish to use an asset class not included among the standard asset classes provided by such a program. In that case the user must separately determine and then enter into the program all of the necessary data for such a nonstandard asset class.
[0011] This invention allows a user to specify the linear coefficients and automatically calculate the necessary asset class data from a combination of data from the standard and previously specified asset classes. For example, a user may desire to explicitly set up real estate investment trusts as a separate asset class. Suppose such an asset class is not a standard asset class, whereas real estate, small-cap stocks, and corporate bonds are among the standard asset classes. The user may use the subject inventive program to create the real estate investment trust asset class by specifying, for example, that the return to the real estate investment trust asset class is to be derived from 50% of the return to real estate, 25% of the return to small-cap stocks and 25% of the return to corporate bonds. Estimates of necessary tax parameters, expected returns, standard deviations and correlations with other asset classes are thus derived from relationships for a linear combination of random variables which may be specified by the user. The preferred embodiment of the invention follows such a calculation methodology. As an example, the calculations for a combination of three variables are as shown in Equations 1, 2, and 3 on the section entitled “Calculation of Estimates for a Derived Asset Class” shown below. However, this invention anticipates permitting the user to change the standard deviation of a derived asset class arbitrarily by use of a specified standard deviation multiplier. For example, suppose an investor holds 40% of his portfolio in a single large-cap stock. In this situation, it may be appropriate to derive an asset class from the large-cap stock asset class to represent the single stock since the stock position is a significant part of the portfolio and therefore may merit special treatment. Now, suppose the single stock is 3 times as volatile as the large-cap stock asset class as a whole. Then, the expected pre-tax return for the single stock asset class would be estimated as the same as the return for the large-cap stock asset class, and the expected pre-tax standard deviation for the single stock asset class would be estimated as 3 times the standard deviation for the large-cap stock asset class.
[0012] The determination of the correlation between the returns to the single stock asset class and the returns to any other asset class is not readily apparent This invention specifies a simple methodology of dividing what would have otherwise been determined as the correlation between the derived asset class and any other asset class by the amount of the specified standard deviation multiplier.
[0013] Calculation of Estimates for a Derived Asset Class
[0014] I. Linear Combination of Asset Classes
[0015] As an example, consider the possible combination of three asset classes:
[0016] Assume W, X, Y and Z are random variables that represent the pre-tax total returns from four different asset classes with means (expected returns) {overscore (w)}, {overscore (x)}, {overscore (y)} and {overscore (z)} and standard deviations given by or, σ w , σ x , σ y , σ z and covariances given by σ wx , σ wy , σ wz , σ xy , and σ yz and pair-wise correlations given by ρ wx , ρ wy , ρ wz , ρ xy , σ xz and ρ yz .
[0017] Let V=α+β 1 X+β 2 Y+β 3 Z represent the return from a derived asset class created by a linear combination of three other asset classes, where α is an arbitrary constant and β 1 , β 2 , β 3 are linear coefficients.
[0018] Then,
{overscore (ν)} (expected return for the derived asset class)=α+β 1 {overscore (x)}+β 2 {overscore (y)}+β 3 {overscore (z)} 1.
σ ν (standard deviation for the derived asset class)=[(β 1 σ x ) 2 +(β 2 σ y ) 2 +(β 3 σ z ) 2 +(2β 1 β 2 σ x σ y ρ xy )+(2β 1 β 3 σ x σ z ρ xz )+(2β 2 β 3 σ y σ z ρ yz )] ½ 2.
ρ wv (correlation between W and V )=[(β 1 σ x ρ wx )+(β 2 σ y ρ wy )+(β 3 σ z ρ wz )]/σ ν 3.
[0019] Note: Each of the factors which are necessary for the calculation of the after-tax total return (e.g. ordinary income, turnover, applicable tax rates, tax basis, etc.) is given by the same linear relationship where:
Combined factor=α+β 1 (factor for asset X )+β 2 (factor for asset Y )+β 3 (factor for asset Z )
[0020] The user is always provided the option to modify any formula result.
[0021] II. Standard Deviation Multiplier
[0022] A unique feature of the inventive process is the ability of the user to specify a multiplier for the derived asset class standard deviation and a method for determining the cross correlation between that derived asset class and any other asset classes. For example, let X and Z be new random variables that represent returns from two different asset classes with expected returns {overscore (x)} and {overscore (z)} and standard deviations σ x and σ z . The covariance between X and Z is given by σ xz . The correlation between X and Z is given by ρ xz .
[0023] Suppose another new random variable Y=X+ε where ε, an error term, is a random variable with expected value of zero and which is assumed to be unrelated to X and Z. Also, suppose that standard deviation of Y, σ y is a multiple of standard deviation of X, σ x , i.e., σ y =k*σ x (k: standard deviation multiplier). Here, Y is a random variable representing the return from a derived asset class created as a by-product of any other asset class. X is the random variable representing the return of any other asset class and by itself may have been a derived asset class.
[0024] Then,
[0025] 1. expected return for Y={overscore (y)}={overscore (x)}
[0026] 2. standard deviation of Y=σ y =k*σ x by specification
[0027] 3. correlation between Y and Z is given by ρ yz =ρ xz /k
[0028] The foregoing methodologies are the preferred embodiment of this invention. However, any method of derivation may be used. Further, the user would have the flexibility to arbitrarily make changes to any of the calculated data, were the user to determine such were suitable to best represent the derived asset class.
[0029] The process of defining an asset class is depicted in FIG. 1. Each asset in the investor's current portfolio is associated with one of the standard asset classes (ovals 1 and 2 ). If not all of the assets (or potential assets that the investor desires to consider for future investment) can be so associated, additional asset classes may be created (boxes 3 , 3 A, 3 B, etc.). The method of creation depends upon whether or not the asset class can be represented by a combination of one or more other asset classes (box 3 B). If not, the user must provide all necessary data for the such nonstandard asset class (box 3 A). If the asset class can be represented by a combination of one or more assest classes, then the user need only specify which classes to combine and in what proportions (boxes, 4 , 4 A, and 4 B). The program would calculate the necessary derived asset class data automatically (box 5 ) using the inventive method detailed above. Finally the user may manually override any data so calculated (box 6 ).
[0030] III. Generalization
[0031] The foregoing calculations for a derived asset class may be generalized for more than three asset classes as set forth below.
DEFINITIONS: TERM DEFINITION x i , i = 1 to n Random variable that represent the return from the existing n asset class (standard and previously derived). The first n classes are those from which the user plans to derive the new n plus first asset class which return = x n+1 {overscore (χ)} I Expected return to asset class i. σ ij Covariance between x i and x j . σ i = {square root over (σ ii )} Standard deviation of x i . ρ ij Correlation between x i and x j . ε A random variable uncorrelated with any of the x i for i = 1 to n and with mean zero. C The standard deviation multiplier specified by the user. βt, i = 0 to m The constant term and linear coefficients specified by the user. X A vector with elements consisting of the x i for i = 1 to m. {overscore (X)} A vector with the elements consisting of the {overscore (χ)} i, for i = 1 to m. B A vector with elements consisting of the βt for i = 1 to m, and B′ indicates the transpose of B. R k A vector of m elements, ρ k,j for j = 1 to m. Σ An m by m matrix of variances and covariances with elements σ ij, i = 1 to m and j = 1 to m. S A diagonal m by m matrix with diagonal elements {square root over (σ ij )} for i = j, i = 1 to m and j = 1 to m and all others elements set to zero.
[0032] Investment Accounts
[0033] This invention provides that the user may establish any number of accounts. An account is simply a segregated grouping of a portion of the investment portfolio for which an efficient frontier is to be determined. Each account may incorporate an arbitrary set of asset classes but each asset class in that account must be subject to one of a number of sets of tax rules. Accounts are also useful because an investor may be restricted by legal or practical considerations from transferring funds between such accounts. For example, an investor may wish to adopt a portfolio strategy that includes his child's custodial assets in order to achieve a global family optimum portfolio. The child's assets may be segregated as a separate account. Additionally, the investor may have an interest in a deferred compensation program through his employer, which effectively allows no withdrawal of funds, but through which he may direct investments into a number of asset classes. The investors interest in this deferred compensation program may be segregated as a separate account. In practice, portfolios considered acceptable to the investor will be such that the aggregate market value of all of the asset classes in each account (except at least one fully-taxable account, as discussed below) will be subject to quantity restrictions. For example, the aggregate may not be allowed to change from its current value or it may not be allowed to exceed its current level.
[0034] Each account is assigned a specific type designation. Each type of account is then attributed with specified tax characteristics that apply to all the asset classes allowed in the account. The invention permits one to set up any number of different tax types. However, for simplicity the preferred embodiment of the invention specifies four types, of which one must apply to each account. The types are arbitrarily designated as: i) fully taxable, ii) tax deferred, iii) tax exempt, or iv) employee stock ownership plan (ESOP) sale proceeds account. Assets in a fully-taxable account are presumed to be taxable on a current basis consistent with the tax specifications assigned to the relevant asset classes. Tax-deferred accounts would typically be set up for 401k plans, regular IRAs, Keogh plans, deferred compensation plans, etc. Assets in a tax-deferred account are presumed to be fully taxable at a specified tax rate only when withdrawn from the account. A tax-exempt account would typically be represented by assets in a Roth IRA. Assets in a tax-exempt account are presumed not to be subject to income tax. Tax rules allow certain individual taxpayers to sell certain securities to an ESOP and to replace those securities with other qualified domestic securities without recognition of capital gain on the securities sold to the ESOP. Assets in an ESOP sale account represents those securities which may be sold to the ESOP and those which are eligible as qualified domestic securities.
[0035] Under the invention, the grouping and inputing of asset classes into an account causes the establishment of a linear constraint on those asset classes in the account—e.g. the sum of all market values of assets in the account must total to a number that equals the current value of all of the assets which the investor currently holds in the account. The specification of account type sets the tax characteristics of all the assets in the account. In effect, for optimization purposes, each asset class within an account is treated as if it were a separate and distinct asset class. As mentioned above, at least one fully taxable account must not be constrained to equal its initial value. This is because a tax may be due as a result of liquidation of assets required to effect a reallocation from the investor's current portfolio to a feasible efficient portfolio, which portfolio will have been specified with regard to after-tax considerations using our inventive method. Thus, allowance is made so that the tax may be paid from at least one account.
[0036] Calculation of After-tax Asset Class Characteristics
[0037] After-tax returns and after-tax standard deviations for each asset class are calculated from the corresponding pre-tax returns and pre-tax standard deviations based upon several specified factors. The preferred embodiment of the invention sets all after-tax correlations equal to pre-tax correlations, because such a relationship is dictated by probability theory under the assumption that the effective tax rate is a constant. This is consistent with current practice in the art. Other assumptions could be utilized and if so, another method of deriving after-tax correlations would be required. Any such method would fall within the scope of this invention.
[0038] After-tax Returns
[0039] The invention is unique in that its calculation of the after-tax expected return for an asset class explicitly accounts for the tax basis of the asset class and the investor's relevant tax time horizon. The tax time horizon is normally the number of time periods included in an investor's planning horizon. However, it may differ for certain asset classes. For example, a user may specify that a single asset constitutes an asset class. The investor may have an emotional attachment to such asset and/or it may be a very low tax basis asset that is a significant proportion of the value of the investor's current portfolio. The tax time horizon for that specific asset may be set to the a priori number of time periods that the investor would normally anticipate holding the asset class. Also, it could be set to the investor's life expectancy and earmarked for exclusion from capital gains taxes due to the statutory step-up in tax basis then allowed.
[0040] As with other commercially available methods, the preferred embodiment of the invention specifically incorporates asset class turnover, the portion of total asset class return that is appreciation, the portion that is realized income, and effective tax rates for both realized gain and income into calculated after-tax total returns. Although non-income-tax transaction costs are contemplated, as well, they are not included in the preferred embodiment, since they are deemed to be minor in comparison to income-tax effects. The preferred embodiment of the invention calculates and automatically assigns each asset class a set of two default tax rates (typically one for income, the other for realized gains) based upon the investor's general tax situation. Uniquely, however, the user may override assigned default rates and specify a different set of applicable tax rates to each asset class. In general terms the invention contemplates the possibility that any number of tax characteristics of total returns may be subject to tax, with each characteristic being subject to a separate effective tax rate and each asset class having some, all, or none of the effective tax rates in common.
[0041] The after-tax expected return is calculated by specifying a series of periodic expected after-tax cash flows. The discount rate which sets the present value of the sum of the expected after-tax cash flows equal to the current asset class value net of contingent tax (formula (7), discussed below), is the expected after-tax return for the asset class. FIG. 2 and the Formulas included herein and described in the formula sheets below illustrate the methodology under the preferred embodiment. Formulas (1) and (2) show one method of how the default tax rates may be determined from the investor's current federal and state marginal income tax rates on income and realized capital gains. Keep in mind that the default rates may be modified to any arbitrary rate as determined by the user. As a first step (circle 1 , FIG. 2) the initial cost basis for each asset class to be considered must be set to its current tax basis, if represented in the investor's current portfolio, set to zero, or adjusted as shown in Formula (4A). Next, the periodic appreciation rate (box 2 , FIG. 2) and the after-tax periodic income rate (box 3 , FIG. 2) are determined from the specified pre-tax total expected return per period and the specified pre-tax income rate for the asset class in question. As indicated in box 4 , FIG. 2, the initial value net of contingent tax is then determined. The contingent tax is the tax that the investor would be required to pay, if he were to liquidate all of his holdings currently in the asset class in question (Formula (4D)). Formula 4B illustrates the calculation of the Asset Appreciation Rate, and Formula 4C shows the calculation of the After-Tax Investment Income. At this point the process is to calculate the series of cash flows, net of tax, that the asset class is expected to provide. This is initiated by calculating the first period's cash flow, assumed to be derived from income, and subtracting out current taxes due for the period (FIG. 2, boxes 5 & 6 ). Such net cash flow would be discounted by the (unknown) after-tax return to obtain its current present value (Formula (4E)). Then the tax basis at the end of the period is updated to reflect the gains realized during the period (FIG. 2, box 7 and Formula (4F). If the tax time horizon has not been reached (FIG. 2 box 8 ), then the net cash flow is calculated for the following period. The process continues in a loop as shown in sequence on FIG. 2 boxes 9 , 10 , 11 , 12 and 13 with present values of cash flows determined according to Formula (4G) and end of period tax bases as shown in Formula (4H). When the tax time horizon is reached (FIG. 2, boxes 8 and 12 ) the final net expected after-tax value of the asset class is calculated (FIG. 2, box 14 and Formula (4I)). As illustrated in FIG. 2, box 15 , the sum of all present values of the expected after-tax cash flows together with the discounted final asset value is then set equal to the initial net-of-contingent-tax value of the asset class. Finally, (FIG. 2, box 16 ) the equation may be solved for the unknown discount rate using well-known numerical methods. The expected after-tax rate of return for the asset class is then the value of the discount rate, so determined. Formula 4J shows the after-tax rate of total return. Note in the case of asset classes assigned to tax-deferred or tax-exempt accounts the forgoing process is not required as after-tax returns equal pre-tax returns (refer to Formula 4K).
[0042] After-tax Standard Deviations
[0043] In the preferred embodiment of the invention the calculation of after-tax standard deviations is a simpler process (FIG. 2, box 17 and oval 18 ). The after-tax standard deviation is simply the complement of the effective tax rate multiplied by the pre-tax standard deviation (Formula (5A)). This follows straight away from statistical theory if the effective tax rate is a constant, which is a typical assumption in the practice of the art. However, the invention allows for the case in which the relative volatility of income and appreciation components of the total pre-tax return may affect the effective tax rate. In this case the effective tax rate may first be approximated as shown in Formula (5B). The use of this formula requires an input item(referred to as Gamma in Formula (5B), and which may vary from 0 to 1) that specifies how stable the ordinary income component of the returns to the asset class may be. In the preferred embodiment the sensitivity factor is set to default to simple approximating assumptions. Thus, asset classes which are fixed income in nature and are of maturity longer than one year are generally assumed to have a Gamma of 1 whereas equity classes assumed to have a Gamma of 0. Users may, of course, override the default sensitivity factors. Other calculation methods of approximating after-tax standard deviations could be used in different embodiments of the invention. Note Formula (5C), which indicates that in the case of asset classes assigned to tax-deferred or tax-exempt accounts the after-tax standard deviation of total returns is set equal to the pre-tax standard deviation of total returns.
[0044] Representation of Current Portfolio
[0045] An investment practitioner skilled in the state of the art typically represents an investor's current portfolio gross of tax, and this is the implied representation used in commercially available portfolio optimization programs. However, this is an incorrect procedure when compared to the portfolio guidance made possible by our invention. An investor can only spend or consume an asset on an after-tax basis. The unrealized income and gains that have accrued to an asset carry a liability to the taxing authorities due on liquidation. In effect, the taxing authorities are co-owners of the asset with the investor. Thus, the taxing authorities have a claim on the asset equal to the contingent tax due on the asset. The contingent tax is the difference between the market value of the asset and its tax basis multiplied by the expected effective tax rate upon liquidation (the contingent tax rate). The value effectively owned by the investor in any asset class is, then, the market value of the asset class less the contingent tax. This is designated the adjusted market value as shown in Formula (7). In the preferred embodiment of the invention the contingent tax rates are as given in Formula (6). Again, the user may arbitrarily change the contingent tax rate for any asset class. The total net value of the current portfolio (or total value of the portfolio, net of contingent tax) is simply the sum of the adjusted market value of each asset class in the portfolio (Formula (8A)). At this point FIG. 3, boxes 1 - 10 , may be used to trace through the process described above. For example, boxes 1 , 2 , and 3 depict inputing data about the investor's portfolio and taax rast. Boxes 4 and 5 depict defining the asset classes, creating accounts, and entering market value and tax bases of asset holdings. Box 7 depicts specification of investment constraints. Boxes 8 A, 8 B, 8 C and 9 catagorize assets and calculate after-tax returns and standard deviations. Box 10 depicts adjusting the values of constraint limits on asset classes.
[0046] Note that in the preferred embodiment of the invention, if an asset class is contained in the current portfolio with a tax basis other than that of the market value, another asset class is automatically derived from that asset class with identical pre-tax characteristics. The original asset class is given a default upper value limit equal to its current market value; this reflects the fact that, in general, an investor cannot purchase an asset that has a tax basis different than its purchase price.
[0047] Adjustment of Constraints
[0048] The next step in determining an optimal after-tax portfolio requires the adjustment of constraints imposed on the portfolio by the investor or the user. Typically one kind of constraint consists of lower and upper bound constraints on each asset class in each account in the investors portfolio. In effect such constraints state a minimum and a maximum investment that must be maintained in an asset class. The invention allows such a minimum or maximum to be specifically applied against either the gross market value or the adjusted market value of the asset class. In the preferred embodiment the convention adopted is that minimum or maximum constraint values which exceed one (i.e. given in dollar terms) are understood to be constraints on gross market value. Constraint specifications which are given as a value between zero and one (i.e. specified as a proportion of the portfolio) are understood to apply to the proportion that the adjusted asset class value bears to the total net value of the portfolio. The invention (FIG. 3, box 11 ) converts all gross market value limits to proportional limits. The adjustment procedures are specified in Formulas (8B) and (8C).
[0049] Another kind of constraint consists of a lower and upper bound for the value of a linear combination of asset classes. For instance, the user may specify that the value of the after-tax holdings of all equity investments is not to exceed a certain proportion of the total net value of the portfolio regardless of the account location of all such asset classes. As another example, the user may specify that all fixed income asset classed in fully taxable accounts must, in total, yield as specified dollar amount of income each period. The first step in adjusting such constraints is to calculate the gross-up ratio of before-tax market value to adjusted market value of each asset class (FIG. 3, box 12 ). The method for doing so is given in Formula (9A). The next step (FIG. 3, box 13 ) is to make any necessary adjustments to the constraints. The method follows the convention set forth in the prior paragraph concerning upper bounds and lower bounds, now as they apply to a linear combination of asset class values rather than to a single asset class. Constraints with bounds greater than one, that is those specified in dollar terms, must be adjusted. Adjustments for equality constraints are given in Formulas (9B). Inequality constraint adjustments are shown in Formulas (9C).
[0050] Efficient After-tax Frontier
[0051] At this point the invention has specified a method of setting up a complete set of constraints for use in a constrained minimization problem where the objective function is the risk function of the portfolio (FIG. 3, box 14 ). In the preferred embodiment the user is given the standard deviation of the portfolio's after-tax total return is the default risk function (mean-variance efficiency.) Each portfolio on the after-tax efficient frontier is determined by solving the constrained minimization problem given by all the aforementioned constraints plus the constraints that i) all the after-tax proportions that each individual asset class constitute of the total after-tax portfolio sum to unity and ii) the total after-tax return is a specified constant. In a well-known procedure, numerous portfolios on the after-tax efficient frontier are located by changing the constant specifying the total after-tax return. Several algorithms exist to solve the problem. They are available as optimization routines in certain commercial computer programs, most preferably a general mathematical analysis program such as MATLAB, a registered trademark of Mathworks, Inc., which can be programmed to interface with the method of the invention. Of course it is intended that all steps of manipulating the portfolio information would be performed on a general purpose electronic computer configured and programmed to perform as we have disclosed.
[0052] Conversion for Presentation and Implementation
[0053] The user is now in possession of the after-tax efficient frontier. For ease of presentation and implementation each optimal (efficient) after-tax portfolio is converted back to a pre-tax format which prescribes the pre-contingent-tax dollar amount that is to be placed in each asset class FIG. 3, box 15 , Formula (10)). The user's last step is (FIG. 3, oval 16 ) to choose from among the identified portfolios provided by the invention that one which is most acceptable to the investor.
Mathematical Formulas Used for the Invention (Formula Sheets)
[0054] I. Effective Ordinary Income Tax Rate
( TI, may differ for each individual asset class, and may be investor-specific)=[Federal Marginal Tax Rate*(1−State Marginal Tax Rate)]+State Marginal Tax Rate (1)
[0055] Note: The symbol, *, indicates the multiplication operator.
[0056] II. Effective Capital Gains Tax Rate
( TC, applies to individual asset class, and may be investor-specific)=Federal Capital Gains Tax Rate+[State Marginal Tax Rate*(1−Federal Capital Gains Tax Rate)] (2)
[0057] III. Account Classification Based on Distinct Tax Treatment
[0058] 1) Fully Taxable—Brokerage Account, Bank Savings Account, and so on
[0059] 2) Tax-Deferred—401k, Profit-sharing Plan, IRAs, Keoghs, and so on
[0060] 3) Tax-Exempt—Roth IRAs
[0061] 4) ESOP Sales—a collection of qualified domestic securities for reinvestment along with the security that may be sold to the ESOP.
[0062] IV. After-Tax Rate of Total Return
[0063] (ATR, for individual asset class in Fully Taxable Accounts and ESOP Sales Accounts)=Internal Rate of Return Based on Stream of Discounted Cash Flows from Investment Over Time Horizon for Tax Consideration
[0064] Inputs: Effective Ordinary Income Tax Rate, Effective Capital Gains Tax Rate, Average Annual Turnover Rate (TR), Before-Tax Rate of Total Return (PTR), Before-Tax Rate of Income Return (IR), Tax Basis (TB), Current Market Value NY), Time Horizon for Tax Consideration (N, specified in number of periods, typically years), Willingness to Liquidate Before Death [TPCODE, Yes(1) or No(0)] Note: By convention a tax basis entered as zero is taken to be market value.
[0065] Define:
COST(initial tax basis, for any asset class)= TB (if MV> 0, i.e., asset is currently held), or 0 (if MV= 0, i.e., asset is not currently held) (4A)
[0066] V. After-Tax Rate of Total Return
[0067] Define:
Asset Appreciation Rate(APR, for individual asset class)=1 +PTR−IR (4B)
After-Tax Investment Income(ATI, in percentage, for individual asset class)= MV*IR *(1− TI ) (4C)
Initial Asset Value(net of capital gain tax payment on unrealized gain)= MV−TC *( MV− COST(initial)) (4D)
[0068] Note: If the asset is not currently held (MV=0), then for the purposes of (4E) through (4J) only, MV and COST(initial) should be set equal to a single arbitrary positive number for fully taxable accounts. In the case of ESOP Sales Accounts, then again for the purposes of (4E) through (4J) only, MV should be set equal to an arbitrary positive number and COST (initial) should be set to a corresponding number such that the ratio of COST(initial) to market value is the same as the security that may be sold to the ESOP.
[0069] For Period(T)=1:
Discounted Cash Flow( F )=[ ATI−TC*TR* ( MV*APR −COST(initial))]/(1 +ATR ) (4E)
[0070] i.e. [Discounted Cash Flow=(After-Tax Investment Income−Tax Payment on Realized Capital Gain)/(1+Discount Rate)]
COST(updated)=COST(initial)*(1 −TR )+ TR*MV*APR (4F)
[0071] Repeat for T=2 to N:
F=[ATI*MV*APR ^ ( T− 1)− TC*TR* ( MV*APR ^ ( T )−COST(previous))]/(1 +ATR )^ ( T ) (4G)
COST(updated)=COST(previous)*(1 =TR )+ TR*MV*APR^ T (4H)
[0072] [0072] Discounted Final Asset Value =
[ MV * APR ^ ( N ) - TC * ( MV * APR ^ ( N ) - COST ( updated at T = N ) ) ] / ( 1 + ATR ) ^ ( N )
( if TPCODE = Yes ) or
[ MV * APR ^ ( N ) ] / ( 1 + ATR ) ^ ( N ) ( if TPCODE = No ) ( 4I )
[0073] To Calculate the After-Tax Rate of Total Return:
Set Initial Asset Value=(Sum of Discounted Cash Flows, F , for T= 1 to N )+Discounted Final Asset Value & Solve for ATR (4J)
[0074] Note: for all asset classes in Tax-Deferred and Tax-Exempt Accounts
ATR (after-tax total return)= PTR (before-tax total return) (4K)
[0075] V. After-Tax Standard Deviation
( ATSD, for individual asset classes in Fully Taxable=Accounts and ESOP Sales Accounts)=(1−Effective Tax Rate)*Before-Tax Standard Deviation (5A)
[0076] [0076] where Effective Tax Rate = 1 - [ ( MATR - ( 1 - TI ) * Gamma * IR ) / ( PTR - Gamma * IR ) ] and Gamma = Ass et Class ' s Se nsitivity to Ordinary Income Tax ( between 0 and 1 )
e . g . ) fixed income asset classes : 1 , equity asset classes : 0
The modified after - tax return ( MATR ) is the ATR calculated as if
COST ( initial ) were equal to MV . ( 5 )
[0077] (Special Case) if PTR=IR, Effective Tax Rate=TI
[0078] Note: for all asset classes in Tax-Deferred & Tax-Exempt Accounts
ATSD =Before-Tax Standard Deviation (5C)
[0079] [0079] VI . Contingent Tax Rates
( TEG , tax rates applied to embedded capital gain )
= TC ( for all asset classes in Fully Taxable accounts
and ESOP Sales Accounts ) or
= TI ( for all asset classes in Tax - Deferred accounts )
or
= 0 ( for all asset classes in Tax - Exempt accounts ) ( 6 )
[0080] VII. Adjustment of Individual Asset Class's Current Market Value due to Contingent Tax
[0081] Assume: Basis(TB) for all asset classes in Tax-Deferred & Tax-Exempt accounts=0
ADJMV (adjusted MV )= MV−TEG *( MV−TB ) (7)
[0082] VIII. Adjustment of Constraint Limit(Lower and Upper) on Single Asset Class due to Contingent Tax
[0083] Convention: All Values of Limits in Percentage (i.e. fractional values between 0 and 1) imply After-Tax Limits & No Adjustments are necessary All Values of Limits in Dollar (i.e.values equal to or greater than 1) imply Before-Tax Limits & need to be converted to After-Tax Percentage Limits
[0084] Common Notation:
VLB<=X<=VUB,
[0085] where
[0086] VLB represents a value of lower limit for constraint on an asset class
[0087] X represents an location for an individual asset class
[0088] VUB represents a value of upper limit for constraint on an asset class
Compute, ATPV (total value of portfolio, net of contingent tax)=Σ ADJMV (sum of all adjusted MV ) (8A)
[0089] [0089] For asset classes in Fully Taxable Accounts and ESOP Sales Accounts :
If VLB > 1 ( => dollar limit )
ADJVLB ( adjusted VLB ) = ( VLB * ADJMV / MV ) / ATPV
( Special Case ) If ADJMV =
0 ( i . e . , asset is not currently held ) ,
ADJVLB = VLB / ATPV
NOTE : FOR EACH ASSET CLASS IN THE ESOP SALES ACCOUNTS THE ADJVLB AND MV VALUES USED IN THE FOREGOING ARE THOSE OF THE SECURITY THAT IS TO BE SOLD TO THE ESOP .
For all asset classes in Tax - Deferred Accounts :
If VLB > 1 ( => dollar limit )
ADJVLB = [ VLB * ( 1 - TI ) ] / ATPV
For all asset classes in Tax - Exempt Accounts :
If VLB > 1 ( => dollar limit )
ADJVLB = VLB / ATPV ( 8B )
[0090] Likewise,
For asset classes in Fully Taxable Accounts or ESOP Sales Accounts : If VUB > 1 ( => dollar limit )
ADJVUB ( adjusted VUB ) = ( VUB * ADJMV / MV ) / ATPV
( Special Case ) If ADJMV = 0 ( i . e . , asset is not currently held ) , ADJVUB = VUB / ATPV
NOTE : FOR EACH OF THE ASSET CLASSES IN THE ESOP SALES ACCOUNTS THE ADJVUB AND MV VALUES USED IN THE FOREGOING ARE THOSE OF THE SECURTIY THAT IS TO BE SOLD TO THE ESOP .
For all asset classes in Tax - Deferred Accounts :
If VUB > 1 ( => dollar limit )
ADJVUB = [ VUB * ( 1 - TI ) ] / ATPV
For all asset classes in Tax - Exempt Accounts :
If VUB > 1 ( => dollar limit )
ADJVUB = VUB / ATPV ( 8C )
[0091] VIV. Adjustment of Linear Constraint Specification & Corresponding Limit (Lower and Upper) on Group of Asset Classes due to Contingent Tax
[0092] Note: A linear constraint refers to investment restriction placed on combination of multiple asset classes across or within amounts
[0093] Common Notation:
BL<=B=Σa t *X i <=BU for i= 1 to N (number of individual asset classes),
[0094] where
[0095] B represents a linear constraint specification,
[0096] BL represents a value of lower limit on a linear constraint,
[0097] BU represents a value of upper limit on a linear constraint,
[0098] X 1 presents an allocation to each asset class, and
[0099] α i represents a fixed portion of X i typically between 0 and 1, usually 0(0%) or 1(100%)
Define : GR ( gross - up ratio , applies to individual asset class )
= B efore - Contingent Tax MV / After - Contingent Tax MV
For asset classes in Fully Taxable Accounts :
If ADJMV > 0 ( i . e . , asset is current held ) ,
GR = ADJMV / MV
If ADJMV = 0 ( i . e . , asset is not current held ) , GR = 1
For all asset classes in ESOP Sales Accounts ,
GR = ADJMV / MV where
the ADJMV and MV used is that of the security that be sold to the ESOP
For all asset classes in Tax - Deferred Accounts ,
GR = 1 / ( 1 - TI )
For all asset classes in Tax - Exempt Accounts , GR = 1
For any equality linear constraint : ( 9A ) If BL = BU > 1 ( => dollar limit )
ADJB ( adjusted linear constraint specification )
= B ( initial , linear constraint specifications ) *
GR or using a common notation
= ∑ GR i * a i * X i for i =
1 to N ( number of individual asset classes ) ,
where GR i
represents a value of gross - up ratio for each asset class
ADJBL ( adjusted BL ) = ADJBU ( adjusted BU )
= BL / ATPV = BU / ATPV ( 9B ) If BL = BU < 1 ( => percentage limit )
ADJB = B , ADJBL = ADJBU = BL ( no adjustment necessary )
For any inequality linear constraint :
If BL > 1 ( => dollar limit )
ADJB = B * GR or using a common notation
= ∑ GR i * a i * X i
ADJBL = BL / ATPV
If BL < 1 ( => percentage limit )
ADJB = B , ADJBL = BL ( no adjustments necessary )
Likewise ,
If BU > 1 ( => dollar limit )
ADJB = B * GV or using a common notation
= ∑ GR i * a i * X i
ADJBU = BU / ATPV
If BU < 1 ( => percentage limit )
ADJB = B , ADJBU = BU ( no adjustments necessary ) ( 9C )
[0100] X. Converting Optimal, After-Tax Portfolio to Before-Tax Portfolio for Presentation & Implementation
[0101] Suppose: OPTPORT=After-Tax, Percentage Allocation for Each Asset Class in an Optimal Portfolio calculated from Optimizer
PTOPPVAL j (before-tax allocation in dollar for each asset class)= OPTPORT j *ATPV*GR j (10)
[0102] for j=1 to M(number of individual asset classes that make up the optimal portfolio)
[0103] While the invention has been described in terms of a preferred embodiment, those skilled in the art will recognize that the invention can be practiced with modification and alteration within the spirit and scope of the appended claims. | There are computerized processes for financial planning for individuals and groups whose financial portfolio would be subject to tax on certain events. But these processes do not take into account these taxes when optimizing investment decisions, since taxes levied on investment outcomes, typically on income and realized capital gains, may have an important impact on net portfolio results. This invention is a method for transforming the usual pretax information for calculation of an efficient frontier, unique to an investor's portfolio, in such a manner that any portfolio on the calculated frontier is efficient after incorporating the effect of taxes on the risk and expected return of each asset class permitted in the investor's portfolio. This invention addresses how this may be done and how certain facets of the process may be incorporated into a computer program or system so as to provide convenience to the potential user. | 6 |
FIELD
[0001] The present teachings relate to a cutting guide for resecting a portion of a bone and more particularly relate to a distal femoral cutting guide that can be selectively adjusted over a medial anterior portion of a distal end of a femur.
BACKGROUND
[0002] A human joint 10 is the junction of four bones: a femur 12 , a tibia 14 , a fibula 16 and a patella 18 , as shown in FIGS. 1-3 . Myriad medical problems can require partial or complete replacement of one or more portions of the aforesaid bones that form the knee joint 10 . When using one or more prosthetic devices to replace one or more portions of the bones of the knee joint 10 , preparation portions of the various bones can be necessary to supply a proper fit for the prosthetic. Preparation can include resection or fashioning of the bones to complement an interior portion of a prosthetic.
[0003] When implanting a prosthetic on a distal end 20 of the femur 12 , portions of the distal end 20 can be resected to provide a proper fit for the prosthetic. For example, a lateral condyle 22 and a medial condyle 24 can be partially or completely resected in preparation for implantation of the prosthetic. A distal femoral planar cut is generally performed relative to a mechanical angle of the knee joint 10 . To vary the angle of the distal femoral planar cut, multiple components typically have to be disassembled and reassembled to provide the proper angle. One or more of the components used to provide the distal femoral planar cut are typically positioned above an anterior surface of the femur. In such a position, access to an anterior portion of the femur and positioning components in the same area can be relatively difficult. While the above methods and components remain useful for their intended purpose, there remains room in the art for improvement.
SUMMARY
[0004] The present teachings generally include a system that locates a femoral cutting guide on a distal end of a femur. The femoral cutting guide establishes at least a first reference plane to perform a distal femoral planar cut. The system generally includes a mounting rod operable to insert into the distal end of the femur. An index member is operable to abut the distal end of the femur. A bridge member extends from the index member. A cutting guide member extends from the bridge member. The cutting guide member includes a first channel that establishes the first reference plane. A mounting mechanism releasably couples the cutting guide member to the bridge member. The mounting mechanism is operable to generate a sliding resistance between the bridge member and the cutting guide member that is generally overcome to position the cutting guide member relative to the femur.
[0005] Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present teachings.
DRAWINGS
[0006] The drawings described herein are for illustration purposes only and do not limit the scope of the present teachings.
[0007] FIG. 1 is a prior art partial front view of a knee joint showing bones, muscle tissue and connective tissue of the knee joint.
[0008] FIG. 2 is a prior art similar to FIG. 1 and shows a patella, the muscles and the associated connective tissue pulled away from respective portions of the knee joint.
[0009] FIG. 3 is a perspective view of the knee joint, absent the muscle and the connective tissue, showing a lateral condyle, a medial condyle and an exemplary plane of resection of a distal end of the femur in accordance with the present teachings.
[0010] FIG. 4 is an exploded assembly view of a distal femoral cutting guide assembly constructed in accordance with the present teachings having an index member, a bridge member and a guide member that can couple to an intramedullary rod with a bushing coupled to the index member.
[0011] FIG. 5A is a partial perspective view of the bushing installed in the index member and disposed over the intramedullary rod of FIG. 4 that is installed on the left femur in accordance with the present teachings.
[0012] FIG. 5B is similar to FIG. 5A and shows the bridge member connected to the index member and receiving the guide member to hold the guide member so that the cutting guide member can be further secured to the bone with suitable fixation pins in a first set of apertures in accordance with the present teachings.
[0013] FIG. 5C is similar to FIG. 5A and shows the cutting guide member secured to the femur with two fixation pins in the first set of apertures.
[0014] FIG. 5D is similar to FIG. 5C and shows the cutting guide member pulled off the fixation pins and the femur without the need to remove the fixation pins from the left femur.
[0015] FIG. 5E is similar to FIG. 5C and shows the cutting guide member placed on the fixation pins that are received by additional apertures in the second set of apertures that position the cutting guide member in a superior direction, i.e., up the left femur.
[0016] FIG. 5F is similar to FIG. 5E and shows the cutting guide member secured to the femur with the fixation pins through a second set and a third set of fixation apertures that can hold the cutting guide member to the femur, while an exemplary resecting tool can make a cut using the guide channels that establish a reference plane on which the resection can be based.
[0017] FIG. 6 is a perspective view of the distal femoral cutting guide assembly showing the distal femoral cutting guide assembly installed on a right femur in accordance with the present teachings.
[0018] FIGS. 7A , 7 B and 7 C are each front views of different bushings showing the angle at which an intramedullary rod that can be received within the bushing would be disposed relative to the index member.
DETAILED DESCRIPTION
[0019] The following description is merely exemplary in nature and is not intended to limit the present teachings, their application, or uses. It should be understood that throughout the drawings, corresponding reference numerals can indicate like or corresponding parts and features.
[0020] The present teachings generally include a cutting guide assembly 100 for resecting a portion of a bone, as shown in FIG. 4 . While the various illustrated aspects of the present teachings pertain to the knee joint 10 ( FIG. 3 ) of the human body, it will be appreciated in light of the disclosure that the teachings may also be applicable to various bones of the human body including, but not limited to, the tibia, the fibula, the humerus, the ulna or the radius. It will also be appreciated that the teachings may be applicable to various bones of other animals, mammalian or otherwise, requiring replacement with prosthetics due to various medical concerns.
[0021] With reference to FIG. 4 , the cutting guide assembly 100 can include an index member 102 , a bridge member 104 and a cutting guide member 106 . The cutting guide assembly 100 can be used in a procedure to resect (i.e., surgically remove part of an organ or a structure) one or more portions of a distal end of a right femur 12 a ( FIG. 6 ) and/or a left femur 12 b ( FIGS. 5A-5E ), which can be collectively referred to as the distal end 20 of the femur 12 . As shown in FIG. 5A , the index member 102 can abut the distal end 20 of the femur 12 . As shown in FIG. 5B , the bridge member 104 can couple the cutting guide member 106 to the index member 102 and can establish a reference plane 108 (an imaginary plane, as shown in FIG. 4 ) that can project through the distal end 20 of the femur 12 . While the bridge member 104 is shown as a separate component, in one example, the bridge member 104 and the cutting guide member 106 can be a single monolithic member or a collection of multiple components.
[0022] In accordance with various aspects of the present teachings and with reference to FIG. 6 , the cutting guide member 106 can be configured to be located over a medial anterior corner of the distal end of a right femur 12 a. Moreover, the bridge member 104 can be configured to hold the cutting guide member 106 over the medial anterior portion of the distal end 20 of the femur 12 . While holding the cutting guide member 106 , the bridge member 104 can be configured to provide a sliding resistance between the cutting guide member 106 and the bridge member 104 in various aspects of the present teachings. The sliding resistance can be overcome by the medical professional as he or she repositions the cutting guide member 106 relative to the bridge member 104 , which will be discussed in further detail herein.
[0023] In accordance with one aspect of the present teachings and with reference to FIGS. 4 and 5A , the index member 102 can be coupled to an intramedullary rod 110 or other suitable mounting rod that can be inserted into the distal end 20 of the left femur 12 b: A first bushing 112 a can be selected from a plurality of bushings 112 , examples of which are shown in FIGS. 7A , 7 B and 7 C. Each of the bushings 112 can couple to the index member 102 and can receive the intramedullary rod 110 . Each of the bushings 112 can be configured to hold the index member 102 at a predetermined angle relative to a longitudinal axis 114 of the intramedullary rod 110 , as discussed in greater detail.
[0024] With reference to FIGS. 7A , 7 B and 7 C, the plurality of bushings 112 can, therefore, have varying configurations that provide for holding the index member 102 at a range of angles relative to the longitudinal axis 114 of the intramedullary rod 110 and, thus, the longitudinal axis 28 of the femur 12 ( FIG. 3 ). The range of angles provided, for example, can include about four degrees to about seven degrees with about one degree angle increments between four and seven degrees. It will be appreciated that other configurations that provide more or less angle increments and/or the size of the increment can be implemented as applicable.
[0025] Returning to FIG. 4 , the index member 102 can have a first surface portion 116 that can abut the distal end 20 of the femur 12 that can include one or more portions of the medial condyle 24 and the lateral condyle 22 . A second surface portion 118 ( FIG. 6 ) can be opposite the first surface portion 116 and one or more wall portions 120 can bound the first surface portion 116 and the second surface portion 118 . The wall portions 120 can be configured in a shape that can be similar to a parallelogram, i.e., a quadrilateral with opposite sides parallel or something similar thereto. Notwithstanding, it will be appreciated in light of the disclosure that the index member 102 can be configured with various suitable polygonal shapes. Moreover, the wall portions 120 can further include connection to and/or be integrally formed with additional surfaces, facets, rounded portions, other suitable configurations and combinations thereof, that can be used to facilitate manipulation and insertion of the index member 102 through the incision 30 and/or a cannula.
[0026] The index member 102 can define a bushing receiving aperture 122 . The bushing receiving aperture 122 can include wall portions 124 that can be configured to abut one of the bushings 112 . Each of the bushings 112 can releasably couple to the index member 102 and/or can lock with the various suitable locking mechanisms thereto. One or more of the suitable locking mechanisms can securely hold one of the bushings 112 to the index member 102 but then can be uncoupled as needed.
[0027] The index member 102 can define one or more holes 126 that can receive one or more complementary posts 128 that can extend from the bridge member 104 . The one or more of the holes 126 can be defined in the one or more wall portions 120 of the index member 102 and can be sized with different diameters or widths, as applicable, to receive the one or more complementary posts 128 on the bridge member 104 . For example, a first post 128 a can be received by a first hole 126 a and, similarly, a second post 128 b can be received by a second hole 126 b. The first hole 126 a and the first post 128 a can have larger but complimentary diameters or width than the second post 128 b and the second hole 126 b that can have smaller but complementary diameters or widths, as applicable.
[0028] The combination of the holes 126 and the complementary posts 128 can be configured such that only a single orientation can exist in which the bridge member 104 can couple to the index member 102 . In one example, as shown in FIG. 5B , the index member 102 can be oriented in a first position that can abut the distal end of the left femur 12 b. With reference to FIG. 6 , the index member 102 can be re-oriented so that the index member 102 is oriented in a second position and can abut the distal end of the right femur 12 a. The bridge member 104 can also have a first orientation ( FIG. 5B ) and a second orientation ( FIG. 6 ). With reference to FIG. 5B , the index member 102 that can abut the left femur 12 b can be configured to only accept the bridge member 104 in the first orientation. With reference to FIG. 6 , the index member 102 that can abut the right femur 12 a can be configured to only accept the bridge member 104 in the second orientation.
[0029] Returning to FIG. 4 , the bridge member 104 can define a first guide assembly 130 and a second guide assembly 132 . The first guide assembly 130 can include a channel 134 that can be operable to receive and/or releasably couple a portion of the cutting guide member 106 . One or more mounting mechanisms 136 can be mounted on one or more wall portions 138 within the channel 134 and can releasably couple the cutting guide member 106 to the first guide assembly 130 . The one or more mounting mechanisms 136 can define one or more magnets, hook and loop fasteners, suitable adhesives and/or one or more suitable combinations thereof. It will be appreciated that one or more other mechanisms can be used to releasably couple the cutting guide member 106 to the one or more wall portions 138 of the first guide assembly 130 . The one or more mounting mechanisms 136 and/or other suitable mechanisms can be made of, wholly or partially, one or more suitable biocompatible materials that can be sterilized.
[0030] The second guide assembly 132 can be similar to the first guide assembly 130 but can be positioned on an opposite side of the bridge member 104 . The second guide assembly 132 can similarly include one or more mounting mechanisms 140 that can releasably couple the cutting guide member 106 to the bridge member 104 . The one or more mounting mechanisms 140 and/or one or more other suitable fastening mechanisms can be mounted on one or more wall portions 142 in the second guide assembly 132 but at a location in the second guide assembly that can be opposite of a location of the one or more mounting mechanisms 136 in the first guide assembly 130 .
[0031] With reference to FIG. 6 , the one or more mounting mechanisms 136 , 140 in the first and the second guide assemblies 130 , 132 can hold the cutting guide member 106 , while the cutting guide member 106 can be adjusted relative to the distal end 20 of the femur 12 a, 12 b. After final adjustment, the cutting guide member 106 can be held by the bridge member 104 until a relatively more secure fastener can couple to the cutting guide member 106 to the femur 12 a, 12 b, an example of which is shown in FIG. 5F . During one or more adjustments, the mounting mechanisms 136 , 140 can provide for a sliding resistance that can be overcome by a medical professional (not shown) when he or she repositions (i.e., the one or more adjustments) the cutting guide member 106 relative to the bridge member 104 and/or relative to the distal end 20 of the femur 12 a, 12 b.
[0032] Returning to FIG. 4 , the cutting guide member 106 can generally define a body portion 142 having a first guide channel portion 144 and a second guide channel portion 146 that can be formed through the body portion 142 and can be spaced from one another. The first and the second channel portions 144 , 146 can each define a generally elongated rectangular aperture through which a suitable tool 148 ( FIG. 5F ), such as a manual or a powered resecting tool, can be placed for cutting a portion of the distal end 20 of the femur 12 , as shown in FIG. 5C . One or more wall portions 152 of the first guide channel portions 144 can establish the first reference plane 154 on which a resection of the medial anterior portion 150 of the femur 12 can be preformed. In addition, the one or more wall portions 156 of the second guide channel 146 can establish a second reference plane 158 .
[0033] The body portion 142 of the cutting guide member 106 can define a generally arcuate shape. The generally arcuate shape can be configured to fit over a medial anterior portion 150 of the femur 12 a, 12 b. It will be appreciated in light of the disclosure the arcuate shape can be configured to be disposed over a medial surface and an anterior surface of the distal end 20 of the femur 12 . In this position, the arcuate shape of the cutting guide member 106 can be disposed over a portion of the medial anterior corner of the femur 12 .
[0034] The first cutting channel 144 and the second cutting channel 146 can be configured with a similar size and/or shape but can be spaced from one another a predetermined distance 160 . In one example, the predetermined distance 160 can be sufficient enough to provide about a three millimeter difference in a distal cutting depth 162 ( FIG. 5C ) between a resection based on the first reference plane 154 and a resection based on the second reference plane 158 . By way of the above example, the medical professional can resect a portion of the femur 12 by placing the suitable resecting tool 148 through the first guide channel 144 . The resecting tool 148 ( FIG. 5F ) can also cut an additional three millimeters from the femur 12 a, 12 b by placing the resecting tool 148 through the second guide channel 146 and cutting the distal end 20 of the femur 12 a, 12 b based on the second reference plane 158 established by the second guide channel 146 .
[0035] The body portion 142 of the cutting guide member 106 can include a plurality of apertures 164 . Each of the apertures 164 can receive one or more fixation pins 166 . The plurality of apertures 164 can include at least a first set of apertures 164 a, a second set of apertures 164 b and a third set of apertures 164 c. With the cutting guide member 106 secured to the femur 12 a, 12 b with the fixation pins 166 either in the first set of apertures 164 a or in the second set of apertures 164 b, the cutting guide member 106 can still be removed from the femur 12 without the need to remove the fixation pins 166 . In this regard, the first set of apertures 164 a and the second set of apertures 164 b are configured so as to permit the cutting guide member 106 to be lifted off the femur 12 a, 12 b with the fixation pins 166 remaining, as shown, for example, in FIG. 5D .
[0036] In contrast, the third set of apertures 164 c are configured such that when the cutting guide member 106 is fixed to the femur 12 using the third set of apertures 164 c, the cutting guide member 106 can only be removed from the femur 12 a, 12 b by removing the fixation pins 166 from the third set of apertures 164 c. As such, securing the cutting guide member 106 to the femur 12 a, 12 b with the third set of apertures 164 c ( FIG. 5F ) relative to the first set of apertures 164 a ( FIG. 5C ) can be shown to provide a relatively more robust securement during a resection procedure. The fixation pins 166 , however, need to be removed from the third set of apertures 164 c before the cutting guide member 106 can be removed from the femur 12 .
[0037] In one example, when one or more of the fixation pins 166 are in the first set of apertures 164 a, the fixation pins 166 are disposed generally normal to an exterior surface 168 of the femur 12 a, 12 b. Because the fixation pins 166 are generally normal to the exterior surface 168 , the cutting guide member 106 can be secured from rotation and/or displacement in directions that are generally parallel to the longitudinal axis 114 ( FIG. 6 ) of the femur 12 a, 12 b.
[0038] The cutting guide member 106 , however, can be pulled away from the exterior surface 168 of the femur 12 a, 12 b so that the cutting guide member 106 can be, for example, repositioned. In this regard, the cutting guide member 106 can be advanced up (i.e., in a superior direction) or down (i.e., in an inferior direction) relative to the longitudinal axis 114 of the femur 12 to adjust the reference planes 154 , 158 for a more deep or a more shallow resection of the distal end 20 of the femur 12 (see, e.g., FIGS. 5C , 5 D, 5 E and 5 F). In doing so, the first set of apertures 164 a can release the fixation pins 166 and the second set of apertures 164 b can receive the fixation pins 166 so that the cutting guide member 106 can be located in a more superior position. In contrast, the third set of apertures 164 c in the cutting guide member 106 can be at an angle 169 ( FIG. 5D ) that, in certain aspects, is not parallel to the first and second set of apertures 164 a, 164 b. The configuration of the angle 169 allows the cutting guide member 106 to be relatively more securely fastened to the femur 12 a, 12 b in that the cutting guide member 106 may not lift off the femur 12 a, 12 b, while the fixation pins 166 are received by the third set of apertures 164 c.
[0039] With reference to FIG. 5F , the suitable resecting tool 148 can be manual or powered. A powered implementation of the resecting tool 148 can be electrical and/or pneumatic. A portion of the resecting tool 148 , for example, a blade 172 can index off (e.g., abut while reciprocating) one of the first cutting channel 144 or the second cutting channel 146 formed in the cutting guide member 106 . In this regard, the resecting tool 148 can cut along (or cut generally parallel to) the reference plane 154 established by the first cutting channel 144 or the second reference plane 158 established by the second cutting channel 146 .
[0040] With reference to FIG. 5A , the intramedullary rod 110 can be configured to fit into an intramedullary canal 176 . In one example, the intramedullary rod 110 can be inserted in a hole i 78 formed between the condyles 22 , 24 of the distal end 20 of the femur 12 . It will be appreciated in light of the disclosure that the intramedullary rod 110 can be inserted in the hole 178 , a sufficient distance so that various components can be installed on an end of the intramedullary rod 110 that is not disposed in the intramedullary canal 176 . A portion of the intramedullary rod 110 can be configured to accept a removable handle 180 that can be used to facilitate installation and/or removal of the intramedullary rod 110 in and from the intramedullary canal 176 and/or to facilitate installation or removal of various components on and from the intramedullary rod 110 .
[0041] With reference to FIG. 4A , a cross-section 182 of the intramedullary rod 110 can be generally oval but can include one or more portions that can be removed from an otherwise whole oval-shape. In one example, two v-shaped grooves 184 can be formed at generally opposite sides of the intramedullary rod 110 . The v-shaped grooves 184 or other suitable portions removed from the intramedullary rod 110 can provide for an anti-rotation functionality. In this regard, one or more components that can be inserted on the intramedullary rod 110 can be keyed (i.e., include key to interconnect with one of the grooves 184 ) to provide an anti-rotation functionality.
[0042] The various components of the cutting guide assembly 100 can be made of one or more suitable bio-compatible materials. One example of a bio-compatible material is a cobalt chrome alloy. Other examples can include titanium and suitable polymers such as an ultra high molecular weight polyethylene.
[0043] With reference to FIGS. 4 , 7 A, 7 B, 7 C, the bushing 112 can couple the intramedullary rod 110 to the index member 102 . The bushing 112 can be configured such that the intramedullary rod 110 can be held at the angle 170 relative to the index member 102 . In this regard, the angle 170 can range from negative four to positive four degrees. As explained above, one bushing 112 a can be selected from the plurality of bushings 112 to select a predetermined angle between the intramedullary rod 110 and the index member 102 . As such, each bushing 112 of the plurality of bushings 112 can be configured to provide a different angle between the longitudinal axis 114 of the intramedullary rod 110 and the index member 102 .
[0044] In operation, one or more incisions 30 can be made near the knee joint 10 to provide access to a portion of the distal end 20 of the femur 12 , as shown in FIG. 3 . With reference to FIGS. 4-5F , the intramedullary rod 110 can be mounted into the hole 178 ( FIG. 5C ) formed in the distal end 20 of the femur 12 . The handle 180 can be removed from the intramedullary rod 110 to provide access and to allow for components to be inserted over the intramedullary rod 110 . One of the bushings 112 can be selected from the plurality of bushings 112 ( FIGS. 7A-7C ) to establish, for example, the reference plane 108 , 154 , 158 that is disposed at the angle 170 ( FIGS. 7A-7C ) relative to the longitudinal axis 114 of the intramedullary rod 1 10 . The angle 170 can be a suitable valgus angle as determined by the medical practitioner.
[0045] When one of the proper bushings 112 is selected, the bushing 112 can be coupled to the index member 102 . The bridge member 104 can be coupled to the index member 102 . The cutting guide member 106 can then be coupled to the index member 102 and held in place in the first guide assembly 130 by the one or more mounting mechanisms 140 or other suitable fasteners. The index member 102 , the bridge member 104 and the cutting guide member 106 can be inserted over the intramedullary rod 110 via the bushing 112 and slid down the intramedullary rod 110 to abut the distal end 20 of the femur 12 .
[0046] When the index member 102 abuts the distal end 20 of the femur 12 , the cutting guide member 106 can be manipulated so as to be positioned around the medial anterior portion 150 of the distal end 20 of the femur 12 . In this regard, the arcuate shape of the cutting guide member 106 can be disposed around the medial anterior portion 150 of the femur 12 a, 12 b to provide the access to that portion of the femur 12 a, 12 b.
[0047] The cutting guide member 106 can be releasably coupled to the bridge member 104 so as to provide a sliding resistance between the cutting guide member 106 and the bridge member 104 . It will be appreciated in light of this disclosure that the medical professional can overcome the sliding resistance as he or she manipulates the cutting guide member 106 relative to the femur 12 as he or she positions the cutting guide member 106 about the medial anterior portion of the distal end 20 of the femur 12 .
[0048] With reference to FIG. 5F , when the cutting guide member 106 is positioned as described above, one or more of the fixation pins 166 can be driven into the first set of apertures 164 a formed on the body portion 142 of the cutting guide member 106 . One or more additional fixation pins 166 can be inserted through the third set of apertures 164 c formed in the body portion 142 of the cutting guide member 106 . Resection of the distal end 20 of the femur 12 a, 12 b along the first reference plane 154 established by the first channel portion 144 can occur with the cutting guide member 106 secured to the femur 12 with the fixation pins 166 in one of the first set of apertures 164 a, the second set of apertures 164 b, the third set of apertures 164 c and one or more combinations thereof. When the fixation pins 166 are received in the third set of apertures 164 c, the fixation pins 166 can be removed so as to allow the cutting guide member 106 to be lifted off the fixation pins 166 received in the first set of apertures 164 a and, for example, advanced up in a direction superior to the distal end 20 of the femur 12 and then re-secured by allowing the second set of apertures 164 b to receive the same fixation pins 166 . In this regard, the cutting guide member 106 is advanced up the femur 12 a, 12 b a predetermined distance.
[0049] Prior to or after the advancement of the cutting guide member 106 of the femur 12 a, 12 b, the medical practitioner can continue to resect the distal end 20 of the femur 12 a, 12 b using the first cutting channel 144 or the second cutting channel 146 , which can be at a predetermined distance from the first cutting channel 144 .
[0050] While specific aspects have been described in this specification and illustrated in the drawings, it will be understood by those skilled in the art in light of the disclosure that various changes can be made and equivalents can be substituted for elements thereof without departing from the scope of the present teachings, as defined in the claims. Furthermore, the mixing and matching of features, elements and/or functions between various aspects of the present teachings are expressly contemplated herein so that one skilled in the art will appreciate from the present teachings that features, elements and/or functions of one aspect of the present teachings may be incorporated into another aspect, as appropriate, unless described otherwise above. Moreover, many modifications may be made to adapt a particular situation, configuration and/or material to the present teachings without departing from the essential scope thereof. Therefore, it is intended that the present teachings not be limited to the particular aspects illustrated by the drawings and described in the specification as the best mode presently contemplated for carrying out the present teachings but that the scope of the present teachings will include many aspects and examples following within the foregoing description and the appended claims. | A system locates a femoral cutting guide on a distal end of a femur. The femoral cutting guide establishes at least a first reference plane to perform a distal femoral planar cut. The system generally includes a mounting rod operable to insert into the distal end of the femur. An index member is operable to abut the distal end of the femur. A bridge member extends from the index member. A cutting guide member extends from the bridge member. The cutting guide member includes a first channel that establishes the first reference plane. A mounting mechanism releasably couples the cutting guide member to the bridge member. The mounting mechanism is operable to generate a sliding resistance between the bridge member and the cutting guide member that is generally overcome to position the cutting guide member relative to the femur. | 0 |
CROSS-REFERENCE TO. RELATED APPLICATIONS
[0001] The present application derives priority from U.S. provisional application No. 60/436,515 for INTEGRATED FLAT PANEL DESK SYSTEM; filed: 27 Dec. 2002.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to computer workstations and, more particularly, to a computer workstation having a pivoting working surface that exposes an integrated flat panel liquid crystal display (LCD).
[0004] 2. Description of the Background
[0005] Of the many varieties of commercially-available computer workstations, some are designed to enclose the computer to offer a multi-use work surface, conserve space, provide data privacy, protect the equipment and wiring, and maintain aesthetics. Examples of typical applications include educational and medical institutions, commercial offices, and retail, hospitality, government, and military entities. In these and other situations, it is desirable to incorporate the computers into the desks.
[0006] The are many exemplary patents for computer desks, most of which stow the CPU and monitor under the desk surface. For example, U.S. Pat. No. 4,766,422 to Wolters shows a desk with a standard computer system case and monitor. U.S. Pat. No. 5,611,608 to Clausen shows a desk with a standard computer system CPU and monitor. The desk is designed with an “L” shaped work area with two levels. The “L” shaped configuration limits the work area, as well as contributing to a setup problem for the student and teacher.
[0007] There are also a number of computer desks in which the monitor is placed below the desk top, employing a glass window or removable cover placed above the monitor so that the monitor remains or can be made visible to the user. For instance, U.S. Pat. No. RE034266 to Schairbaum shows a work station with an underdesk display. U.S. Pat. No. 5,957,059 to Burhman depicts a desk with a work surface that retracts to expose a computer system case and monitor. A hinged panel is manipulated to enable the user to see the viewable surface of the monitor. The foregoing systems are acceptable for cathode ray tube (CRT) monitors because they generate a positive light image which can easily he viewed from any angle.
[0008] However, with the advent of flat panel LCDs, the situation has changed. LCD flat panel displays transmit images in a different manner, requiring the user to view them straight on. The highly directional images and lower light emission levels make it difficult to view an LCD screen through a glass surface or to position the display so that the user can view it straight on in an ergonomic manner.
[0009] LCDs offer many advantages over CRT monitors such as requiring less room and using less energy. There is, therefore, a need for a more functional, ergonomically correct, and convenient multi-use computer workstation accommodating LCDs in which the display may be pivoted from a closed secure position into an ergonomically appropriate open position in front of a user.
[0010] Additionally, due to the increased energy management capabilities of LCDs, when combined with the advantages of a pivoting display mechanism, the workstation is able to provide convenient data security without shutting clown the computer workstation or requiring a lengthy warm-up period before re-accessing the screen. The addition of automatic activation and brightness adjustment upon opening the LCD will increase the display's useful life and make LCD units more appropriate for use in a broad variety of situations such as darkened classroom presentations and work locations where screen brightness may be used to eliminate problems with glare.
SUMMARY OF THE INVENTION
[0011] It is, therefore, an object of the present invention to provide a compact, functional, ergonomically correct and convenient multi-use computer workstation in which a pivoting flat panel integral to the work surface rotates a LCD into a vertical position in front of a user.
[0012] It is another object to provide a computer workstation with an integral flat panel as described above in which the pivoting of the flat panel from a closed to an open position is triggered automatically by the user extending a sliding (i.e. pull-out) input device platform.
[0013] It is another object to provide a computer workstation with an integral flat panel as described above with locking sliding (i.e. pull-out) input device platform, and in which the flat panel display (and optionally, integral personal computer) are securely stowed and locked in a closed position until the input device platform is unlocked and extended, thereby providing ample security of the hardware and data therein.
[0014] It is another object to provide a computer workstation with an integral flat panel as described above in which the action of pivoting the flat panel, even when done abusively, from a closed to an open position is controlled so as to protect the delicate circuitry of the equipment and prevent personal injury and/or damage to the workstation, as well as positioning the LCD and flat panel at the ideal angle when open and perfectly level to a work surface when closed.
[0015] It is still another object to provide a computer workstation with a flat panel LCD as described above in which the LCD is automatically pivoted into a viewable position by extending the input device platform, is automatically turned on when it attains the viewing position, and is automatically adjusted for display brightness in accordance with the ambient light conditions in the room.
[0016] According to a preferred embodiment of the present invention, the above-described and other objects are accomplished by providing a computer workstation having a desktop/work surface defined by a central aperture, and a pivoting, integral LCD support panel positioned in the aperture. A flat panel LCD is mounted on the support panel which is, in turn, affixed to two rotatable shafts. In addition, a sliding input device platform (e.g. keyboard shelf) is mounted on telescoping roller brackets underneath the front end of the work surface. Pivoting lever assemblies include lever arms coupled to the rotatable shafts and links coupled to the roller brackets. A hydraulic damper is coupled at one end to one of the lever arms and slidably attached at the other end in a slotted bracket affixed to the underside of the desktop/work surface. The lever assemblies serve to automatically pivot the LCD support panel to an upright position upon extension of the input device platform. The damper freely extends as the LCD support panel is opened to its upright position, but is engaged as the support panel is closed to bring the support panel and attached LCD to a safe and gentle stop. In this preferred embodiment, the LCD additionally includes a mercury switch for turning the LCD on once it has attained an upright position (i.e. the support panel is in the fully open position), and for turning it off when the support panel is in the closed position.
[0017] As a preferred option, the sliding input device platform includes a locking device which prevents unauthorized access to the input device and to the LCD display to protect the hardware. In addition, it is contemplated that the computer workstation may be integrally incorporated with the display, in which case the locking device prevents unauthorized data access as well. While the locking device may be a simple keylock, the presently preferred embodiment includes a Dialock® system by which multiple computer desks all with pivoting LCD support panels may be centrally unlocked using a single transponder stick inserted in a wall receptacle. This intelligent key system is completely tamper-proof.
[0018] An alternative multi-display embodiment of the present invention incorporates a large tabletop/work surface defined by multiple (i.e. two or more) apertures, with a pivoting, integral LCD support panel positioned in each of the apertures. A flat panel LCD is mounted on each of the support panels and a sliding input device platform is mounted on telescoping roller brackets underneath the edge of the work surface directly in front of each support panel and LCD. The pivoting mechanism for each LCD is as described above, and each LCD may be pivoted to an uptight position; independently of the others, by extending the corresponding input device platform.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Other objects, features, and advantages of the present invention will become more apparent from the following detailed description of the preferred embodiment and certain modifications thereof when taken together with the accompanying drawings in which:
[0020] FIG. 1 is a front perspective view of a computer workstation 10 , shown with a LCD support panel 14 in the closed position and a sliding input device platform 30 in a fully retracted position, according to a preferred embodiment of the present invention.
[0021] FIG. 2 is a side perspective view of the computer workstation 10 of FIG. 1 , shown with the support panel 14 in a closed position.
[0022] FIG. 3 is a side perspective view of the computer workstation 10 of FIGS. 1 and 2 , shown with the support panel 14 in a partially open position.
[0023] FIG. 4 is a side perspective view of the computer workstation 10 of FIGS. 1-3 , shown with the support panel 14 and integrated flat panel LCD 60 in a fully open position.
[0024] FIG. 5 is a front perspective view of the computer workstation 10 of FIGS. 1-4 , shown with the support panel 14 and integrated flat panel LCD 60 in the fully open position, and the sliding input device platform 30 in a fully extended position.
[0025] FIG. 6 is a bottom perspective view of the computer workstation 10 of FIGS. 1-5 , shown with the support panel 14 and integrated flat panel LCD 60 in the closed position.
[0026] FIG. 7 is a top perspective view of a multi-station computer workstation/conference table 110 shown with two LCD support panels 114 in an open position, six support panels 115 in a closed position, and two sliding input device platforms 130 in a fully extended position, according to an alternative embodiment of the present invention.
[0027] FIG. 8 is a system diagram of a Dialock® system by which all of the pivoting LCD support panels 14 , 114 in multiple computer workstation 10 or in multi-station computer workstations/conference tables 110 , as described above, may be centrally locked and/or unlocked using a single transponder stick inserted in a wall receptacle 90 .
[0028] FIG. 9 is an exploded diagram of the Dialock® locking device which is installed at each of the sliding input device platforms 30 , 130 to lock/unlock them.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] FIG. 1 is a front perspective view of a computer workstation 10 according to a preferred embodiment of the present invention. The computer workstation 10 generally includes a sliding input device platform 30 and a pivoting support panel 14 in a work surface 12 , the support panel 14 being adapted to support an integrated flat panel LCD 60 (see FIG. 5 ) mounted thereon. In accordance with the present invention, a mechanism is provided (described below) by which extension of the input device platform 30 into a working position (see FIG. 5 ) automatically and gently rotates the flat panel LCD 60 to a viewable position in front of a user. Additionally, the rotation may automatically turn the LCD 60 on by means of a gravity switch.
[0030] FIGS. 2-4 are side perspective views of the computer workstation 10 with the support panel 14 and integrated flat panel LCD 60 shown, respectively, in closed, partially open, and fully open positions, according to a preferred embodiment of the present invention. The computer workstation 10 generally includes a desktop/work surface 12 defined by a central aperture 13 and a pivoting support panel 14 for supporting a flat panel LCD 60 positioned within the aperture 13 . The support panel 14 sits flush within the aperture 13 of the work surface 12 when it is closed.
[0031] The desktop/work surface 12 sits atop a foundation 11 (see FIG. 1 ) which is a conventional computer workstation frame bounded on three sides by side walls and having a built-in power strip 19 (see FIG. 1 ) for powering the computer and other auxiliary/peripheral equipment. The computer CPU (not shown in the Figures) may be a separate component from the flat panel LCD 60 , in which case the CPU is stowed in a compartment 18 (see FIG. 1 ) inside the foundation 11 . Alternatively, the CPU may be integrally built into the flat panel LCD 60 .
[0032] The support panel 14 is side-mounted by two, collinear, pivot shafts 46 (sec FIG. 6 ) which extend into bearing blocks 44 (see FIG. 6 ) mounted to the support panel 14 . Lever assemblies 20 , attached to the blocks 44 and thereby engaged with the support panel 14 , rotate the panel 14 from a closed position to a fully open position. The lever assemblies 20 are manually-actuated by the input device platform 30 , which is slidably suspended beneath the front edge of the work surface 12 (on roller brackets 26 which are affixed to the underside of the work surface 12 in a spaced relationship). Each lever assembly 20 further comprises a lever arm 22 and a link 24 . Each link 24 is pivotally attached at one end to a roller bracket 26 via, for example, a shoulder bolt 50 . A hydraulic, double-ended or uni-directional damper 170 , commercially available from AVM, Inc. of Marion, S.C. (i.e. as part/model no. sd200acjps006), is pivotally attached via a block/pin assembly 174 and a spring 175 to one of the lever arms 22 and slidably attached via a second block/pin assembly 176 to a slotted bracket 180 affixed to the underside of the desktop/work surface 12 . With the support panel 14 in the closed position of FIG. 2 , the spring 175 is fully compressed and the damper's shaft 172 is fully retracted with the block/pin assembly 176 positioned at the back end of the slot 182 formed in the bracket 180 .
[0033] The support panel 14 is pivoted to the partially open position of FIG. 3 by pulling the input device platform 30 out from under the front edge of the work surface 12 . This action extends (i.e. telescopes outward) the two roller brackets 26 simultaneously. Movement of the roller brackets 26 then begins to draw the links 24 outward. The other ends of links 24 are pivotally attached to one end of the lever arms 22 . Therefore, as links 24 move in response to the movement of the input device platform 30 , lever arms 22 are pulled forward and slightly downward. Lever arms 22 in turn, via fixed attachments to bearing blocks 44 (see FIG. 6 ), rotate the support panel 14 from the closed position of FIG. 2 to the partially open position of FIG. 3 . As the lever arms 22 respond to the extension of the input device platform 30 , the spring 175 first begins to extend before eventually setting the damper 170 into motion. Movement of the damper 170 then causes the block/pin assembly 176 to traverse the slot 182 in the bracket 180 .
[0034] FIG. 4 shows the computer workstation 10 with the support panel 14 in a fully open position due to the complete extension of the input device platform 30 . The lever assemblies 20 are fully engaged with the support panel 14 to rotate it to an approximately 80 degree vertical upright position (the angular position is a matter of design choice). It can now be seen that a flat panel LCD 60 is fixedly mounted to the underside of support panel 14 .
[0035] As the support panel 14 opens (i.e. rotates between the partially open position of FIG. 3 and the fully open position of FIG. 4 ), the block/pin assembly 176 traverses (left to right) the slot 182 in the bracket 180 . However, the block/pin assembly 176 reaches the forward end of the slot 182 before the support panel 14 reaches its fully open position. When the motion of the block/pin assembly 176 is halted at the forward end of the slot 182 , the shaft 172 of the damper 170 is freely extended as the support panel 14 opening process is completed. The extension of the shaft 172 in this manner readies the damper 170 for operation during the closing of the support panel 14 . The damped movement of the support panel 14 during the closing process occurs in the following manner.
[0036] As the support panel 14 is returned to the closed position of FIG. 2 , the block/pin assembly 176 traverses (right to left) the slot 182 in the bracket 180 and reaches the back end of the slot 182 before the panel 14 reaches the closed position. When the motion of the block/pin assembly 176 is halted at the back end of the slot 182 , the shaft 172 of the damper 170 is pushed into the damper's body, thereby engaging the its internal, unidirectional motion damping system to bring the support panel 14 and attached LCD 60 to a safe and gentle stop in the closed position.
[0037] The spring 175 creates a minimal amount of shaft 172 extension just as the opening process commences (see FIG. 3 ). This minimal amount of shaft 172 extension, generating a small amount of motion damping capability in the damper 170 , is a safety feature designed to prevent the support panel 14 from slamming shut should the opening process be accidentally aborted prior to completion (e.g. a user inadvertently letting go of the input device platform 30 when the support panel is in the position shown in FIG. 3 , whereupon gravity would act to return the panel to the closed position of FIG. 2 ).
[0038] A stop bracket 42 is secured by, for example, a plurality of screws to the underside of the work surface 12 along the front edge of the aperture 13 . The stop bracket 42 extends into the aperture 13 a short distance to limit the rotation of the support panel 14 and attached LCD 60 , thereby ensuring that support panel 14 comes to rest flush with the work surface 12 when the desk 10 is closed (as in FIG. 2 ).
[0039] The LCD 60 is preferably a 15″-20″ flat panel LCD with a power cord that plugs into the power strip resident in the computer workstation 10 . The LCD 60 is conventional in most respects, but also includes an OEM-supplied and retrofitted mercury switch 62 (see FIG. 5 ) for selectively applying power to the unit dependent on its orientation. The mercury switch 62 is mounted such that power is supplied to the LCD 60 when it is positioned at approximately an 80 degree upright angular orientation.
[0040] FIGS. 1 and 5 are front perspective views of the computer workstation 10 shown with the support panel 14 in the closed and fully open positions, respectively, and the input device platform 30 in the fully retracted and extended positions, respectively.
[0041] FIG. 6 is a bottom perspective view of the computer workstation 10 , shown with the support panel 14 and integrated flat panel LCD 60 in the closed position, which further illustrates the lever assemblies 20 . The lever assemblies 20 on either side are identical, and only one need be explained in detail. As explained previously, the support panel 14 is side-mounted by a shaft 46 . Each shaft 46 extends into a bearing block 44 at one end and a mounting block 48 at the other end. The bearing block 44 is rotatably engaged with the shaft 46 and is anchored to the support panel 14 by, for example, a plurality of screws. The mounting block 48 is fixedly attached to the shaft 46 and is mounted to the underside of the work surface 12 by, for example, a plurality of screws. At a point between the two blocks 44 , 48 , one end of lever arm 22 is fixedly attached to the bearing block 44 and extends rearwardly and slightly downwardly therefrom. The other end of lever arm 22 is pivotally attached at hinge 40 to one end of link 24 as shown. The other end of link 24 is, in turn, pivotally attached to a roller bracket 26 via a hinge 50 (i.e. shoulder bolt) such that inward or outward movement of the input device platform 30 telescopes the roller bracket 26 and operates the lever arm 22 and link 24 , thereby pivoting the support panel 14 . The commercially-available hydraulic damper 170 is, via its shaft 172 , pivotally attached by a block/pin assembly 174 and a spring 175 to one of the lever arms 22 and slidably attached via a second block/pin assembly 176 to a slotted bracket 180 affixed to the underside of the desktop/work surface 12 .
[0042] The foregoing computer workstation 10 serves to automatically pivot the support panel 14 , positioned in the work surface 12 , and the attached flat panel LCD 60 into a vertical position in front of a user. The flat panel LCD 60 moves from a closed to an exposed position and is powered automatically when the user extends the sliding keyboard shelf 30 . The mercury switch 62 in the LCD 60 closes upon attaining a substantially upright position, thereby ensuring that the LCD 60 is on only when desired.
[0043] FIG. 7 is a top perspective view of an alternative embodiment of the present invention. A multi-station computer workstation 110 , or conference table, incorporates a tabletop/work surface 112 defined by two or more apertures 113 , with a pivoting, integral LCD support panel 114 , 115 positioned in each of the apertures 113 . The eight-station embodiment of FIG. 7 shows two LCD support panels 114 in an open position and six support panels 115 in a closed position. Each support panel 115 sits flush within the aperture 113 of the work surface 112 when it is closed. The work surface 112 sits atop a conventional conference table foundation 111 . A plurality of built-in power strips (not shown in FIG. 7 ) for powering multiple computers and other auxiliary/peripheral equipment are affixed to the foundation 111 . The computer CPUs (not shown in FIG. 7 ) may be separate components from the flat panel LCDs 160 , in which case the CPUs are stowed in compartments (not shown in FIG. 7 ) inside the foundation 111 . Alternatively, the CPU may be integrally built into the flat panel LCD 160 .
[0044] Each of the support panels 114 , 115 is mounted and cycled between its open and closed positions in the manner described above with respect to FIGS. 1-6 (i.e. utilizing the combination of two lever assemblies 20 and a hydraulic damper 170 ). Flat panel LCDs 160 are fixedly mounted to the underside of support panels 114 , 115 and a sliding input device platform 130 is mounted on telescoping roller brackets 126 underneath the edge of the work surface 112 directly in front of each support panel 114 , 115 and LCD 160 . FIG. 7 shows the computer workstation 110 with the two support panels 114 in a fully open position (i.e. an 80 degree vertical upright position) due to the complete extension of the corresponding input device platforms 130 (supporting computer keyboards 132 ). Stop brackets (not shown in FIG. 7 ) secured by, for example, a plurality of screws to the underside of the work surface 112 along the front edge of the aperture 113 . Each stop bracket extends into the corresponding aperture 113 a short distance to limit the rotation of the support panel 114 , 115 and attached LCD 160 , thereby ensuring that support panel 114 , 115 comes to rest flush with the work surface 112 when the desk 110 is closed (see specifically, support panels 115 ).
[0045] As above, each LCD 160 is preferably a 15″-20″ flat panel LCD with a power cord that plugs into one of the power strips resident in the computer desk 110 . The LCD 160 is conventional in most respects, but also includes an OEM-supplied, or retrofitted, mercury switch (not shown in FIG. 7 ) for selectively applying power to the unit dependant on its orientation. The mercury switch is mounted such that power is supplied to the LCD 160 when it is positioned at approximately an 80 degree upright angular orientation.
[0046] The foregoing alternative computer workstation/conference table 110 allows one or more users to automatically pivot a support panel 114 , 115 and the attached flat panel LCD 160 into a vertical, viewable position. Each LCD 160 may be pivoted from a closed to an exposed position and be powered automatically, independently of the others, by extending the corresponding input device platform 130 . The mercury switch in each LCD 160 closes upon attaining a substantially upright position, thereby ensuring that an LCD 160 is on only when desired.
[0047] As a preferred option, the sliding input device platforms 30 , 130 , in the embodiments described above with respect to FIGS. 1-7 , are each equipped with a locking device, which prevents unauthorized access to the keyboard and the LCD 60 , 160 , when protection of either the hardware and/or data is desired (as set forth previously, it is contemplated that the computer CPU may be integral to the display 60 , 160 , in which case the locking device prevents unauthorized data access as well). While the locking device may be a simple keylock, the presently preferred embodiment includes a Dialock® system by which multiple computer workstations 10 all with pivoting LCD support panels 14 may be centrally unlocked using a single transponder stick inserted in a wall receptacle. This particular intelligent key system is commercially-available and completely tamper-proof. The Dialock® system is incorporated as follows.
[0048] FIG. 8 is a system diagram of a Dialock® system by which all of the pivoting LCD support panels 14 , 114 in multiple computer workstations 10 or in multi-station computer workstations/conference tables 110 , as described above, may be centrally locked and/or unlocked using a single transponder stick inserted in a wall receptacle 90 . The system generally includes a programmable central controller 70 , a wall-mount receptacle 90 connected to the central controller 70 for insertion of a key-transponder, and multiple remote lock assemblies 80 a - d connected to the central controller 70 . The lock assemblies 80 a - d are installed proximate each of the sliding input device platforms 30 , 130 to lock them and the corresponding LCDs 60 , 160 in the closed position, subject to authorized key access via receptacle 90 . All of the foregoing components are commercially available from The Häfele Group.
[0049] FIG. 9 is an exploded diagram of one of the Dialock® remote lock assemblies 80 a - d (see FIG. 8 ) installed at each of the sliding input device platforms 30 , 130 to lock/unlock them. Each remote lock assembly 80 a - d further comprises a locking shaft 92 which is secured to the inside edge of the sliding input device platform 30 , 130 (by screws), a reinforcing receptacle plate 93 which is secured inside a computer workstation 10 , or a multi-station computer workstation/conference table 110 , in a position corresponding to the closed position of the sliding input device platforms 30 , 130 and an electronic lock 94 which is secured to and behind receptacle plate 93 . When the locking shaft 92 is inserted into the electronic lock 94 by closure of the sliding input device platforms 30 , 130 (and commensurate closure of the corresponding LCDs 60 , 160 ), the electronic lock 94 locks it in the closed position subject to keyed access at receptacle 90 (see FIG. 8 ). This option allows multiple computer workstations 10 all with pivoting LCD support panels 14 to be centrally unlocked using a single transponder stick inserted in wall receptacle 90 , and renders the enclosed keyboard and LCD completely tamper-proof.
[0050] Having now fully set forth the preferred embodiments and certain modifications of the concept underlying the present invention, various other embodiments as well as certain variations and modifications of the embodiments herein shown and described will obviously occur to those skilled in the art upon becoming familiar with said underlying concept. It is to be understood, therefore, that the invention may be practiced otherwise than as specifically set forth herein. | A computer workstation having a desktop/work surface defined by a central aperture and a pivoting liquid crystal display (LCD) support panel mounted on pivot shafts in the aperture. In addition, a sliding input device platform is mounted on telescoping roller brackets underneath the front edge of the work surface. Lever arms are rotatably engaged with the pivot shafts and are linked to the roller brackets. The lever arms automatically pivot the LCD support panel to an upright position upon extension of the input device platform, and vice versa, and a hydraulic damper brings the LCD support panel to a safe, gentle stop. Aa mercury switch turns the LCD on and off automatically upon opening or closing. Two or more such LCD support panels and associated hardware can be included in a single desktop/work surface for a computer training and/or conferences. | 0 |
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
This Patent Application is related to co-pending U.S. patent application Ser. No.: 08/979,748, now U.S. Pat. No. 6,275,937 issued Aug. 14, 2001, filed Nov. 26, 1997, entitled “Collaborative Server Processing of Content and Meta-Information with Application to Virus Checking in a Server Network,” by B. Hailpern et al. This Patent Application is also related to co-pending U.S. patent application Ser. No.: 09/027,832, now U.S. Pat. No. 6,122,666 issued Sep. 19, 2000, filed Feb. 23, 1998, entitled “Method for Collaborative Transformation and Caching of Web Objects in a Proxy Network”, by J. Beurket et al.
FIELD OF THE INVENTION
This invention relates to data networks and, more particularly, to an ability to perform distributed object rendering on a data network. Specifically, a plurality of collaborative proxy servers perform distributed object rendering so that object contents can be displayed on or consumed by various kinds of client devices, based on their respective device capabilities and specifications.
BACKGROUND OF THE INVENTION
As the Internet becomes ever more popular, more non-personal computer (PC) devices, such as so-called smart phones and PDAs (personal digital assistants), are connected to the Internet, either by wired or wireless connections. The Internet is becoming the so-called pervasive computing environment, where various kinds of information appliances/devices, as well as PCs and other server computers, are all connected. In such a pervasive computing environment it is expected that the individual appliances/devices will have different computing powers and display capabilities. For example, some devices may be capable of displaying color images while others can only display black-and-white images. Also, some devices may have large, easily viewed displays while others may have only a relatively much smaller display. It can thus be appreciated that in such a pervasive computing environment the same information objects may have to be rendered in different forms or resolutions according to different device display specifications. Various techniques have been developed to represent information in various resolutions. In “A Framework for Optimization of a Multiresolution Remote Image Retrieval System” by A. Ortega et al., Proceedings of IEEE InforCom, 1994, a system was disclosed to transmit images and video in multiple resolutions. In “The JPEG Still Picture Compression Standard,” by G. Wallace, IEEE Transactions on Consumer Electronics, vol. 38, no. 1, February 1992, the JPEG image compression standard was described to represent images in multiple different resolutions.
The rendering of an object into different forms or resolutions can be performed in different locations. One possible location is within the content servers. However, the content servers may easily become overloaded, especially with a large number of different client requests all coming to the same content servers. Another possible location to render the object is within a client machine which will actually consume the object. However, this is an undesirable solution since many typical client machines tend to be too limited in computing power to perform the necessary rendering function.
Alternatively, the rendering can be done by one or more proxy servers, which are positioned in the data network between the content servers and the client devices. In this scenario the device-specific information can be piggybacked on the meta-information associated with the objects, and the proxy server can perform object rendering according to the meta-information. Once the object rendering is performed by the proxy server the result can be cached (stored) at the proxy server. In this case any subsequent requests for the same object, from the same kind of device, can be served directly from the stored copy in proxy server cache. As a result, the repeated rendering of the object for the same kind of device can be avoided. In order to improve the response time, many PC servers, such as the IBM NETFINITY servers, are being deployed in the Internet as a network of proxy servers (IBM and NETFINITY are both registered trademarks of the International Business Machines Corporation). These proxy servers can work collaboratively in object rendering and caching.
For example, in the above-referenced commonly assigned U.S. Patent Application by B. Hailpern et al., entitled “Collaborative Server Processing of Content and Meta-Information with Application to Virus Checking in a Server Network,” a method was disclosed to perform virus checking based on the meta-information on the proxy network by choosing one proxy server. This approach discloses a method to perform certain computations on the object based on the meta-information by one of the proxies in the network. No specific attention was paid to the aspect of caching the objects after the computation. Also, the computation is done completely by the chosen proxy server, and is not done by more than one proxy server in a distributed way.
In the above-referenced commonly assigned U.S. Patent Application by J. Beurket et al., entitled “Method for Collaborative Transformation and Caching of Web Objects in a Proxy Network,” a method was proposed to locate one or more specialized proxies to perform the transformation and caching. Once the transformation/rendering is done and cached, all subsequent requests for the desired resolution are served by these specialized transformational proxies. In this approach the caching and rendering of an object is completely done on the same specialized proxies, and the rendering of objects is not readily performed in different stages or collaboratively by more than one different proxies in a distributed way.
In an approach described by A. Fox, entitled “Adapting to Network and Client Variation Using Infrastructural Proxies: Lessons and Perspective,” IEEE Personal Communications, pp. 10-19, August 1998, a method was disclosed to perform datatype-specific distillation on a cluster of proxies. Object rendering and caching are all performed by the specific cluster of proxies. A centralized manager is used to perform load balancing among the proxies in the cluster. A drawback of this approach is that object rendering and caching is completely done on the same cluster of proxies, and is not done in a distributed way. Other proxies in the network, but not in the same cluster, cannot participate in some of the stages in the object rendering process.
In view of the foregoing, it can be appreciated that there exists a need for a collaborative proxy system that can deploy object rendering in a distributed fashion. Prior to this invention, this need was not fulfilled.
OBJECTS AND ADVANTAGES OF THE INVENTION
It is a first object and advantage of this invention to provide a collaborative proxy system that performs object rendering in a distributed fashion.
It is another object and advantage of this invention to provide a technique to distribute object rendering processing throughout a proxy network, and to not concentrate the object rendering processing in only specialized object rendering proxies.
It is a further object and advantage of this invention to provide a collaborative proxy network wherein object processing tasks, such as rendering, are distributed in an adaptive fashion based on, for example, dynamic loading characteristics of the proxy network.
SUMMARY OF THE INVENTION
The foregoing and other problems are overcome and the objects and advantages are realized by methods and apparatus in accordance with embodiments of this invention.
In accordance with the teachings of this invention a distributed object rendering method for a collaborative data network is disclosed. The data network, which may include the Internet, has attached computing nodes, including object requestor nodes, object source nodes, and intermediate nodes which may be proxy servers. The method can allow each participating proxy server, which may be referred to simply as a “proxy” and in the plural form as “proxies”, to adapt to the dynamic load conditions of itself as well as proxies, as well as to the dynamic traffic conditions in the data network. The determination of which proxy or set of proxies is to perform object rendering and caching is based on a distributed, collaborative method that is adopted among the proxies. The criteria for such a method can include the bandwidth and current load of the network links among proxies, and/or the respective CPU usage of the proxies. If an object rendering can be staged, e.g., different resolution rendering, it can be performed by more than one of the proxies. The determination of which proxy performs which stage of the multistage rendering can also be adaptive to the dynamic load conditions, as well as network conditions.
As a result, a participating proxy, upon serving an object, first determines if object rendering processing is needed based on the client device type. If the object rendering processing is found to be required, then based on the requested object type and the collaborative information about other proxies in the network, the participating proxy can choose to (a) perform the complete object rendering by itself, (b) perform a partial rendering if the rendering process can be staged, or (c) do nothing and let another proxy perform the rendering task. The objective is to distribute the rendering processing throughout the proxy network, not just in the specialized object rendering proxies.
This invention thus provides a distributed, dynamic, hierarchical rendering method in a network comprised of interconnected computing nodes. The method includes steps of, at an object requesting node or at a proxy node coupled to the object requesting node, including with an object request certain meta-information describing the capabilities of the object requesting node (referred to herein as receiver hint information (RHI) or as requestor-specific capability information); at an intermediate node, receiving an object request and forwarding the request to another intermediate node (or to a source of the requested object), if the requested object is not available locally, while modifying the RHI to include information for specifying its local condition for providing the rendering service; otherwise, the intermediate node determines the required rendering, and invokes a selection function to determine, based on the RHI, what part or subset of the required rendering is to be carried out by the intermediate node. The intermediate node then performs the rendering and passes the rendered object to the requesting node. As a part of this invention another intermediate node that receives a partially rendered object invokes a selection function to determine, based on the RHI, what portion (or all) of the remaining required rendering is to be carried out by this intermediate node, and then performs the rendering and passes rendered object to the requesting node.
At an intermediate node having a less detailed version of the requested object the method includes such information in the RHI, forwards the request to another node, and at another intermediate node that has a more detailed version of the requested object, the node decides whether to return the more detailed version of the requested object, without further local rendering, or to instead perform some rendering and return a partially rendered object, or to instead return a completely rendered object.
The local condition information can include the loading and/or capacity of the node (such as CPU utilization), and can be a function of the network delay (from the requesting node). The local condition information can further include a type of rendering that can be performed at the node (which can depend on the software available at the node). The local condition information can further include the storage availability at the local node.
A selection method is provided for each intermediate node to decide dynamically and independently of other nodes what portion of the required rendering to perform locally using the RHI information. The selection method can include steps of (a) dividing a remaining rendering operation into steps; (b) selecting one or more rendering steps to be performed locally in order to optimize a given objective function, using the RHI information as an input parameter; and (c) performing the one or more rendering steps selected for the current node. The objective function can be to perform the rendering steps with the most bandwidth reduction first, and/or to perform the rendering steps so as to reduce load unbalancing among the remaining nodes on the path to the requesting client device node. The objective function can also be an estimated response time from this node to the requesting node, based on the RHI information.
Alternatively, the selection method can includes steps of (a) dividing the remaining rendering operation into steps; (b) assigning, in accordance with an assignment plan, the rendering steps to other nodes on a path to the requesting client device node to optimize the given objective function using the RHI information as the input parameter; and (c) performing the rendering step or steps that are assigned to the current node. It is also within the scope of the teaching of this invention to pass the assignment plan as meta information associated with the rendered object to a next node, which is then free to modify the assignment plan according to local considerations, such as CPU loading at the next node.
The rendered object and/or the received object can be passed to a cache manager for a caching consideration, such as a cost to produce the rendered object.
In general, different intermediate nodes can choose to use different selection functions for rendering, and each intermediate node may choose a different selection function depending upon the local condition of the node (e.g., CPU loading).
Each node may also periodically collect load statistic information from neighboring nodes, instead of including the information in the RHI associated with each request.
BRIEF DESCRIPTION OF THE DRAWINGS
The above set forth and other features of the invention are made more apparent in the ensuing Detailed Description of the Invention when read in conjunction with the attached Drawings, wherein:
FIG. 1 is a block diagram of an Internet environment in accordance with an exemplary embodiment of the present invention.
FIG. 2 is a block diagram which illustrates a proxy environment in accordance with an exemplary embodiment of the present invention.
FIG. 3 is a flowchart diagram which illustrates the configuration of proxy servers in accordance with an exemplary embodiment of the present invention.
FIG. 4 is a flowchart diagram which illustrates operations of a proxy server when it receives an object request in accordance with an exemplary embodiment of the present invention.
FIG. 5 is a flowchart diagram which illustrates operations of a proxy server when it receives an object in accordance with an exemplary embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a block diagram illustrating the overall architecture of a proxy network in accordance with an exemplary embodiment of the present invention. As is shown, various clients 130 , 131 may be connected through proxy servers (or proxies) 110 , 111 , 112 to access information objects in the content servers 120 , 121 . The clients, proxies and content servers may be all connected through a network 101 , such as the Internet. The proxies 110 , 111 , 112 are generally employed to improve access times, and to provide services such as caching and content filtering. For example, an ISP (Internet Service Provider) may comprise a hierarchical network of proxy servers 110 , 111 , 112 positioned at various locations (e.g., local, regional and national proxy servers). Alternatively, and also be example, there may be one or more proxy servers that function within a private or semiprivate local area network (LAN) or wide area network (WAN), and the one or more proxy servers may be located behind a firewall that provides security for the LAN or WAN.
Object renderings are performed by the proxies 110 , 111 , 112 based on objects retrieved from the content servers 120 , 121 . The specific device capabilities, referred to herein as receiver hint information (RHI), as well as the object data type (generally referred to herein as object-specific descriptor information) are included such as by being appended to the meta-information associated with requests and requested objects. The RHI can be included with an object request by the requesting client device 130 , 131 , or by one of the proxies (e.g., the first proxy coupled to the requesting device.) In the latter case the proxy 110 , 111 , 112 can access a table of device capabilities, based on an identifier of the requesting device sent with the request, and can construct the RHI based on the stored information in the table. As an example, and assuming an ISP arrangement, the local proxy server has access to a table wherein are stored the characteristics (e.g., type of display, size of graphics memory, etc.) of the various client devices that can be serviced by the local proxy. The table entry for a particular client device 130 , 131 can be stored when the device first registers with the ISP. Thereafter, the local proxy server receives an identifier of the client device when the client device makes a request, accesses the table, and constructs the appropriate RHI for inclusion with the object request. In a similar manner the source of the requested object can add the object-specific descriptor information to the returned object, or this information can be added by the proxy server local to the source of the requested object (for the case where a proxy server does not fulfill the request from a copy of the object stored in the proxy, as described in further detail below.)
In a presently preferred embodiment of this invention the RHI is implemented using PICS™ (“Platform for Internet Content Selection”) information, and this aspect of the invention is discussed in further detail below.
When a requested object passes through the proxy network, any proxy server 110 , 111 , 112 can perform a complete or partial rendering based on the associated RHI. For example, if the entire rendering process can be partitioned into two or more steps, a given one of the proxy servers (e.g., 110 ) may decide to perform only one of the rendering steps, and to then forward the partially rendered object to another proxy server (e.g., 111 ). The proxy server 110 also modifies the RHI to reflect the processing that it performed, and forwards the modified RHI as well to the proxy server 111 . Furthermore, local conditions about a given one of the proxy servers 110 , 111 , 112 , such as the CPU load and the network traffic load, can also be included in the RHI and passed along through the network 101 . These aspects of the invention are discussed below in further detail.
In an exemplary embodiment of this invention the clients 130 , 131 may include, for example, a personal computer (PC), a workstation, a smart phone, a personal digital assistant (PDA), etc. Proxy servers 110 , 111 , 112 may comprise a PC server, a RISC SYSTEM/6000 server, or a S/390 server running, for example, Internet Connection Server (ICS) available from IBM (RISC SYSTEM/6000, S/390, and Internet Connection Server are all trademarks of the International Business Machines Corporation). The network 101 may be, for example, the Internet, the World Wide Web, an Intranet and local area networks (LANs). Content servers 120 , 121 may include a PC server, a RS/6000 server, or an S/390 server running Lotus Go Web server, or Lotus Domino Go server (Go Web and Domino Go are trademarks of Lotus Development Corporation).
FIG. 2 is a block diagram illustrating a general proxy environment in accordance with an exemplary embodiment of the present invention. Proxy server node 201 (which could be, by example, any one of the proxy servers 110 , 111 , 112 of FIG. 1) is used to represent a computing node that can service requests through a network 212 , such as the network 101 of FIG. 1 . Proxy server node 201 preferably includes a CPU 211 , memory 202 such as RAM, and storage devices 210 such as disk storage devices or, more generally, a direct access storage device (DASD). The proxy server logic 203 may be stored within the memory 202 , and is preferably embodied as computer readable and executable code which is loaded from disk 210 into memory 202 for execution by CPU 211 . The proxy server logic 203 , which is described in more detail with reference to FIG. 3, includes an object handler 204 (described in further detail in FIG. 5) and an object request handler 205 (described in further detail in FIG. 4 ). An object renderer 206 , which performs object rendering according to the RHI associated with a particular object, may also be included in the proxy server logic 203 . Object renderer may be a computer program which renders, by example, a color image into a black-and-white image, or one that reduces a complex HyperText Markup Language (HTML) text into a simple HTML text containing only a summary of the HTML headers. Proxy server logic 203 may also include a cache manager 207 which maintains a local copy of the partially rendered or completely rendered objects in order to avoid repeating some object rendering operations with the same proxy server.
FIG. 3 is a flow chart diagram that depicts the general operations of the proxy server node 201 when it is receiving input in accordance with an exemplary embodiment of the present invention. At step 301 , the proxy server node 201 waits for the input. Depending on the input received, different actions are taken. If the input received is an object request at step 302 (e.g., a HyperText Transfer Protocol (HTTP) request from a PDA-type of client 130 , 131 ), then the object request handler 205 is invoked at step 303 . The HTTP is generally used for retrieving document contents and/or descriptive header information. A detailed implementation of object request handler 205 is described in FIG. 4 . If the input received is an object, step 304 , (e.g. an object returned to the present proxy server node 201 in response to a request made by the proxy server node 201 ) the object handler 206 is invoked at step 305 . A detailed implementation of the object handler 206 is described in FIG. 5 . For other types of requests, such as file transfer protocol (FTP) requests, a miscellaneous handler is invoked at step 306 . After invoking the appropriate handler, control returns to step 301 to wait for the next input to the proxy server node 201 from the network 212 .
FIG. 4 is a flow chart diagram illustrating the operations of the object request handler 205 in accordance with an exemplary embodiment of the present invention. At step 401 , the object request handler 205 checks with the cache manager 207 to determine if the requested object is available in the cache. It should be noted that the cache may contain a less detailed version of the requested object, or it may contain a more detailed version. A less detailed version of the object does not satisfy the requirement and a request for the object must be sent out, typically to the appropriate one of the content servers 120 , 121 or to another proxy server. However, a more detailed version of the object may be further rendered by the proxy server 110 , 111 , 112 in order to satisfy the request. If the requested object cannot be found in the cache, at step 404 , the proxy server 110 , 111 , 112 modifies the associated RHI to indicate its ability for providing rendering services and then sends the request and the modified RHI to another proxy server or to the content server 120 , 121 , depending on the position of the proxy server in the entire proxy chain.
If a copy of the requested object can be found in the local cache, at step 402 , the proxy server checks the cached object against the RHI to see if any further rendering is necessary. Note that the RHI contains the capability specification of the receiving device (i.e. the device that originally requested the object that was just found in the cache). By checking the RHI, the proxy server 110 , 111 , 112 can determine if any further rendering is necessary. If no further rendering is necessary, the proxy server modifies the RHI to indicate its local condition for providing rendering services and returns the object at step 403 . If further rendering is found to be necessary, based on the RHI or the requesting device, then the proxy server executes at step 405 a selection function to determine whether or not it wishes to perform the rendering locally. If the proxy server decides not to perform any rendering locally, the proxy server modifies the RHI to indicate its local load condition for providing such rendering services and returns the object along with the modified RHI at step 406 . If the proxy server instead decides to perform the rendering locally, it checks the RHI at step 407 to determine if it wishes to complete the entire rendering process, or just some part of the required rendering process. If the proxy server wishes to perform only a portion of the rendering process, then it executes at step 409 another selection function to determine which part of the rendering process to perform. In either case, and after making the decision to perform local rendering at step 405 , the proxy server 110 , 111 , 112 calls the object renderer 206 to perform the object rendering at step 408 . After the rendering process is complete (either a complete or partial rendering), the cache manager 207 is called at step 410 to determine whether or not to cache a copy of the rendered object locally. The proxy server 110 , 111 , 112 then modifies the RHI at step 406 to reflect its local condition and returns the rendered (completely rendered or partially rendered) object along with the modified RHI.
Those skilled in the art will appreciate that, at step 404 , a proxy server 110 , 111 , 112 may indicate in the RHI that it has a less detailed version of the requested object in the cache, and then send a request for the object to another proxy server. A proxy server that has stored a more detailed version of the requested object may then decide to send the more detailed object to the requesting proxy server, or it may instead send whatever information that is needed in order for the requesting proxy server to render the object to the necessary resolution. Alternatively, the proxy server 110 , 111 , 112 containing the more detailed version of the requested object may decide to perform the necessary rendering for the requesting proxy server and return the completely rendered object to the requesting proxy server. This type of decision can be based on, for example, the loading of the requesting proxy server versus the loading of the proxy server that stores the more detailed version of the requested object.
Those skilled in the art will thus further appreciate that there are many different variations in the selection function for determining whether or not a given one of the proxy servers 110 , 111 , 112 is to perform the entire remaining rendering locally, or what part of the object rendering will be performed locally.
For example, the selection criteria may include the current CPU load and/or the network delay from the requesting node, as well as the load condition of the requesting node. The criteria may further include the type of rendering that is to be performed and the availability of the software needed to do the rendering. For example, a given one of the proxy servers 110 , 111 , 112 may be lightly loaded, yet lack a particular type of software that is required to render the object in a manner consistent with the display capabilities of the requesting one of the clients 130 , 131 . The criteria may also include the local storage availability. However, if a particular proxy server is the last one on the path to the requesting device, then it must be able to perform any remaining rendering locally.
Those skilled in the art will also appreciate that if a given one of the proxy servers 110 , 111 , 112 decides to perform partial rendering, it can first divide the remaining rendering operation into multiple steps and then select one or more of the steps for its own local processing. The goal is to optimize a given objective function using the associated RHI as input parameters. Moreover, a given one of the proxy servers 110 , 111 , 112 may also assign the remaining steps to the remaining proxy server(s) along on the path to the requesting client device 130 , 131 . Any proxy server receiving such an assignment plan may alter the assignment based on its own local condition (e.g., based on loading, storage, and/or the availability of the software necessary to perform its allocated portion of the assignment plan.) The objective function, which is desired to optimize, can be to reduce the greatest amount of bandwidth, to reduce the greatest amount of load imbalance among the remaining proxies on the path to the requesting device, or a combination of the two. It can also be to minimize the estimated response time from the current proxy server 110 , 111 , 112 to the requesting client device 130 , 131 , based on the RHI.
FIG. 5 is a flow chart diagram illustrating the object handler 204 of the proxy server logic 203 . At step 501 , when a proxy server receives an object, it first tests the associated RHI to determine if further rendering is necessary. If not, it passes the object to the cache manager 207 for caching consideration at step 502 . At step 503 , the received object is returned to the requesting client device 130 , 131 , or to another proxy server 110 , 111 , 112 on the path to the receiving client device. In returning the object, the proxy server may modify the associated RHI to indicate its local condition.
If the proxy server instead determines at step 501 that further rendering of the object is necessary, it determines at step 504 whether or not it will perform the rendering based on its local condition(s), such as CPU loading. If it decides not to perform the local rendering, at step 505 it modifies the RHI and then return the object to another proxy server on the path to the requesting client device 130 , 131 . If, on the other hand, the proxy server determines at step 504 to perform local rendering of the object, at step 506 the proxy server further determines if it will perform the entire remaining rendering process locally. If not, it may divide the remaining rendering process into multiple steps, and then select a subset of the steps to perform locally at step 508 . Object renderer 206 is then called to perform the local rendering at step 507 . After the rendering computations, at step 509 , the cache manager 207 is called to determine if the rendered object should be cached. The proxy server 110 , 111 , 112 then modifies the associated RHI and returns the object either to the requesting client device 130 , 131 , or to another proxy server on the path to the requesting client device 130 , 131 .
It is possible that different intermediate proxy servers will choose different selection functions for determining the amount of object rendering to perform locally. In addition, each node in the proxy network can periodically collect load statistics from neighboring proxy server nodes, instead of including such load conditions in the RHI associated with each request.
Those skilled in the art will appreciate that the cache manager 207 , in managing the cache, may take into consideration the processing cost of producing the rendered object. Therefore, the cache manager may maintain a separate stack for locally rendered objects in addition to a regular stack for other objects. It may also cache objects rendered by other proxy servers if it is beneficial to do so.
Having thus described this invention with respect to exemplary embodiments thereof, a more detailed explanation of certain aspects of this invention, in particular the presently preferred implementation for the receiver hint information (RHI), will now be provided, as will an example of the use of this invention.
In general, meta-data information can be stored in HTTP request headers and response headers, much the same way as the PICS™ (“Platform for Internet Content Selection”). Most generally, the PICS™ specification enables labels (metadata) to be associated with Internet content. PICS™ specifies a method of sending meta-information concerning electronic content, and is a Web Consortium Protocol Recommendation (see http://www.w3.org/PICS). PICS™ was first used for sending values-based rating labels for electronic content, but can also facilitate other uses for labels, such as code signing and privacy. However, the format and meaning of the meta-information is fully general. In PICS™, meta-information that is descriptive of electronic content is grouped according to a producer-and-intended-usage of the information, and within one such group, any number of categories or dimensions of information can be transmitted. Each category has a range of permitted values. For a specific piece of content, a particular category may have a single value or multiple values. In addition, the meta-information group, known as a “PICS™ label”, may contain expiration information. Each PICS™ label for a specific piece of electronic content may be added or removed from the content independently.
Reference may be had to a publication entitled “PICS Label Distribution Label Syntax and Communications Protocols”, REC-PICS-labels-961031, Version 1.1, W3C Recommendation 31-October-96, which is available at http://www.w3.org/PICS, and which is incorporated by reference herein in its entirety. Reference can also be had to an article entitled “Filtering Information on the Internet”, Paul Resnick, Scientific American, March 1997.
In accordance with the teachings of this invention, and by example, an image file may be sent from a server with a PICS label having a field or fields set to indicate the resolution of the image. Such a resolution label can be specified by a pair of color encoding and image size, r(c 16 s 1000), where “c” and “s” are transmit names for various meta-information types, and the applicable values for this image content are 16 (for c) and 1000 (for s), indicating a 16-bit color encoding and 1000M bytes image size. Those proxy servers 110 , 111 , 112 that participate in the distributed object rendering are aware of how to interpret these categories and values. Other device capabilities, as well as load conditions of proxy servers, can also be similarly encoded as PICS™ labels and transmitted together with the HTTP request headers and/or response headers.
For example, the device capability of a personal digital device (PDD), such as a PDA, can be specified as a pair of color encoding and image size, d(c 1 s 2), indicating that the PDD can only display (d) an image size (s) of up to 2M bytes (two megabytes) with a 1-bit color encoding (c). This device capability PICS label can be inserted into a HTTP request header sent among different proxy servers 110 , 111 , 112 , either by the PDD or by a proxy server coupled to the PDD, as was described above. This PICS label is referred to in the context of this invention as the receiver hint information (RHI).
It can be appreciated that a proxy server 110 , 111 , 112 that receives an image object having the above-noted PICS label r(c 16 s 1000), in response to a request from the PDD having the above-noted RHI d(c 1 s 2), will be informed that the PDD is incapable of displaying the image object as received, and that the image object will need to be rendered into a form that the PDD is capable of displaying. The proxy server may perform the entire rendering process, and will then modify the PICS label of the image object to be r(c 1 s 2), i.e., to indicate a format compatible with the requesting PDD's display capabilities. If, however, for some reason the proxy server elects to not completely render the image object, or to not render the image object at all, due to, for example, loading considerations or a lack of suitable software, then the PICS label of the image object will not reflect a condition compatible with the display capabilities of the PDD. For example, assume that a given one of the proxy servers 110 , 111 , 112 elects to only modify the color encoding of the received image object from 16 level to 1, then the modified PICS label as received by a next proxy server will be r(c 1 s 1000), which is a form still not compatible with the PDDs' RHI of d(c 1 s 2). The next proxy server 110 , 111 , 112 may then elect to render the received image object to reduce the image size from 1000 megabytes to 2 megabytes, resulting in the modified PICS label of r(c 1 s 2), which is a form that is compatible with the PDDs' RHI of d(c 1 s 2).
As a further example of distributed object rendering, assume that a personal digital device PDD is requesting an image file and such image file is not currently present in any of the proxy servers 110 , 111 , 112 in the network 101 . The request is first sent to a local proxy server A, such as a local ISP (Internet Service Provider), and then forwarded to a regional proxy server B, and then to a national proxy server C. The national proxy server C then makes a request to the appropriate content server 120 or 121 .
In accordance with an aspect of the teachings of this invention the local proxy server A recognizes that a HTTP request for an image file comes from a specific device PDD by recognizing the device's ID. The local proxy server A then looks up a table or directory stored in local memory or in another memory to find the device capabilities of the device PDD and the corresponding device capability PICS label, such as d(c 1 s 3), indicating this device can only display an image size of up to 3M bytes with 1-bit color encoding. Such a PICS label is then put into the HTTP request header (as the RHI for the PDD) and is subsequently sent to regional and national proxy servers B and C. In response to the request from the national proxy server C, the content server 120 or 121 prepares a resolution PICS label, r(c 16 s 100), and inserts it into the response HTTP header. The image file is then sent to the national proxy server C. After comparing the resolution PICS label against the device capability PICS (RHI) label, proxy server C determines that rendering is needed for this image file. Proxy server C then decides whether to do the rendering locally. If it is to perform the rendering locally, the national proxy server C then decides whether to complete all of the rendering itself, or to divide the rendering into multiple steps so that only some of it is performed locally. Assume that the national proxy server C determines that it will perform a partially rendering, it partially renders the image file and then updates the resolution PICS label accordingly. Next assume that the resulting resolution PICS label is sent, together with the partially rendered image file, to the regional proxy server B. Similarly, proxy server B determines if it will perform the remaining rendering locally. If not, it simply forwards the previously modified resolution PICS label, together with the partially rendered image file, to the local proxy server A. When proxy server A finally receives the image file, it determines if any remaining rendering needs to be done. If yes, it completes the rendering locally, since proxy server A is the last proxy server 110 , 111 , 112 in the proxy network before the PDD client device 130 , 131 . Proxy server A completes the rendering so that the image satisfies the device specification indicated by the PICS label d (c 1 s 3), and sends the rendered image file to the requesting PDD client device 130 or 131 .
Those skilled in the art should realize that a number of possible network topologies and architectures can benefit from and operate in accordance with the teachings of this invention, and the teachings of this invention are thus not intended to be construed to be limited to only the specific exemplary embodiments that were described above.
Furthermore, the teachings of this invention are not limited to using PICS™ formatted labels or data structures for implementing the RHI.
Also, objects other than image objects can be requested, returned and also processed by one or more intermediate computing nodes. As one example, audio objects can be handled in the same or a similar manner as the above described image objects, wherein the RHI could indicate the audio playback capability of the requestor. The teachings of this invention can also be applied to complex HTML documents, containing many headers and paragraphs of text, for simplifying the documents when requested by devices, such as PDDs, having limited display capabilities.
It should also be realized that the teachings of this invention encompass a computer program embodied on a computer-readable medium (such as the disk 210 ) for providing individual ones of servers in a network of collaborative servers capable of performing object processing, such as image rendering, in accordance with the capabilities of a device which is to consume the object. The computer program includes a code segment, responsive to requestor-specific capability information included with a request for the object, as well as object-specific information included with the received object, for processing the object either partially or entirely for causing the object to conform to the capabilities of the requester.
The invention also encompasses a program storage device, readable by a machine, that tangibly embodies a program of instructions executable by the machine to perform method steps enabling individual ones of computing node machines in an interconnected hierarchical network of collaborative computing nodes to perform object processing, such as rendering, in accordance with the capabilities of a device which is to consume the object. The method is responsive to requestor-specific capability information that is included with a request for the object, and is further responsive to object-specific information included with the object as received from a source of the object or another computing node machine, for processing the object either partially or entirely so as to cause the object to conform to the capabilities of the requestor to consume the object.
Thus, while the invention has been particularly shown and described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that changes in form and details may be made therein without departing from the scope and spirit of the invention. | A distributed object rendering method and system for a collaborative data network is disclosed. The data network, which may include the Internet, has attached computing nodes, including object requestor nodes, object source nodes, and intermediate nodes which may be proxy servers. The method can allow each participating proxy server to adapt to the dynamic load conditions of itself as well as proxies, as well as to dynamic traffic conditions in the data network. The determination of which proxy or set of proxies is to perform object rendering and caching is based on a distributed, collaborative method that is adopted among the proxies. The criteria for such a method can include the bandwidth and current load of the network links among proxies, and/or the respective CPU usage of the proxies. If an object rendering can be staged, e.g., different resolution rendering, it can be performed by more than one of the proxies. The determination of which proxy performs which stage of the multistage rendering can also be adaptive to the dynamic load conditions, as well as network conditions. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is the United States national phase of International Application No. PCT/MX2013/000163 filed Dec. 13, 2013, and claims priority to Mexican Patent Application No. MX/a/2012/014536 filed Dec. 13, 2012, the disclosures of which are hereby incorporated in their entirety by reference.
The Sequence Listing associated with this application is filed in electronic format via EFS-Web and is hereby incorporated by reference into the specification in its entirety. The name of the text file containing the Sequence Listing is 154952_ST25.txt. The size of the text file is 1,261 bytes, and the text file was created on Jun. 15, 2015.
FIELD OF THE INVENTION
The present invention relates to the use of Paecilomyces carneus for the prevention and/or control and/or eradication of phytoparasitic nematodes, migratory and sedentary endoparasites belonging to families Anguinidae, Aphelenchidae, Aphelenchoididae, Criconematidae, Dolichodoridae, Hemicycliophoridae, Heteroderidae, Hoplolaimidae, Iotonchidae, Neotylenchidae, Pratylenchidae, Sphaerulariidae, Tilenchidae, and Tylenchulidae: Suborder Tylenchina; Longidoridae: Suborder Dorylaimina; Trichodoridae: Suborder Diphtherophorina. The compositions and processes of the present invention are useful in the prevention and/or control and/or eradication of phytoparasitic nematodes that infect and/or infest the vast majority of cultures for animal and human consumption, while optimum conditions are created in the soil for improving crop yield, with the option of getting organic products.
BACKGROUND OF THE INVENTION
Pests are a biological factor that damages crops regardless of the region where they are. Damage caused by pests in the crops reduces the quality of the product and the amount of production, since they prevent plants to have an optimal development, and depending on the pest and the level of infestation, they can cause the death of the host.
Among the pests that affect the crops significantly, both in quality and in quantity, are the phytoparasitic nematodes, which are microscopic and depending on their life cycle they affect the plant in different ways. Some of the damages they cause to the crops are: withering, chlorosis, dwarfism, rickets, defoliation, lack of vigor, necrosis of the affected parts, resulting in a weak crop or the death thereof, and therefore production loss. In an effort to control pests that attack crops, farmers are in need to use chemical pesticides. Some of the disadvantages of them are the high risk posed when applied; the presence of the same in food products can result in damage to the health of consumers; also the alteration of pH and the contents of minerals in phytotoxic amounts as a consequence of the excessive application of chemical pesticides results in the loss of fertility of the soil; additionally they can have an effect in the quality of the product, as well as generating resistance to the chemical agents, which results in the need of make use of a larger amount thereof.
In the state of the art diverse methods for nematode control are described; among them are chemical methods, such as: use of 2R,5R-dihidroxymethil-2R,4R-dihidroxypyrrolidine (Pat. No. WO/1999/059414); a chemical agent with condensed formula C27H30O9 (Pat. No. WO/1993/002083); use of fluopiram for nematode control (Pat. No. WO/2012/038476); fertilizer composition based on 1-70% potassium hypophosphite and ammonium phosphite, 1-307 boric fertilizer (Pat. No. CN101492323), among others.
On the other hand, there are biological methods where microorganisms are used for nematode control, these include: Sphingobacterium strain spiritivorum C-926 and Corynobacterium paurometabolum C-924 (Pat No. MX 250042); Pasteuria spp. (Pat No. MX 193344); fungi of the genus Arthrobotrys (Pat No. U.S. Pat. No. 4,666,714); Bacillus thuringiensis (Pat No. U.S. Pat. No. 5,270,448); Streptomyces dicklowii ATCC 55274 (Pat No. U.S. Pat. No. 5,549,889); fungus Pochonia chlamydosporia var. chlamydosporia (Pat No. US2009169518); Verticillium chlamydosporium CC 334168 (Pat No. WO/1991/001642), among others.
Another option is the combination of chemical compounds with biological agents, such as: Buprofezina and Paecilomyces sp. (U.S. Pat. No. 5,885,598); Silafluofen and/or Etofenprox with Paecilomyces sp. (U.S. Pat. No. 5,888,989), among others. Finally, there are methods that involve genetic modification for generating crops resistent to nematodes, such as those described in the following patent documents: GEP20002245, U.S. Pat. No. 6,294,712, U.S. Pat. No. 7,576,261, CN1903014, WO/2003/080838, among others.
The disadvantages that have been observed with chemical methods are those described above for the application of nematicides; as regarding the combination of chemical agents with biological agents, although sometimes is achieved to decrease the amount of the chemical agent, the disadvantages do not disappear; the genetic alteration of crops in order to create pest-resistant crops is an option that, besides having a high cost, poses a long-term risk for the consumers, since there is no certainty about the implications that the consumption of such products will have in the long term.
Nowadays, the biological methods are the most accepted and convenient, because they use microorganisms that are safe for the final consumer and help preserve the quality of soils, crops and thus of the final product.
Currently, the fungus of genus Paecilomyces spp. is used as nematicide, since it attacks nematodes effectively and without damaging crops. Patent documents U.S. Pat. No. 7,435,411 B2, CN101418264 and US 20050008619 describe the use of a composition containing Paecilomyces lilacinus for pest control in the soil; patent documents U.S. Pat. No. 5,989,543, CN101422168, DE102005024783, CN101081982, CA2059642, U.S. Pat. No. 5,360,607, U.S. Pat. No. 5,989,543, CN101518265 describe the use of Paecilomyces lilacinus; Paecilomyces fumosoroseus, Paecilomyces lilacinus 251, Paecilomyces lilacinus 252, Paecilomyces lilacinus 253, and Paecilomyces lilacinus 254; and Paecilomyces cicadae for nematode control and finally, in patent application MX/a/2011/004510 the use of Paecilomyces carneus strain IE-431 is described for the prevention and/or control and/or eradication of cyst-forming nematodes in solanaceous crops.
Among the highest-risk nematodes for crops are the gall-inducer nematodes of genus Meloidogyne spp., among others; root-lesion and root-borers, which are migratory endoparasites, including nematodes of genera Ditylenchus spp., Pratylenchus spp. and Radopholus spp., among others; and migratory and sedentary endoparasites, including nematodes of genera Helicotylenchus spp., Criconemoides spp., and Xiphinema spp., among others. The main crops affected by said nematodes are shown in Table 1:
TABLE 1
Crops affected by nematodes
Common
name
Scientific name
Meloidogyne
Pratylenchus
Helicotylenchus
Criconemoides
Swiss chard
Beta vulgaris
X
Agave
Agave atrovirens
X
X
X
X
Avocado
Persea americana
X
X
X
X
Garlic
Allium sativum
X
Alfalfa
Medicago sativa
X
X
X
Cotton
Gossypium
X
X
X
hirsutum
Sugar-apple
Anona spp.
X
X
Rubber tree
Hevea brasiliensis
X
Rice
Oryza sativa
X
X
Oat
Avena sativa
X
Bamboo
Bambusa spp.
X
Begonia
Begonia spp.
X
Eggplant
Solanum
X
melongena
Peanut
Arachis hypogea
X
X
X
Coffee
Coffea ar á bica
X
X
Cocoa
Theobroma cacao
X
X
Zucchini
Cucurbita pepo
X
She-oak
Casuarina spp.
X
Camellia
Camelia spp.
X
Sweet potato
Ipomea batatas
X
Cinammon
Cinnamomum zeylanicum
X
Sugar cane
Sacharum officinarum
X
X
X
Safflower
Carthamus tinctorius
X
X
White onion
Allium cepa
X
X
Cedar
Chamaecyparis spp.
X
Citrus plants
Citrus spp.
X
X
X
Coconut tree
Cocos nucifera
X
Cauliflower
Brassica oleracea var. Botrytis
X
X
X
Carnation
Dianthus caryophyllus
X
X
X
Chrysanthemum
Chrysantemum morifolium
X
Chayote
Sechium edule
X
Chili
Capsicum annum
X
X
Peach
Prunus persica
X
X
Epazote
Chenopodium ambrisioides
X
Spinach
Spinacea oleracea
X
Loofah
Lufa cylindrica
X
Strawberry
Fragaria spp.
X
X
X
White ash
Fraxinus americana
X
Bean
Phaseolus vulgaris
X
X
X
Gardenia
Gardenia jasminoides
X
Chickpea
Cicer arietium
X
Gladiolus
Gladiolus spp.
Guava
Psidium guajava spp.
X
Broad bean
Vicia faba
X
Fig
Ficus carica
X
Mexican Yam
Pachirizus angulatus
X
Lettuce
Lactuca sativa
X
X
X
Lemmon
Citrus lim {acute over ( o )} n
X
Maize
Zea mays
X
X
X
Apple tree
Malus spp.
X
X
X
Mango
Manguifera indica
X
X
X
Daisy
Aster spp.
X
Shasta Daisy
Chrysantemum m {acute over ( a )} ximum
X
X
Melon
Cucumis melo
X
X
X
X
Mint
Mentha piperita
X
X
X
Yam
Dioscorea spp.
X
Walnut tree
Juglans regia
X
X
X
Prickly pear
Opuntia spp.
X
X
Okra
Abelmoschus esculentus
X
Papaya
Carica papaya
X
Potato
Solanum tuberosum
X
X
X
Barnyard grass
Echinocloa spp.
X
X
Cucumber
Cucumis sativus
X
Banana
Musa spp.
X
X
X
Jamaica pepper
Pimenta dioica
X
Pine
Pinus spp
X
Mexican mountain pine
Pinus hartwegii
X
Pineapple
Ananas comunus
X
X
X
X
Pummelo
Citrus maxima
Watermelon
Citrullus lanatus
X
X
White willow
Salix alba
X
Sorghum
Sorghum vulgare
X
Soy
Glycine max
X
X
Tobacco
Nicotiana tabacum
X
X
Tomato
Lycopersicon esculentum
X
X
X
Ground cherry
Physalis spp.
X
X
Common wheat
Triticum aestivum
X
Trigo
Buckwheat
X
Vine
Vitis vinifera
X
X
X
Madagascar periwinkle
Vinca rosea
X
African violet
Saint paulina spp.
X
Carrot
Daucus carota
X
Common
name
Scientific name
Radopholus
Hoplolaimus
Xiphinema
Ditylenchus
Swiss chard
Beta vulgaris
Agave
Agave atrovirens
X
X
Avocado
Persea americana
X
X
X
Garlic
Allium sativum
X
X
Alfalfa
Medicago sativa
X
X
X
Cotton
Gossypium
X
X
hirsutum
Sugar-apple
Anona spp.
X
Rubber tree
Hevea brasiliensis
Rice
Oryza sativa
X
X
Oat
Avena sativa
Bamboo
Bambusa spp.
Begonia
Begonia spp.
Eggplant
Solanum
melongena
Peanut
Arachis hypogea
X
Coffee
Coffea ar á bica
Cocoa
Theobroma cacao
X
X
X
Zucchini
Cucurbita pepo
She-oak
Casuarina spp.
X
Camellia
Camelia spp.
Sweet potato
Ipomea batatas
Cinammon
Cinnamomum zeylanicum
X
Sugar cane
Sacharum officinarum
X
Safflower
Carthamus tinctorius
White onion
Allium cepa
X
Cedar
Chamaecyparis spp.
Citrus plants
Citrus spp.
X
X
X
X
Coconut tree
Cocos nucifera
Cauliflower
Brassica oleracea var. Botrytis
X
X
Carnation
Dianthus caryophyllus
X
Chrysanthemum
Chrysantemum morifolium
Chayote
Sechium edule
X
Chili
Capsicum annum
X
X
Peach
Prunus persica
X
X
X
Epazote
Chenopodium ambrisioides
Spinach
Spinacea oleracea
Loofah
Lufa cylindrica
Strawberry
Fragaria spp.
X
X
X
White ash
Fraxinus americana
Bean
Phaseolus vulgaris
X
X
Gardenia
Gardenia jasminoides
X
Chickpea
Cicer arietium
X
Gladiolus
Gladiolus spp.
X
Guava
Psidium guajava spp.
Broad bean
Vicia faba
Fig
Ficus carica
Mexican Yam
Pachirizus angulatus
Lettuce
Lactuca sativa
Lemmon
Citrus limon
Maize
Zea mays
X
X
X
Apple tree
Malus spp.
X
X
Mango
Manguifera indica
X
Daisy
Aster spp.
Shasta Daisy
Chrysantemum maximum
Melon
Cucumis melo
X
Mint
Mentha piperita
X
Yam
Dioscorea spp.
Walnut tree
Juglans regia
X
X
Prickly pear
Opuntia spp.
Okra
Abelmoschus esculentus
Papaya
Carica papaya
X
X
Potato
Solanum tuberosum
X
X
X
Barnyard grass
Echinocloa spp.
X
X
X
X
Cucumber
Cucumis sativus
X
Banana
Musa spp.
X
X
X
Jamaica pepper
Pimenta dioica
Pine
Pinus spp
X
Mexican mountain pine
Pinus hartwegii
Pineapple
Ananas comunus
X
Pummelo
Citrus maxima
X
Watermelon
Citrullus lanatus
X
White willow
Salix alba
Sorghum
Sorghum vulgare
X
X
Soy
Glycine max
X
Tobacco
Nicotiana tabacum
X
X
Tomato
Lycopersicon esculentum
X
Ground cherry
Physalis spp.
Common wheat
Triticum aestivum
X
Trigo
Buckwheat
Vine
Vitis vinifera
X
Madagascar periwinkle
Vinca rosea
African violet
Saint paulina spp.
Carrot
Daucus carota
Sedentary endoparasitic nematodes are those that deform the roots of different crops due to inducing the overgrowth of the cells in the feeding site within which causes root galls ( Meloidogyne spp.).
Migratory endoparasitic nematodes completely penetrate in the root of its host, traveling through the cortex and feeding on the cytoplasm of the cells, thus causing extensive destruction of tissues, and causing atrophy in the radicular system of plants ( Ditylenchus spp., Pratylenchus spp., and Radopholus spp., among others).
Semiendoparasitic nematodes are deeply affixed to the host plant, leaving part of the body exposed to the outside. The juvenile are released to soil when hatching out, and subsequently they affix to the root of the plant ( Heterodera spp., and Punctodera spp., among others).
Sedentary ectoparasitic nematodes only introduce the cephalic part of their body in the host plant, and usually do not become detached, except for reproduction. They oviposit directly in the soil ( Helicotylenchus spp., Tylenchorhinchus spp., and Criconemoides spp., among others).
Migratory ectoparasites feed on a specific place during a short time and only introduce the stylet in the root of the plant. Some induce the formation of syncytia; a multi-nucleated hyperplastic cell where the nematode feeds ( Xiphinema spp., Longidorus spp., and Trichodorus spp., among others).
Agriculture is the most important productive sector on most of the countries, where has a significant place in employment generation, the overall increase in agricultural incomes is a necessary condition for stimulating the growth of the entire economy, including non-agricultural sectors that sell their products and services to the rural population.
Mexico has a national territory of 198 million hectares, of which 145 million are dedicated to livestock, this is why agriculture represents an important productive sector, with a contribution of 4% to the national gross domestic product, is a core activity in rural areas, in which a highly significant part of the national population still inhabits.
The climatic differences between different regions of the world and even between regions in each country are significant in terms of climate and ecosystem, so pest control in crops in those regions is vital for farmers to be competitive nationally and internationally.
Therefore, it is necessary to have a method for pest control that works in different conditions of the soil and ambient, which also do not affect the quality of the product or the health of producers and/or consumers; in the present invention is disclosed the use of a fungus for nematode control, with outstanding efficacy and efficiency and inexpensive.
OBJECT OF THE INVENTION
The present invention relates to the use of the biologically pure strain Paecilomyces carneus , as well as compositions, methods and use for the prevention and/or control and/or eradication of phytoparasitic nematodes, migratory and sedentary endoparasites belonging to families Anguinidae, Aphelenchidae, Aphelenchoididae, Criconematidae, Dolichodoridae, Hemicycliophoridae, Heteroderidae, Hoplolaimidae, Iotonchidae, Neotylenchidae, Pratylenchidae, Sphaerulariidae, Tilenchidae, and Tylenchulidae: Suborder Tylenchina; Longidoridae: Suborder Dorylaimina; Trichodoridae: Suborder Diphtherophorina, that infect and/or infest crops in order to obtain safe quality products for animal and human consumption.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 . Meloidogyne spp. parasitized by Paecilomyces carneus strain IE-431.
FIG. 2 . Development of Paecilomyces carneus strain 418 over Pratylenchus spp. at 72 hrs.
FIG. 3 . Development of Paecilomyces carneus strain 418 over Pratylenchus spp. at 120 hrs.
FIG. 4 . Pathoenicity plot for Paecilomyces carneus strain 418 over Hoplolaimus spp.
FIG. 5 . Pathoenicity plot for Paecilomyces carneus strain 418 over Criconemoides spp.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to the use and application of one or more cells of Paecilomyces carneus for the control and/or prevention and/or eradication of phytoparasitic nematodes from the groups of migratory endoparasites and/or sedentary endoparasites of the families Anguinidae, Aphelenchidae, Aphelenchoididae, Criconematidae, Dolichodoridae, Hemicycliophoridae, Heteroderidae, Hoplolaimidae, Iotonchidae, Neotylenchidae, Pratylenchidae, Sphaerulariidae, Tilenchidae, and Tylenchulidae: Suborder Tylenchina; Longidoridae: Suborder Dorylaimina; Trichodoridae: Suborder Diphtherophorina, that infect and/or infest cropland.
The Paecilomyces carneus strains IE-412, IE-416, IE-418, IE-419, IE-431, IE-451, and IE-452 are deposited, preserved and stored in the ceparium of fungi of the Instituto de Ecologia A.C. (INECOL), production and/or isolation and/or preservation of such strains is performed by breeding them on a solid culture medium consisting of at least one source of nitrogen and/or at least one carbon source and/or one or more mineral salts and/or at least a suitable carrier and/or at least one antibiotic agent and/or at least one growth promoting agent. The incubation temperature of the fungus in the culture medium is about 13-37° C.
Propagation and reproduction of the fungus consist in the inoculation of cells in compositions of solid or liquid mediums comprising one or more amino-acids, and/or one or more long-chain carbohydrates, and/or one or more mineral salts, and/or one or more vehicles, and/or one or more antibiotic agents, and/or one or more buffers in sufficient quantities. The culture is fixed or static and with uninterrupted oxygenation in a percentage between 40% and 90% of oxygen content to allow the optimum development of the fungus Paecilomyces carneus.
The mechanism of action of Paecilomyces carneus is characterized by the production of specific enzymes that allow it to degrade the cuticle and penetrate to the interior of the nematode in any of its stages (juvenile and adult eggs, among others), where it grows and reproduces until causing the death of the different taxonomic groups of phytoparasitic nematodes.
The 1E-418 strain of Paecilomyces carneus is characterized by having the DNA nucleotide sequence coded as follows:
GGGATCATTACCGAGTTTACAACTCCCAAACCCCCTGTGAACTTATACCA
TTTACTGTTGCTTCGGCGGGTCACGGCCCCGGGGAAGGACAGCGGTCGCC
GTCAGGCCTCAGCTGCCCGCCCCCGGAAACAGGCGCCCGCCGGGGAACTC
AAACTCTTCTGTATTTCTTTATCTAATATATACTGTCTGAGTAAAAACTA
AAATGAATCAAAACTTTCAACAACGGATCTCTTGGTTCTGGCATCGATGA
AGAACGCAGCGAAATGCGATAAGTAATGTGAATTGCAGAATTCAGTGAAT
CATCGAATCTTTGAACGCACATTGCGCCCGCCAGTATTCTGGCGGGCATG
CCTGTTCGAGCGTCATTTCAACCCTCAAGTCCCCTGTGGACTCGGTGTTG
GGGACCGGCGAGACAGCCGCGGATCTTCTTCCGCAGCGAGTCGCCGCCCC
CCAAATGACTTGGCGGCCTCGTCGCGGCCCTCCTCTGCGTAGTATAGCAC
ACCTCGCAACAGGAGCCCGGCGAATGGCCACTGCCGTAAAACCCCCCAAC
TTTTTCAGAGTTGACCTCGAATCAGGTAGGAATACCCGCTGAACTTAAGC
ATATCA (SEQ ID NO: 1).
The IE-418 strain of Paecilomyces carneus has the following structural features:
Mycelium with radial growth, upright conidiophores, in PDA grows 12 mm in 10 days, white hairy dusty mycelium, in EMA grows from 9 to 11 mm in ten days. In both media it stains dark green 29F8 the back of the culture medium plate according to the 1961's Farver i Farver color chart from Wanscher and Kornerup. White mycelium, filamentous dusty texture. In oatmeal agar (OA) it grows from 18 to 20 mm in ten days. Mycelium with dusty texture due to the sporulation, which turns from white to slightly pinkish 7A2 in OA in a time greater than 55 days after inoculation. It stains slightly the culture medium in the back of the case with grayish yellow 3C3 or 3C4 irregularly after 35 days, and in the oldest parts with olive green 3E7. Bottle-shaped conidiogenic cells, tapering towards the tip in a very thin neck, monophialidic, or in well-defined verticillia of 2-5 cells, although groups of three cells predominate, with a minimum length of: 7.2-8.8 μm; the more frequent length is: 9.6-10.4 μm and the greater length is between: 11-14.4 μm. The width is 1.6-2.4 μm. Subglobose conidia, ellipsoidal to spheric, equinulated, arranged in chains. The spores are 2.4-4.0 μm long and 1.6-2.4 μm. width. In 5 mm discs, the sporulation is 25×10 6 spores.
The IE-418 strain from Paecilomyces carneus product of the present invention, is characterized by having the ability to infect and/or infest phytoparasitic nematodes from groups of: migratory endoparasites, and/or sedentary endoparasites, and/or semiendoparasites, and/or migratory ectoparasites, and/or sedentary ectoparasites from the classification according to the molecular analysis proposed by De Ley P. and Blaxter. M. in 2004, from the following families: Anguinidae, and/or Aphelenchidae, and/or Aphelenchoididae, and/or Criconematidae, and/or Dolichodoridae, and/or Hemicycliophoridae, and/or Heteroderidae, and/or Hoplolaimidae, and/or Iotonchidae, and/or Neotylenchidae, and/or Pratylenchidae, and/or Sphaerulariidae, and/or Tilenchidae, and/or Tylenchulidae: Suborder Tylenchina; and/or Longidoridae: Suborder Dorylaimina; and/or Trichodoridae: Suborder Diphtherophorina.
During the investigation of the use and application of the IE-431 strain of Paecilomyces carneus in the control, and/or prevention, and/or eradication of phytoparasitic nematodes, migratory and sedentary endoparasites, semiendoparasites, and migratory and sedentary ectoparasites it was established that said strain, even when infects such nematodes, requires at least 15 days for the infection without controlling and/or eradicating the nematodes, except in the case of Meloidogyne spp. Surprisingly and unexpectedly it was found that the IE-418 strain of Paecilomyces carneus infests and/or infects the phytoparasitic nematodes in less than 72 hours, controlling and eradicating the above-mentioned families of nematodes.
A first stage of evaluation of the effectiveness and efficiency of the IE-418 strain of Paecilomyces carneus , was carried out placing cells (conidiospores, and/or blastospores, and/or hyphal fragments) in a suspension of Paecilomyces carneus IE-418 in contact with migratory and sedentary endoparasitic nematodes, semiendoparasites and migratory and sedentary ectoparasites, among which are: Meloidogyne spp., Pratylenchus spp., Radopholus spp., Helicotylenchus spp., Criconemoides spp.; Hoplolaimus spp.; Xiphinema spp. and, separately the same nematodes were placed in contact with Paecilomyces carneus strain IE-431.
The results of this first stage for the IE-431 strain of Paecilomyces carneus were the following:
1. The viability of the juvenile and adult egg masses of nematodes of genus Meloidogyne spp. is reduced.
2. At 24 hours after being brought into contact, the fungus germinated and penetrated to the host.
3. At 72 hours the mycelium was found in development both inside and outside of the egg masses and females of Meloidogyne spp.
4. At 120 hours the fungus completely invaded the whole egg mass and the interior of the females of Meloidogyne spp. ( FIG. 1 ).
The results of this first stage for the IE-431 strain of Paecilomyces carneus with Pratylenchus spp., Hoplolaimus spp., and Criconemoides spp. were the following:
1. At 120 hours after being brought into contact, some fungal spores germinating on the cuticle of the nematode were seen.
2. At 15 days, the mycelium had an incipient development outside the nematode, so it is not possible to control or to eradicate the same.
The results of this first stage for the IE-431 strain of Paecilomyces carneus were the following:
1. At 48 hours after being brought into contact, the fungus germinated and penetrated to the nematode.
2. From 72 ( FIG. 2 ) to 120 hours ( FIG. 3 ) the mycelium was found in development both inside and outside the nematode, which indicates the potential for control and/or eradication thereof.
In a second stage, it was carried out the assessment of pathogenicity expressed as % mortality for IE-418 strain of Paecilomyces carneus in contact with ectoparasitic nematodes ( FIG. 4 ):
1. 2% mortality was obtained in individuals of Hoplolaimus spp. at 24 hours of exposition to Paecilomyces carneus IE-418.
2. At 24 hrs of exposition to the fungus a 68% mortality was found for Hoplolaimus spp. At 120 hrs of exposition to the fungus a 78% mortality was found for individuals of
3 . Hoplolaimus spp.
4. On the contrary, in the blank treatment it was found only 26% individuals of Hoplolaimus spp. dead at 120 h after the start of the experiment.
In the assessment of pathogenicity expressed as mortality for IE-418 strain of Paecilomyces carneus in contact with Criconemoides spp. ( FIG. 5 .)
1. 46% mortality of individuals of Criconemoides spp. was obtained at 24 hrs of exposure to IE-418 strain of Paecilomyces carneus.
2. At 72 hrs of exposure to IE-418 strain of Paecilomyces carneus more than 80% individuals of Criconemoides spp. were found parasited with the fungus.
3. Finally at 120 hrs after having infected the nematodes Criconemoides spp. with IE-418 strain of Paecilomyces carneus 96% individuals were found dead, and with visible sporulation.
4. On the contrary, in blank treatment, it was not seen evidence of mycelium and only a 16.6% mortality was found.
In a third stage, the application procedure of Paecilomyces carneus was combined with crop rotation and application of Beauveria bassiana and Lecanicillium lecanii for combating in parallel other existing crop pests such as: thrips (Order Thysanoptera), whitefly (Order Hemiptera), greenfly Aphis spp. (Order Hemiptera) (which may affect the plant since its early stages, which significantly affect production), and the chafer, Macrodactylus spp. (Order Coleoptera), which is an omnivorous insect and can destroy a crop in a few days; and diseases caused by Helotiales, such as Botrytis fabae (chocolate spot disease), and/or B. cinerea (grey rot), and/or diseases caused by Uredinales, such as Uromyces spp., and/or Puccinia spp., and/or Tranzschelia spp. (rusts), which producers of various crops can no longer control with chemicals sold in the market.
For the prevention, and/or control, and/or eradication of nematodes and also said pests and diseases, Lecanicillium lecanii was used in early stages of plant growing, applied separately or in combination with Paecilomyces carneus in the soil.
Surprisingly, the results obtained were the significant reduction of thrips, whitefly and greenfly pests, and an almost complete reduction of chocolate spots. With regard to the rust, the crop remains clean until the production of sheaths and filling thereof in the case of broad bean, i.e., when the seed is ripe and ready to be harvested.
Additionally, Beauveria bassiana was applied for the control of Macrodactylus spp. In 2 or more days such pest starts to die and diminish significantly the culture damage. To obtain better results, the fungus Beauveria bassiana is applied during farm work to affect before the larval stage and thus reduce the population.
The results obtained were an increment in the yield of wide bean plants in plots treated with biological control, in comparison with plots with chemical control (50% less sheaths) and the blank plot.
Therefore, the strain IE-418 of Paecilomyces carneus is characterized by reducing the nematode population since the first application with total efficacy reached in three to five days for nematodes of Families Anguinidae, and/or Aphelenchidae, and/or Aphelenchoididae, and/or Hemicycliophoridae, and/or Heteroderidae, and/or Hoplolaimidae, and/or Iotonchidae, and/or Neotylenchidae, and/or Pratylenchidae, and/or Sphaerulariidae, and/or Tilenchidae, and/or Tylenchulidae: Suborder Tylenchina; and/or Longidoridae: Suborder Dorylaimina; and/or Trichodoridae: Suborder Diphtherophorina. However, the strain IE-431 fails to carry out its nematicide action in most of the above-mentioned phytoparasitic nematodes, but it is extremely effective and specific in endoparasitic and/or semiendoparasitic nematodes of Family Heteroderidae.
The present invention discloses a method for isolation, and/or preservation, and/or massive reproduction of Paecilomyces carneus , as well as the use, and/or application thereof for the control, and/or prevention, and/or eradication of nematodes infecting and/or infesting areas for cultivation of Swiss chard, agave, avocado, garlic, alfalfa, cotton, sugar-apple, rubber tree, myrtle, rice, oat, baricoco, bamboo, begonia, egg plant, broccoli, peanut, coffee, cocoa, star apple, zucchini, pumpkin, courgette, bitter berry, she-oak, camellia, sweet potato, cinnamon, sugar cane, starfruit, apricot, safflower, barley, onion, cedar, citron, plumb, citrus plants, coconut tree, cabbage, cauliflower, carnation, chrysanthemum, ice-cream bean, chicozapote, pea, chili, peach, epazote, spihach, loofah, raspberry, strawberry, ash, bean, gardenia, chick pea, gladiolus, pomegranate, guava, wide bean, fig, Mexican yam, lettuce, lime, lemon, maize, mamee, tangerine, apple tree, mango, daisy, shasta daisy, melon, quince, mint, blackberry, yam, orange, nectarine, walnut tree, prickly pear, okra, papaya, potato, barnyard grass, cucumber, pear, banana, pepper, pine, pineapple, dragon fruit, pummelo, watermelon, white willow, satsuma, sorghum, soy, tobacco, tomato, ground cherry, grapefruit, wheat, vine, Madagascar periwinkle, African violet, carrot, yellow mombin, yellow chapote, cherimoya, soursop, paradise plum, cashew tree, melon, loquat, cucumber, persimmon, rose apple, watermelon, yellow sapote, white sapote, black sapote, sugar apple, between other crops in which this type of parasite spreads.
The compositions with cells of Paecilomyces carneus can be developed for application in the form of suspension, granules, powder, lyophilized, pellets, controlled release forms, ecological pump, gels, jellies, pastes, capsules, immobilized cells, emulsion, micro-emulsion, solution, and/or combinations thereof.
EXAMPLES
Nematicide compositions of Paecilomyces carneus obtained are provided below in a descriptive and not restrictive way:
Example 1: Composition 1 of Paecilomyces carneus Strain 418
COMPONENT
AMOUNT
Paecilomyces carneus cells
0.5 × 10 7 cells/mL
Carrot juice
80-100 mL
Yeast
0.1-5.0 g/L
Ampicillin
500 mg
Water
q.s. 1000 mL
Example 2: Composition 2 of Paecilomyces carneus Strain 418
COMPONENT
AMOUNT
Paecilomyces carneus cells
0.5 × 10 7 cells/mL
Oat
20-50 g/L
Yeast
0.1-5.0 g/L
Chloramphenicol
1000 mg
Water
q.s. 1000 mL
Example 3: Composition 3 of Paecilomyces carneus Strain 418
COMPONENT
AMOUNT
Paecilomyces carneus cells
0.5 × 10 7 cells/mL
Oat
5-25 g/L
Yeast
0.1-5.0 g/L
Chloramphenicol
1000 mg
Water
q.s. 1000 mL
Example 4: Composition 4 for Isolation and Preservation of Paecilomyces carneus Strain IE-418
COMPONENT
AMOUNT
Paecilomyces carneus cells
0.5 × 10 7 cells/mL
Carrot
50-160 g/L
Potato
20-50 g/L
Chloramphenicol
1000 mg
Water
q.s. 1000 mL
Example 5: Composition 5 for Isolation and Preservation of Paecilomyces carneus Strain IE-418
COMPONENT
AMOUNT
Paecilomyces carneus cells
0.5 × 10 7 cells/mL
Rye
15-50 g/L
Chloramphenicol
1000 mg
Water
q.s. 1000 mL
The application method of one or more compositions of Paecilomyces carneus generally consists in:
One or more applications of the composition(s) of Paecilomyces carneus to the soil at least 10 days prior to sowing for disinfecting it. The number of applications depends on the species of the phytoparasitic nematodes and its population density.
In the case of crops whose sowing is carried out from tubers, bulbs, rhizomes, corms, among others, the application consists in immerse them in the composition(s) for at least one hour before the sowing.
For the transplantation of shrub and/or tree crops, the application is performed directly to the root of the plant and/or to the soil where they will be sown.
In the case of crops planted by seeds, the composition(s) are applied in the furrow before laying the seed and/or directly in the seed shortly before sowing.
Optionally and without limitations, the application of the composition(s) is performed after sowing and/or during the growing of the crop.
During and/or after the harvest, and/or during the culture rotation period, and/or the soil rest the application of the composition(s) is done to the soil in order to prevent new infestations and/or control and/or eradicate the phytoparasitic nematodes population remaining. This practice prepares the soil for the next growing cycle.
Complementarily, it can be added to said composition one or more biological agents for nematode control, selected from the following: Bacillus thuringiensis, Bacillus thuringiensis ATCC 55273, Bacillus firmus CNCMI-1582 , Sphingobacterium strain spiritivorum, Corynobacterium paurometabolum, Arthrobotrys spp., Pasteuria penetrans 98-35 , Streptomyces dicklowii, Stevia rebaudiana, Streptomyces rubrogriseus, Pochonia chlamydosporia, Monacrosporium ullum, Bacillus amyloliquefaciens, Verticillium chlamydosporium CC 334168, Bacillus subtillis No. DSM17231, and/or Bacillus licheniformis DSM 17236, Verticillium chlamydosporium, Paecilomyces lilacinus, Paecilomyces fumosoroseus, Paecilomyces lilacinus 251, Paecilomyces lilacinus 252 , Paecilomyces lilacinus 253, and Paecilomyces lilacinus 254, Rhizoctonia solani AG-4, Fusarium oxysporum, Pythium sp., Phytophthora nicotiana, Verticillium dahliae, Paecilomyces cicadae, Sphingobacterium spiitivorum C-926, and/or Corynebacterium paurometabolum C-924 Paecilomyces carneus strain IE-431, and/or Beauveria bassiana , and/or Lecanicillium lecanii , and/or Calcarisporium spp., and/or combinations thereof.
In a comprehensive manner, the present invention provides the following advantages:
1. Biological method for rational management of nematode pests in crops.
2. Quality improvement of soil for cultivation.
3. Remediation of soil damaged by chemical agents like pesticides.
4. Obtaining high-quality agricultural products and forestry resources.
5. Improvement in crop and/or forest resources yield.
6. Favors the provision of macro elements such as phosphorus in the soil to the plant and improves soil fertility. Its phosphate solubilization efficacy is comparable to that of Penicillium spp. and Aspergillus spp.
7. The eradication of phytoparasitic nematodes is seen from the first application in less time compared to other control methods.
8. Nematicide compositions obtained are safe for humans, plants, and animals.
9. It allows the combination with other control methods such as crop rotation, soil rest, among others.
10. Is a sustainable method of prevention, and/or control, and/or eradication of phytoparasitic nematodes, easy to manage and apply.
11. It is an economic and profitable method in the short, medium and long term.
12. The specificity is due to the production of specific enzymes that attack the phytoparasitic nematodes without affecting the free-living nematodes beneficial to the agricultural system.
IE-418 strain was also deposited in the Chilean Collection of Microbial Resources (CChRGM) with the access number RGM2140 Date Dec. 13, 2013 | Provided herein are methods of preventing/controlling phytoparasitic nematodes in migratory and sedentary endoparasites belonging to families Anguinidae, Aphelenchidae, Aphelenchoididae, Criconematidae, Dolichodoridae, Hemicycliophoridae, Heteroderidae, Hoplolaimidae, Iotonchidae, Neotylenchidae, Pratylenchidae, Sphaerulariidae, Tilenchidae, and Tylenchulidae: Suborder Tylenchina; Longidoridae: Suborder Dorylaimina; Trichodoridae: Suborder Diphtherophorina using Paecilomyces carneus . The compositions and processes disclosed herein are useful in the prevention and/or control and/or eradication of phytoparasitic nematodes that infect and/or infest the vast majority of cultures for animal and human consumption, while optimum conditions are created in the soil for improving crop yield, with the option of getting organic products. | 2 |
BACKGROUND OF THE INVENTION
The continuously increasing extent of the functionality of applications which are provided in data processing systems has resulted in the amount of data which needs to be controlled by the data processing systems increasing to a similar extent. The desire to use the extended functionality of applications (for example, for supporting complete business processes) is a further motivation for increasing networking of data processing systems and for increased integration of different applications provided there, in order to form workflow management systems. The increasing networking of data processing systems and the increased integration of applications have increasingly led to the need to take account of the problems associated with multiple access to memory devices in the data processing systems. Increasing amounts of data and multiple access not only result in new requirements for data maintenance and distribution, but also require new strategies for access to memory resources by data processing systems.
The present invention is, therefore, directed toward a method for fast and efficient control of access to a memory device, and a computer program for implementing the method.
SUMMARY OF THE INVENTION
Accordingly, in an embodiment of the present invention, a method is provided for controlling access to a memory device, wherein the method includes the steps of: visualizing text and/or graphics contents from a control file on a user interface; receiving a first selection input from a user; reading a first address value, which is associated with the first selection input, from the control file; transmitting the first address value to an address allocation device; addressing, on the basis of the first address value, a memory element in the memory unit which is associated with the address allocation device; visualizing text and/or graphics contents from the memory element, to which second address values are allocated, via which addressing information for the memory device or for a memory element is identified; receiving a second selection input which is made based on the visualized text and/or graphic contents of the memory element; selecting a second address value which is associated with the second selection input; and reading a memory area identified by the second address value in the memory element, or addressing a memory element based on the addressing information, which is identified by the second address value, for reading and evaluating further second address values.
In a further embodiment of the present invention, a computer program is provided which can be loaded into a main memory of the computer and which has at least one software code section, wherein the running of the computer program affects the above-described method for controlling access of a memory device.
One major aspect of the present invention is that, even with a complex data storage structure, access is made to memory areas within the memory device with a minimal number of selection inputs required for selection of a desired memory area. This is achieved by providing first address values from a control file and second address values from a memory element in a memory unit which is associated with an address allocation device, in the sense of information precompression. The first and the second address values are each associated with text and graphics contents in the control file and/or in a memory element, which are visualized on a user interface in order to assist the selection of the address values. Specific preparation for access to desired data in a selected memory area of the memory device takes place in the address allocation device by evaluating the second address values, which identify addressing information for the memory device or for a memory element.
A further aspect of the present invention is the provision of a substantially complete overview of a complex data storage structure with a fine breakdown.
Additional features and advantages of the present invention are described in, and will be apparent from, the following Detailed Description of the Invention and the Figures.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows a flowchart of the method according to the present invention.
FIG. 2 shows a schematic illustration of an arrangement for carrying out the method according to the present invention.
FIG. 3 shows an example of access to different memory devices during a main process.
FIG. 4 shows a schematic illustration of a main process navigation system as an exemplary embodiment of the method according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The flowchart shown in FIG. 1 is used to illustrate the method of operation of the method according to the present invention for controlling access to a memory device DB. The method according to the present invention is preferably implemented by a computer program. The arrangement illustrated schematically in FIG. 2 relates to an example of devices which are involved in carrying out the method according to the present invention, and of the signal flow between these devices. Depending on the requirement, electronic, magnetic or optical storage media may be used, for example, for the storage device DB.
In step 1 as shown in FIG. 1 , text and graphics contents TGI 1 from a control file CF are visualized on the user interface UI (see also FIG. 2 ). The user interface UI may, for example, be in the form of a personal computer or a workstation, and has a display device DIS and at least one input appliance KB; for example, a keyboard or a mouse. According to step 2 in the flowchart illustrated in FIG. 1 , once a first selection input SI 1 , which is entered via the input appliance KB of the user interface UI, has been received from a user, a first address value AD 1 , which is associated with the first selection input SI 1 , is read from the control file (see also FIG. 2 ).
The first selection input SI 1 , may, for example, be linked to address information, or may contain this information. A memory area in the control file can be addressed on the basis of the address information, in order to read the first address value AD 1 as the contents of this memory area. The text and graphics contents TGI 1 from the control file CF as well as the first selection input SI 1 can be transmitted between the user interface UI and the control file CF, such as via a data bus, which is not illustrated in any more detail in FIG. 2 , between the user interface UI and a read/write apparatus for the control file CF.
The first address value AD 1 is transmitted to an address allocation device AAD in a corresponding manner to step 3 in the flowchart. Furthermore, the first address value AD 1 is used to address a memory element in a memory unit SD which is associated with the address allocation device AAD. Text and graphics contents TGI 2 from the addressed memory element are then visualized (step 4 ).
The visualization likewise should be produced on the user interface UI. The text and graphics contents TGI 2 from the addressed memory element are associated with second address values, which identify addressing information for the memory device DB or for a memory element of the memory unit SD. A converter CONV for the address allocation device AAD may be used, by way of example, to distinguish whether this addressing information relates to the memory device DB or to a memory element in the memory unit SD, and addresses either the memory device DB or the memory unit SD as a function of the addressing information.
According to step 5 , once a second selection input SI 2 has been received, a second address value AD 2 is selected, which is associated with the second selection input SI 2 . The second address value AD 2 is selected on the basis of the visualized text and graphics contents TGI 2 of the addressed memory element. The second address value AD 2 may, for example, be associated with the second selection input SI 2 in a simple manner by the second selection input SI 2 being transmitted as address information from the user interface UI via a data bus which is not illustrated in any more detail in FIG. 2 , to the memory unit SD. The address information which is transmitted to the memory unit SD can be used to address a memory element for reading the second address value AD 2 . The second address value AD 2 in this case represents the contents of this memory element. The text and graphics contents TGI 2 which need to be visualized in order to select the second address value AD 2 also may be transmitted via the data bus between the user interface UI and the memory unit SD. Once the second address value AD 2 has been read, it is advantageously transmitted to the address allocation device AAD for further evaluation.
Since the second address value AD 2 can identify addressing information AI 2 a for the memory device DB or addressing information AI 2 b for a memory element in the memory unit SD, a check is then carried out to determine whether this address information relates to the memory device DB or to a memory element in the memory unit SD (step 6 ).
This check may, for example, be carried out once again by the converter CONV for the address allocation device AAD, which addresses either the memory device DB or the memory unit SD as a function of the addressing information. If the addressing information relates to a memory element in the memory unit SD, then a jump is made back into step 3 within the flowchart that is illustrated in FIG. 1 . As such, a memory element in the memory unit SD is addressed on the basis of the addressing information AI 2 b , which is identified by the second address value AD 2 for reading and evaluating further second address values. The text and graphics contents TGI 2 of the respectively addressed memory elements are advantageously visualized once again on the user interface UI for reading and evaluating further second address values.
If the addressing information identified by the selected second address value AD 2 relates to the memory device DB, then, according to step 7 in the flowchart illustrated in FIG. 1 , a memory area in the memory device DB is read on the basis of this addressing information AI 2 a . Text and graphics contents TGI 3 which are stored in this memory area likewise are preferably transmitted to the user interface UI where they are visualized. As an alternative to this, it is also possible to transmit the memory area contents in the sense of file transfer, provided the user interface UI has its own memory device.
Once the second selection input SI 2 has been received, the second address value AD 2 is preferably selected via a sequence controller RTC or via the address allocation device AAD. The first address value AD 1 is advantageously read by the sequence controller RTC once the first selection input SI 1 of the user interface UI has been received. This also applies to the reading of the memory area which is identified by the second address value AD 2 in the memory device DB. According to one preferred embodiment of the present invention, the address allocation device AAD and the sequence controller RTC are in the form of program modules APM 1 and APM 2 , respectively, which run on an application device APD (see FIG. 2 ).
According to a further preferred embodiment of the method according to the present invention, once the data has been read from the memory area which is identified by the second address value AD 2 in the memory device DB, an application is started which is associated with the read data by an operating system OS in the application device APD. A procedure such as this is possible not only in the situation where the functionality of the user interface UI is restricted to a display device DIS and an input appliance KB, but also in the situation where the user interface UI is in the form of a personal computer or a workstation in the sense of a client/server architecture. In both situations, it has been found to be advantageous to store the contents of the memory unit SD in a non-volatile form in the control file CF, to at least partially read the control file CF when starting access control to the memory device DB, and to write them to a main memory MEM for the application device APD. This implies that the control file CF and the memory unit SD are combined to form a common access control file.
Furthermore, the access control file and/or the control file CF and the memory unit SD as well as the memory device DB may not only be accommodated on a common data medium but also distributed over a number of data media. Furthermore, the memory element in the memory unit SD which is associated with the address allocation device AAD should, for signal-processing reasons, be addressed by the address allocation device AAD on the basis of the first address value AD 1 read from the control file CF.
FIG. 3 shows an example of access to different memory devices DB 1 , DB 2 , DB 3 by a number of users u 1 , u 2 , u 3 during a main process PRC. The main process PRC is, in turn, subdivided into a number of process elements A, B, C, D. The memory devices DB 1 , DB 2 , DB 3 contain, for example, documents with information which is read, evaluated and possibly edited in the course of the main process PRC by the users u 1 , u 2 , u 3 who are involved with this process. In the present example, one user u 1 , u 2 , u 3 is, in each case, responsible for processing one process element A, B, C, D. In this case, it is actually not unusual for a user u 1 , as in the present example, to be responsible for processing two process elements A, D. A high level of matching and reprocessing effort is often necessary during the handling of main processes such as the main process PRC as a result of the overlaps, as can be seen in FIG. 3 , between access by the users u 1 , u 2 , u 3 to the memory devices DB 1 , DB 2 , DB 3 .
A main process navigation system, which is illustrated schematically in FIG. 4 as an application example of the method according to the present invention, simplifies access to jointly used memory devices by a large number of users who are involved in one main process. In the example illustrated in FIG. 4 , there are two control files CF 1 , CF 2 . The text and graphics contents may selectively be visualized either for one control file individually or for both control files jointly on one user interface UI as is illustrated in FIG. 2 .
A first control file CF 1 contains information relating to the running of a main process which is subdivided into a number of process elements A, B, C, D, in the same way as the main process PRC shown in FIG. 3 . The information relating to the running of a main process also may be supplemented by details relating to tasks and responsibilities within individual process elements. A second control file contains information relating to individual task packets within a main process or within process elements, in the sense of activity lists. The two control files CF 1 , CF 2 thus contain information relating to the provision of an overview of data which needs to be controlled by the main process navigation system. The use of two control files in this case allows an overview from two different perspectives. The number of control files may be increased further, depending on the requirement and structure of a database.
Once a first selection input has been received, a first address value AD 1 is read from one of the two control files CF 1 , CF 2 in an analogous manner to the above description relating to FIGS. 1 and 2 . This address value AD 1 is once again transmitted to an address allocation device, which is not shown in any more detail in FIG. 4 . The transmitted address value is used for addressing a memory element in a memory unit which is associated with the address allocation device. According to the exemplary embodiment illustrated in FIG. 4 , the memory elements are formed by matrices M 1 to Mv. The matrices also contain text and graphics contents with reference to information which is relevant for a main process in the sense of convenient user control.
Once a second selection input has been received, which is based on the visualized text and graphics contents of the matrix M 1 , an associated second address value AD 2 is selected for addressing the further matrices M 2 to Mv or the memory devices Dba or DBb. The selection input that is made is illustrated graphically in FIG. 4 by a shaded area within the matrix M 1 .
Although the present invention has been described with reference to specific embodiments, those of skill in the art will recognize that changes may be made thereto without departing from the spirit and scope of the present invention as set forth in the hereafter appended claims. | A method and computer program are provided for controlling access to a memory device wherein, even with a complex data storage structure, access is made to memory areas within the memory device with a minimal number of selection inputs required for selection of a desired memory area. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to gas compressor systems and, more particularly, to an electric switch gauge control apparatus for a rotary screw compressor.
2. Description of Related Art
Helical lobe rotary compressors, or "screw compressors," are well-known in the refrigeration and natural gas processing industries. This type of gas compressor generally includes two cylindrical rotors mounted on separate shafts inside a hollow, double-barreled casing. The side walls of such compressor casings typically form two parallel, overlapping cylinders which house the rotors side-by-side, with their shafts parallel to the ground.
As the name implies, screw compressor rotors have helically extending lobes and grooves on their outer surfaces. During operation, the lobes on one rotor mesh with the corresponding grooves on the other rotor to form a series of chevron-shaped gaps between the rotors. These gaps form a continuous compression chamber that communicates with the compressor inlet opening, or "port," at one end of the casing and continuously reduces in volume as the rotors turn and compress the gas toward a discharge port at the opposite end of the casing. The compressor inlet is sometimes also referred to as the "suction" or "low pressure side" while the discharge is referred to as the "outlet" or "high pressure side."
Compressor operations are sometimes described in terms of a "pressure ratio" comparing the discharge pressure produced at the compressor outlet to the pressure of the gas supplied at the compressor inlet. Since the pressure and volume of a gaseous fluid are related by the its ratio of specific heats, pressure ratios are sometimes alternatively expressed in terms of a "volume ratio." Compressor operations are also described in terms of the volumetric flow rate of the gas flowing through the compressor referred to as "capacity." However, this latter term must be considered in the context in which it is used since it can also refer to the maximum output of a particular device.
U.S. Pat. No. 4,080,110 discloses a control system for a variable capacity compressor which senses changes in electrical current flow to a motor. A current transformer and a converter provide a first electrical signal which is proportional to compressor capacity for comparison against a second signal which proportional to a system condition. The first and second signals are compared by a proportioning relay to provide a third signal for adjusting a slide valve so as to regulate compressor capacity.
The rate at which energy is consumed by the compression process is generally referred to as the "load" on the compressor and is typically expressed in units of "horsepower." The load on a compressor is mainly a function of the volume ratio and capacity of the compressor. In broad terms, the load on a compressor changes in proportion to the product of the volume ratio and capacity at which the compressor is operated. Consequently, compressor horsepower increases when either the volume ratio or capacity of the compressor are increased. Similarly, compressor load decreases when the volume ratio or capacity are decreased.
The maximum anticipated compressor load is a significant factor for determining the power output required from the prime mover which rotates the compressor. An underpowered prime mover can be easily overloaded and damaged by the compressor. An overpowered prime mover unnecessarily increases the initial cost of the compression system and may overspeed the compressor. It is therefore important to match the power output of the prime mover to the anticipated load on the compressor and/or to control the load on the compressor so as not overload the available power output from the compressor.
It is particularly important to control the load on the compressor during start-up and shut-down when the compressor is likely to receive its highest and lowest loads, respectively. For example, most screw compressor manufacturers recommend gradually loading screw compressors during start-up in order to prevent overpowering the prime mover. A typical start-up procedure begins with blocking the inlet gas source and opening the suction and discharge lines to atmosphere (to minimize volume ratio). Then, the compressor is slowly rotated (to increase capacity) before bypassing the compressor discharge line to the suction line (to further increase capacity). Finally, the gas supply to the compressor inlet is opened while slowly opening the compressor discharge to the back pressure of the process (to increase volume ratio). Similar procedures are used to gradually unload the compressor during shut-down to prevent the prime mover from over-speeding. A variety of other start-up and shut-down procedures are also well known.
In addition to matching the compressor load to the power output of the prime mover, the volume ratio and capacity of the compressor must be individually matched to the requirements of the downstream process. For example, if the volume ratio of the compressor is too high, the compressor may discharge compressed gas at a higher pressure than is required by the downstream process. Alternatively, if the capacity of the compressor is too high, the compressor will draw down the pressure of the low pressure gas source. Both of these energy inefficient operating conditions cause an unnecessary increase to the load on the compressor and thus waste a portion of the power being supplied by the prime mover.
It is well known that the volume ratio and capacity of a screw compressors can be adjusted using a slide stop and slide valve arrangement. For example, U.S. Pat. No. 4,678,406 discloses a typical configuration where the compressor operates at full capacity when the slide valve and slide stop are in contact with each other as shown in FIGS. 1-3 of the patent. In that patent, the position of the two slides together controls the volume (and pressure) ratio of the compressor and their position is adjusted in response to a signal from a pressure sensor connected to the discharge line from the compressor. When the discharge pressure drops below a set value, the slides move toward the discharge end of the compressor in order to increase the volume ratio of the compressor and prevent under compression of the gas. When the discharge pressures rises above a different value, the slides move in the other direction to decrease the volume ratio and prevent over-compression of the gas. FIG. 4 of U.S. Pat. No. 4,678,406 illustrates a slightly different configuration for operating the compressor at less than full capacity where the slide valve and stop are separated by a gap. In FIG. 4 of that patent, the position of the slide stop, and hence capacity, are adjusted in response to a signal from a pressure sensor in the suction line.
As noted above, the load on a compressor is mainly a function of the volume ratio times the capacity of the compressor. Although the arrangement discussed with respect to above can change the compressor load by individually adjusting the volume ratio and/or the capacity, it cannot sense the actual compressor load because there is no way to multiply these two variables. Thus, that arrangement cannot be used to control the load on the compressor.
One solution to this problem is to provide some type of additional control means for calculating compressor load based upon volume ratio, capacity, and/or other process variables. For example, U.S. Pat. No. 4,336,001 discloses a solid state compressor control system which indirectly calculates compressor load based on the position of a slide valve. Since the position of the slide valve indicates mostly the volume ratio of the compressor, the control system must make an assumption about capacity in order to calculate load. The safest assumption to use is that the compressor is operating at maximum capacity so that the actual load on the compressor is always maintained at less than the calculated load.
Although this assumption results in a margin of safety when the compressor is operated at less than full capacity, it also limits the volume ratio at which the compressor will operate at less than full capacity. Consequently, it does not allow the compressor load to be matched to the load capacity of the prime mover. In addition, such computer control systems are often complex, and therefore, difficult and expensive to implement, operate, and maintain.
SUMMARY OF THE INVENTION
The invention disclosed below addresses these and other drawbacks associated with conventional compressor systems by providing a control apparatus for measuring pressure in relation to a rotary screw compressor with capacity control means and a prime mover including a first pressure sensor to monitor the prime mover manifold pressure, and a series of relays which, when tripped by the pressure sensor, will engage a pressure mechanism to engage the capacity control means on the compressor. The pressure mechanism is preferably selected from the group consisting of a hydraulic and a pneumatic pressure mechanism. The apparatus may further include a second pressure sensor to monitor the inlet gas pressure to the compressor and a third pressure sensor to monitor discharge pressure of the gas compressor.
The pressure sensor may have at least two signals each capable of providing a signal to a control means to engage a pressure mechanism to move the capacity control means on the compressor. The pressure mechanism is preferably selected from the group consisting of hydraulic and pneumatic pressure mechanisms and the capacity control means preferably consists of a moveable slide valve run by a hydraulic actuator or controlled by a solenoid valve. The capacity control means may be selected from the group consisting of a poppet valve, a slide valve, and a herring bone unloader. The prime mover is a power source that may be selected from the group consisting of natural gas engines, steam engines, diesel engines, electric motors, gas and steam turbines, windmills, or other power sources.
In a preferred embodiment, the control apparatus includes as the series of relays, two sets of contact points normally in the open position and capable of closing magnetically when a signal is received from a sensor, a solenoid valve to move the capacity control means, a timer for shutting off the supply of electrical power to the control apparatus, and a power supply. More particularly, the preferred embodiment includes a two pole double throw switch connected to each of the sensors, and two sets of contact points normally in the open position which are capable of closing magnetically when a signal is received from a sensor connected via the two pole double throw switch; The apparatus may further include a timer for shutting off the supply of electrical power to the control apparatus. The power supply for the control system may be selected from the group including a standard automotive battery, a deep cycle battery, solar power, or the commercial electrical grid.
In another embodiment, the invention includes a control apparatus for measuring amperage draw of a prime mover of a rotary screw compressor with capacity control means including a first amperage sensor to monitor amperage draw on the prime mover, and a series of relays which, when tripped by the sensor will engage a pressure mechanism to engage the capacity control means on the compressor.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic process flow diagram of a gas compression process and compressor system.
FIG. 2 is a cross-sectional illustration of a variable orifice assembly for use with the gas compressor and process shown in FIG. 1.
FIG. 3 is an enlarged portion of FIG. 1 with a schematic illustration of a throttling control scheme.
FIG. 4 is a schematic electrical diagram of a switch gauge for use with the control system shown in FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a schematic diagram of a gas compression process and compressor system including a rotary screw gas compressor 2. The compressor 2 is preferably a Model TDSH (163 through 355) rotary screw compressor available from Frick Company in Waynesboro, Pa. However, a variety of other oil flooded and oil free screw compressors, and other types of compressors, may also be used.
In FIG. 1, a raw gas feed stream 4 from a natural gas well (not shown), or other gaseous fluid source, is supplied to a scrubber 6 for separating fluids and any entrained solids from the raw gas stream 4. The scrubber 6 may be any suitable two- or three-phase separator which discharges a liquid stream 8 to a disposal reservoir (not shown) and an essentially dry low pressure gas stream 10 to the compressor 2. The gas may also be dried using other well-known conventional processes. The dry low pressure gas stream 10 is then supplied to an inlet stream 12 and may also be supplied to a fuel stream 13 for fueling a prime mover 14. Although the prime mover 14 shown in FIG. 1 is a natural gas engine, a variety of other power plants, such as diesel engines or electric motors, may also be used to drive the compressor 2 through a coupling 16.
The compressor 2 receives low pressure gas through an inlet port 18. A suitable lubricant is supplied to the inside of the casing of the compressor 2 through a main oil injection port 20 where it is mixed with the gas to form a low pressure gas/oil mixture. The low pressure gas/oil mixture is then compressed and discharged from the compressor 2 through a discharge port 22 into a high pressure gas/oil mixture stream 24. A separator 26 receives the high pressure gas/oil mixture stream 24 and separates the gas from the oil and/or other lubricant in the mixture stream 24. The discharge temperature of the gas/oil mixture from compressor 2 may be monitored by a temperature sensor 25.
The separator 26 discharges a high pressure gas stream 28 for further processing and/or distribution to customers. In addition, the separator also discharges a high temperature oil stream 30 to a lube-oil cooler 34, preferably through a lube-oil collection reservoir 32 via one- to three- inch diameter stainless steel tubing, or other suitable conduit. The lube-oil collection reservoir may also be arranged in the bottom of the separator. The lube-oil cooler 34 preferably cools the high temperature lube-oil stream 30 from a temperature of 190° F. to 220° F., or preferably 195° F. to 215° F., to a temperature in the range of 120° F. to 200° F., and preferably in the range of 140° F. to 180° F., or nearly 170° F. for an oil flow rate of about 10-175 gallons per minute.
Typical coolers that may be used with the disclosed compressor system include shell and tube coolers such as ITT Standard Model No. SX 2000 and distributor Thermal Engineering Company's (of Tulsa, Okla.) Model Nos. 05060, 05072, and others. Plate and frame coolers, such as Alfa Laval MGFG Models (with 24 plates) and M10MFG Models (with 24 or 38 plates) may also be used, as may forced air "fin-fan" coolers such as Model L156S available from Cooler Service Co., Inc. of Tulsa, Okla. A variety of other heat exchangers and other cooling means are also suitable for use with the compressor system shown.
In a preferred embodiment, the temperature of the lubricant leaving the lube-oil cooler 34 is controlled using a by-pass stream 44 and a thermostat 36 which is preferably a three-way thermostatic valve such as Model No. 2010 available from Fluid Power Engineering Inc. of Waukesha, Wis. Although the manufacturer's specifications for this particular type of valve show it as having one inlet port and two outlet ports, it may nonetheless be used with the present system by using one of the valve's outlet ports as an inlet port. Other lube-oil temperature control systems besides thermostats and/or thermostatic control valve arrangements may also be used.
As shown in FIG. 1, the high temperature oil stream 30 is split into two branches (or "flows") by a two-way splitter 38 prior to reaching the thermostat 36. The splitter 38 is preferably formed from T-shaped stainless steel tubing; however, other "T" fittings may also be used. The first branch 40 of high temperature lube-oil stream 30 goes directly into the cooler 34 where it is discharged through a cooled lube-oil branch 42 into the thermostat 36. The second, or "by-pass," branch of high temperature lube-oil stream 30 bypasses the cooler 34 and goes directly into the thermostat 36 where it may be mixed with lubricant from the cooled lube-oil branch 42 to control the temperature of a mixed (first and second branch) cooled lube-oil stream 46 leaving the thermostat 36. By controlling the amount of lube-oil from each of the first and second branches 42 and 44 flowing through the thermostat 36, the thermostat can control the temperature of the cooled lube-oil stream 46 leaving the thermostat.
The cooled lube-oil stream 46 then flows through a filter assembly 48 to create a filtered stream 56. The filter assembly 48 includes a housing 50 for supporting a plurality of filters 52. A preferred filter housing 50 is available from Beeline of Odessa, Tex., for supporting four filters 52, such as Model Nos. B99, B99 MPG, and B99HPG available from Baldwin Filters of Kearney, Nebr. However, a variety of other filters and filter housings may also be used. Pressure indicating sensors 54 may also be provided at the inlet an outlet of the filter housing for determining the pressure drop across the filters 52 and providing an indication as to when the filters need to be changed. The filter assembly 48 may also be arranged in other parts of the process, such as between the reservoir 32 and two-way splitter 38.
Downstream of the filter assembly 48, the filtered lubricant stream 56 flows into a three-way splitter 58 forming a discharge bearing and seal branch 60, an orifice branch 62, and a suction bearing branch 64. The discharge bearing branch 60 provides filtered and cooled lube-oil to the seals and discharge bearings of the compressor 2 through a lubrication port 66 while the inlet bearing branch 64 provides filtered and cooled lube-oil to the inlet bearings, and possibly a balance piston, through lubrication port 68.
The orifice branch 62 of the filtered and cooled lube-oil stream 56 supplies filtered and cooled lubricant to an external orifice assembly 70. As shown in FIG. 2, the orifice assembly 70 preferably includes an internally threaded orifice housing 72 for receiving an externally threaded (preferably steel) tube 74 having a bore 76 through which cooled and filtered lube-oil from the orifice branch 64 can flow through the injection oil branch 78 (see FIG. 1) to the main oil injection port 20 on compressor 2 (also shown in FIG. 1). In the preferred embodiment shown in FIG. 2, the orifice assembly 70 may further be provided with a moveable plug 80, or other flow control means, for manipulating the flow rate of lube-oil through the bore 76. A variety of conventional choke valves are suitable for providing the throttling effect of moveable plug 80.
The orifice assembly 70 may also include two pressure sensing ports 82 and 84 connected to a differential pressure sensor 86 such as a Model No. 25-DP-LTP-150 differential switch pressure gauge available from Frank W. Murphy Manufacturer of Tulsa, Okla. When the differential pressure sensor 86 senses a pressure difference across the orifice (and therefore a flow rate through the orifice assembly) which is too low, it provides a signal on a control line 88 to a control panel 90 which then sends another control signal over control line 92 to the prime mover 14 that automatically shuts down the prime mover and/or the compressor 2. The set point of the differential switch pressure gauge for this system will typically range from 20-300 psid, or preferably 20-100 psid, so that the lube-oil flow through the orifice assembly ranges from 5-250 gallons per minute ("gpm"), or preferably 10-175 gpm. However, a variety of other set points and flow rates may also be used. Alternatively, the low main oil injection flow signal from the differential pressure sensor 86 may simply produce an alarm or may be transmitted directly to the prime mover 14 and/or the compressor 12 without going through the control panel 90.
The prime mover 14 and/or compressor 2 may also be shut down based upon a signal from temperature sensor 25 which may or may not travel through the control panel 90. Similarly, the control panel 90 may be linked to the pressure sensors 54 to provide an indication when the filters 52 need to be changed.
The compressor system discussed above has been found to require 20-35 psid less differential pressure between the compressor inlet port 18 and the discharge port 22 than conventional screw compressors systems without lube-oil circulation pumps. Consequently, the disclosed compressor system provides greater operational flexibility for a lower initial cost than similar conventional compressor systems.
FIG. 3 is an enlarged portion of FIG. 1 which has be augmented to include a schematic illustration of a control system. In FIG. 3, the prime mover 14 may be fueled by a fuel gas stream 13, as in the case of a gas engine or gas turbine, or an electrical power source 94, in the case of an electric motor. Other prime movers and power sources may also be used, such as steam engines and turbines, gasoline and diesel engines, windmills, waterwheels, or others.
A capacity control device 96 (not shown in FIG. 1) is arranged in the compressor 2. Although the capacity control device 96 is illustrated as a slide valve and actuator, a variety of devices for controlling the capacity and/or volume ration for the compressor 2 may also be used including manually operated valves of various types, variable orifice assemblies, poppet valves, slide valves, and herring bone unloaders. For example, a preferred configuration available from Frick Company of Waynesboro, Pa. includes a Variable Volume Ratio moveable slide valve stop arrangement on the compressor discharge for allowing the compressor to be adjusted from 10-100% full capacity. A variety of techniques for actuating the slide valve and/or slide stop may be used such as pneumatic and hydraulic pressure actuators, servomotors, solenoid valves.
FIG. 3 also shows pressure indicating and transmitting sensors 98, 100, and 102 arranged near the compressor intake port 18, discharge port 22, and intake manifold of the prime mover 14, respectively, for sensing and monitoring the various pressures at these points in the system. The pressure transmitting sensors 98-102 are preferably switch gauges which can determine, and possibly indicate, the status of a process variable and throw a switch when that process variable reaches a set value. Preferred switch gauges are equivalent to Model No. 45 PEBP available from Frank W. Murphy Manufacturers of Tulsa, Okla. Murphy Model Nos. 45PE and 45PEF, and others, may also be used.
In general, the intake manifold pressure of an engine will increase as the throttle is opened to allow the engine to consume more fuel and produce more horsepower. In a preferred embodiment, the intake manifold of a natural gas engine for driving the compressor 2 will draw about 18 in. Hg of vacuum when the compressor is lightly loaded and a weaker vacuum when it is more heavily loaded. Consequently, the pressure sensor 102 is preferably a vacuum pressure sensor that will sense less vacuum as the load on compressor 2 is increased.
In order to prevent an engine prime mover 14 from overloading and breaking down, the pressure sensor 102 preferably sends a control signal to the capacity control device 96 whenever the vacuum pressure measured by sensor 102 increases in magnitude, such as around 5 in Hg. for a naturally aspirated engine. (Higher positive pressures may be used as the set point for turbo-charged engines.) That control signal will signal the actuator for capacity control device 96 to cause the device to reduce the capacity of the compressor 2, and thus unload the compressor, the load on the prime mover gets too high.
Alternatively, or in addition to the control signal produced by pressure sensor 102, pressure sensor 98 may be arranged to transmit an unload signal to the capacity control device 96 when the suction pressure gets too low, as can occur when the demand for compressed gas rises. The temperature sensor 25 may also be used for sending a signal to the capacity control device for decreasing the capacity when the discharge temperature of the compressor 2 gets too high. In a preferred embodiment, a switch is provided for switching the capacity control from sensor 98 to sensor 102.
Alternatively, or in addition to the temperature and/or pressure sensors 98 and 102, the compressor system may include a pressure sensor 100 for transmitting a signal to the capacity control device for unloading the compressor when the discharge pressure gets too high, as might occur when the discharge stream is blocked by a pig.
If the compressor 2 is powered by an electric motor, a current or power sensor 104 may be provided for sensing the current drawn, power used, and/or other electrical variables for an electric prime mover 14 and providing a control signal to the throttling device 96 for loading or unloading the compressor.
The control signals provided by transmitting sensors 98-102 may be hydraulic, pneumatic, electric, or of another form. Various power supplies may be used to produce the control signals including a standard automotive battery, a deep cycle battery, solar power, or the commercial electrical grid. In order to simplify the drawing, a single control line 106 has been shown for all of the sensors. However, in practice, each sensor will have its own independent transmitter and independent communication line. The signals on those control lies may travel directly to the capacity control device 96 as shown conceptually in FIG. 3, or they may first travel through a control panel and/or process controller as with the sensors shown in FIG. 1.
Since it is usually preferable to change the compressor capacity very slowly, the control signals from the sensors 98-102 may be placed on a timer (not shown), or through an integral controller, that prevents actuation of the capacity control device 96 until a control signal has been sent from one of the sensors for a certain continuous period of time. A timer or integral controller is particularly useful for quick actuators like servomotors or solenoids. The timer may also be used to shut-off the power for the control lines 106 in order to reset (or set) the sensors after a control action has taken place and during start-up or shut-down. Other types of controllers, such as proportional, integral, and computerized controllers, may also be employed.
In a preferred embodiment, the sensors 98-102 each include a transmitter having plurality of relays. The transmitters preferably include two single pole double throw (preferably snap-acting) switches, a double pole double throw switch, or a two pole double throw switch. In addition, the relays preferably include two sets of normally open contact points which are closed when a signal is received from a sensor transmitter connected via the two pole double throw switch. The relays, when tripped by the sensor, will drive the actuator to cause the capacity control device 96 to control the flow through the compressor.
FIG. 4 is a schematic electrical diagram for one embodiment of a switch gauge for use with the control system shown in FIG. 3. The illustrated switch gauge includes an indicator 108 having a double pole single throw switch 110, and a relay 112 having a double pole double throw switch 114 with two sets of contacts driven by magnetic solenoid actuator 116 connected to the switch 110. In a typical application, the switch gauge includes a common connection 118, a negative or neutral connection 120, a positive or line connection 122, a set connection 124, and a reset connection 126. In this way, a low voltage control signal transmitted through the line and neutral connections controls power transmission through the relay 112.
The control system disclosed above offers a simple and inexpensive means for automatically controlling a screw compressor based upon compressor inlet pressure, discharge pressure, and prime mover load. It can be easily retrofitted on a manually controlled compressor in order to reduce the labor required for loading and unloading the compressor during start up, shut down, upsets and other capacity changing process events.
While the compressor system, control system, and processes described above have been discussed with respect to certain drawings, vendors, products, and preferred configurations, this description is merely illustrative of some of the various useful forms in which the invention might be reduced to practice by one of ordinary skill in the art. The scope of the actual invention, on the other hand, is defined by the subject matter of the following claims. | A control apparatus, for measuring pressure in relation to a rotary screw compressor with capacity control means and a prime mover, including a pressure sensor to monitor the prime mover manifold pressure, and a series of relays which when tripped by the pressure sensor will engage a pressure mechanism to engage the capacity control means on the compressor. The pressure mechanism may be a hydraulic or a pneumatic pressure mechanism and the apparatus may further include a second pressure sensor to monitor the inlet gas pressure to the compressor and a third pressure sensor to monitor discharge pressure of the gas compressor. | 5 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] The present application is a Continuation of U.S. application Ser. No. 11/274,090, filed Nov. 16, 2005, which is incorporated herein in its entirety which claims priority to Provisional U.S. Application No. 60/627,970, filed Nov. 16, 2004, which is incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a system for covering wood decking and other surfaces that provides a durable final finish. It also relates to a method of manufacturing an ideal polymer covering material and a method of application of the covering material.
[0003] Wood structures are prone to deterioration by weather, ultraviolet rays in sunlight and abrasion from traffic and the like. Commercial wood replacement materials that have improved weathering durability are expensive and the refurbishment of existing wood decking with these synthetic substitutes is both expensive and complicated. There are many types of coatings that have been developed to slow the deterioration of wood structures and improve the appearance of deteriorated wood. Most of these coatings are applied in the liquid state via brushing or using spraying equipment. Many of these coatings are applied from solvent based formulations and thus generate large amounts of VOC (volatile organic compounds) that are released into the atmosphere upon drying. In addition, when the wood of a deck surface or other structure has been significantly deteriorated the typical coatings available cannot return the deck surface to a high quality appearance Expansion and contraction of wood relative to ambient moisture conditions leads to wood splitting, chipping and splintering. Conventional thin polymer coatings that are applied to achieve water repellency often fail in use as a consequence of the woods' expansion and contraction caused by ambient moisture changes. Therefore, there exists a need for an alternative to the prevalent coating approach to restoring and preserving wood deck surfaces.
SUMMARY OF THE INVENTION
[0004] The present invention relates to the restoration and protection of wood and other surfaces through the application of a preformed polymer film that can be readily applied to the desired surface. The preformed polymer film is manufactured in rolls. The preformed polymer film as pre-slit rolls are applied to the surface with adhesive and the edges are uniformly held in place with specially designed channels. The adhesive used can either be a permanent adhesive or a temporary adhesive. The temporary adhesive could be used in situations where it is desirable to change the deck covering material for special events, seasonal events or some other reason.
[0005] The deck covering preformed polymer film must have superior weather resistance, abrasion resistance, elasticity, and UV resistance. The preformed polymer film of the present invention can be polyurea, polyurethane, hybrid polyurea-polyurethane or other outdoor durable materials like but not limited to the vinyl family of polymers.
BRIEF DESCRIPTION OF THE FIGURES OF THE DRAWING
[0006] FIG. 1 a - d show the deck covering of the present invention as it is installed.
[0007] FIG. 2 shows a close up of one design of the locking channel.
[0008] FIG. 3 shows the slot dye coating manufacturing process for making the deck covering preformed films.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0009] Polyureas are well known, and are often classified as a heterochain macromolecular compound which contains urea groups in its structure. Polyurethanes are also well known, and include materials that incorporate the carbamate function group as well as other functional groups such as ester, amide ether and urea. Commerical polyureas and polyurethanes are well known, which are used as films and coatings. Any such polyureas and/or polyurethanes can be used and imprinted in accordance with the present invention.
[0010] In a preferred embodiment, the polyurethane/polyurea protective film or substrate/surface is produced by reacting an isocyanate with a polyol in the presence of a diamine or triamine. Preferably, the diamine or triamine is aliphatic and of low moleculare weight. The polyol is preferably a polyester polyol, a polyether polyol or an acrylic polyol. The reaction is also preferably run in the presence of a catalyst, e.g., a tin, zirconium or bismuth based catalyst.
[0011] The basic polyurea/polyurethane chemistry has been shown to yield excellent physical properties in spray applied applications and brush applied applications. The system of the present invention will allow much less skilled technicians to easily install the preformed polyurea/polyurethane deck covering. In addition, the use of complicated commercial spray equipment is eliminated with this system.
[0012] While one of the primary applications envisioned for the polyurea and/or polyurethane based preformed pre-slit panels is protecting and restoring wooden decking the material can be used on virtually any surface in need of upgrade. Walls, ceilings, exterior and interior building panels, structural steel and the like will benefit from application of the deck covering material.
[0013] The deck covering material ideally will be manufactured in widths appropriate for typical standard lumber dimensions such that enough excess panel material will be available for wrapping over the edge of individual boards on a deck. For typical 5/4 decking which is 5.5 inches wide nominally a roll of deck cover will be produced at approximately 7.5 inches wide. The deck cover will be laid out and any trimming that is necessary can be accomplished prior to applying the adhesive. The adhesive is then applied to the area the deck cover is placed over and the deck cover is put in position. The next board is then also covered in the same manner. The overlap material is placed down into the groove between the boards. The channel is then pressed into the groove and secured with the pressure from the tapered channel edge applying pressure to assure a neat final finish. FIG. 1 shows the step by step application of the polyurea deck cover system.
[0014] In FIG. 1 a, 5/4 decking 1 , 5½ inches wide are laid out with gaps 2 ranging from ¼ to ½ inch. In FIG. 1 b, a polyurea/polyurethane film 3 is layered over the deck boards, which are held in place with a non-aggressive, repostionable adhesive. FIG. 1 e shows channel strips 4 pushed into the gaps between the deck boards. In such a case, screw clips can be used, e.g., at an interval of every 16 inches, to hold the channel and edges in place. FIG. 1 d shows the channel end view and the channel screw section in more detail.
[0015] In FIG. 2 , a preferred embodiment of a channel/gap fastener is shown. This particular channel strip 5 is simply pushed down into the gap and preferably screwed down to secure its position. Water drainage holes 6 are present in the channel fastener. Also, the outward force of the channel fastener holds the film against the sides of the deck boards.
[0016] In FIG. 3 , a slot dye coating manufacturing process is depicted for making deck covering preformed films. Three feeds to the slot dye are used, i.e., the isocyanate feed 10 , the solvent flush 11 , and the polyamine/polyol feed 12 . The isocyanate and polyamine/polyol are fed through the dye and begin to react. The reactant mixture is cast onto a release base and then passed into a curing oven 15 to effect completion of the reaction and curing of the polyurea/polyurethane polymer. The curing oven is often run at a sufficient temperature to effect the cure, but is generally kept in the temperature range of from 250-300° F. The temperature may vary based upon residence time in the oven. Near zero emissions are realized from the oven.
[0017] A relatively slow cure material is preferably used, whether it is by choice of reactants or catalyst. The choice is made in order to effect an accelerated cure in the curing oven. The solvent flush, using any suitable organic solvent, e.g., acetone, is generally activated immediately when the isocyanate and polyamine/polyol feeds are stopped, in order to prevent curing of residual material in the die.
[0018] The preformed polyurea based deck cover can be produced on coating machines similar to those used in the manufacture of photographic films. The polyurea based film is made from a two component mixture that is mixed just prior to casting onto a carrier/release sheet. The polyurea based film is then peeled off the carrier sheet and rolled up into rolls and pre-slit for final use.
[0019] Conversely, the polyurea based deck cover material can also be produced by spraying via spray equipment. Equipment for example manufactured by Glas-Craft or Gussmer can be used.
[0020] The locking channel can be made from materials such as but not limited to polyvinyl chloride, polyurea, polyurethane and the like. Typical extrusion equipment can be used to manufacture the locking channel.
EXAMPLE
[0021] A polyurea deck cover sheet is manufactured by controlled spray application of a two component system via a Glas-Craft MIX unit. The preformed polyurea film of approximately 2 mM thickness is then peeled off the release sheet and cut into 7.5 inch wide strips. The 5/4 wood decking to be covered is then coated with a high strength adhesive. The deck cover strips are then laid in place and the overlap material tucked into the gap between the boards. Finally, the locking channel is pressed between the boards and yields a neat trim finish. The polyurea based film of this example is manufactured according to the following formula;
[0022] Part A Isocyanate: 50 parts Bayer N3400/50 parts ARCPP-100
[0023] Part B Polyamine; 50 parts Clearlink 1000/50 parts ARCdiamirie-100
[0000] Spray unit pressure of 2200 psi, temperature of 170° C. for Part A, 150° C. for Part B
[0024] While the preferred embodiments of the invention have been disclosed in detail, other embodiments within the described invention obvious to those skilled in the art are considered to be part of the present invention and are intended to be included in the claims below. | Provided is a system and method for protecting and restoring a surface by applying thereto a preformed polymer based film and securing the film to the surface. Particular application is found where the surface is a deck surface. | 2 |
FIELD OF THE INVENTION
The present invention relates to a fluid or liquid jet recorder.
DISCUSSION OF THE PRIOR ART
A liquid jet recorder which includes at least one jet nozzle which is connected to a pressure medium conduit for the ejection of an electrically-conductive recording liquid onto a recording carrier, and which includes at least one control electrode connected to a signal source for modulation of the liquid jet in the context of carrying out spot or point wise recording, is described in German Published Specification No. 1,271,754. In this prior art liquid jet recorder, modulation of the liquid jet between a jet nozzle and the recording carrier is facilitated through the intermediary of a suitable voltage which is applied intermediate the recording liquid and the associated control electrode. The known liquid jet recorder thus facilitates that an image, which is constituted of lines, may be inscribed or recorded on the recording carrier. In an embodiment of the known liquid jet recorder for linewise image recording, the recording carrier is stretched or mounted on a rotatably supported drum. The drum is rotated about its longitudinal axis in synchronism with line impulses from an image transmitter, while being concurrently displaced in the axial direction. The unmodulated liquid jet impinges perpendicularly against the recording carrier. The image signal is thereby applied to the control electrode for effecting the linewise image recording.
In the known liquid jet recorder, for the recording of a color image which is constituted of three different basic colors such as, for example, the colors yellow, red and blue, there are provided three jet nozzles. Each image point is provided in a sequential order with the required color component from each jet nozzle.
In the recording of an image point or spot which is formed of the three basic colors, it is necessary that each color be sprayed at its desired proportion. Thus, if for example, an image point should consist of 20% yellow, 30% red and 50% blue color proportions, it is necessary to so control the voltage for each of the three electrodes during the inscribing or recording of the respective color on the image point, to thereby achieve the desired color intensity. For this purpose, it has been proposed in the above-mentioned publication that the high-voltage at the control electrode be correspondingly selected. This, however, has the disadvantage that complex and expensive circuit arrangements must be utilized for effecting variation of the high-voltage at the control electrodes.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a liquid jet recorder of the above-mentioned type, which in a simple manner facilitates that the intensity of a recording color may be controlled within a predetermined range of accuracy.
The foregoing object is inventively achieved in that the signal source comprises a number of impulse generators which correspond to the number of desired color steps for each image point, whose impulse sequences are in synchronism, which possess equal impulse amplitudes and may be differentiated from each other with respect to the sensing relationship of the color steps; and including means for connecting the required impulse generator required for the recording of a desired color step on an image point to the associated electrode, while providing an identical recording time for all image points. In contrast with the state of the technology, the high-voltage applied to a control electrode for modulation of the liquid jet, in the present invention, remains constant. The intensity modulation is carried out by sensing of the high-voltage and thereby of the liquid jet, whereby the sensing ratio corresponds to the intensity of the recorded color. The inventive liquid jet recorder is applicable as a color recorder without requiring any appreciable additional circuitry requirements.
In a preferred embodiment of the invention, provision is made that the liquid jet recorder be monitored with respect to the satisfactory function thereof so as to prevent that, in an undesirable manner, apparatus components may be struck by the recording liquid and thus made dirty.
BRIEF DESCRIPTION OF THE DRAWINGS
Further details of the invention may now be ascertained from the following description of an exemplary embodiment thereof, taken in conjunction with the accompanying drawings; in which:
FIG. 1 shows a schematic representation of the liquid jet recorder constructed pursuant to the invention;
FIG. 2 is a circuitry detail in the liquid jet recorder of FIG. 1;
FIG. 3 shows three impulse sequences during the operation of the circuitry of FIG. 2;
FIG. 4 shows a circuit diagram of a monitoring installation used in connection with the recorder; and
FIG. 5 illustrates a circuit diagram of a control installation for the liquid jet recorder of FIG. 1.
DETAILED DESCRIPTION
The fluid or liquid jet recorder, as shown in FIG. 1, includes a drum 1 on which there is stretched or mounted a recording carrier 2 constituted of a sheet of paper. For recording there are employed three recording or scribing systems 3 through 5 which, respectively, consist of a control electrode 6 through 8, and a jet nozzle 9 through 11. The jet nozzles 9 through 11 project the required recording liquid from supply receptacles 12 through 14 through the use of pumps 15 through 17, through the control electrodes 6 through 8. Between the jet nozzles 9 through 11 and pumps 15 through 17 there may also be, respectively, positioned pressure regulators 18 through 20.
The three recording systems serve for the recording or inscribing of three varied colors, for example, the colors blue, red and yellow, so that a colored image is inscribed on the recording carrier 2. The control electrodes 6 through 8 are passed through by the liquid jet ejected from jet nozzles 9 through 11. These liquid jets disintegrate into drops within the tubularly-shaped control electrodes so that, upon application of a high voltage between the control electrodes and the recording liquid, there is produced a vapor cloud. This vapor cloud precipitates on the control electrodes, the latter of which are formed of a porous material, and are then aspirated by a suction conduit 21 through the intermediary of a suction pump 22. The control impulses for the control electrodes 6 through 8 emanate from a control installation 23. If a control impulse is lacking, then a color point is generated on the recording carrier 2; however, if a control impulse is present, then the flow of liquid between the respective jet nozzles 9 through 11 and the recording carrier 2 is interrupted.
The recording systems 3 through 5 are fastened onto a plate 24 which is longitudinally displaceably supported on two rails 25. The recording systems 3 through 5 and the plate 24, in the position shown in FIG. 1, are illustrated in their inactive position away from the recording carrier 2. The recording is carried out in a manner wherein the plate 24 is uniformly moved along rails 25 in the direction of arrow 26 over the entire length of the drum, while the drum 1 is uniformly rotated in the direction of arrow 27, or reversely. The recording thus is effected in a helix-like path on the recording carrier 2. The signals of the control installation 23 contain the image information.
After the completion of a recording or inscription, the plate 24 together with the recording systems 3 through 5, is again moved back into the illustrated inactive or initial position.
In order that residuals or excesses of the recording liquid may be removed from the recording systems 3 through 5, there is provided a suction pad 28 which is supported in a pan 29, and which is commonly associated with the control electrodes 6 through 8. The pan 29 is movable in the direction of arrow 30 in such a manner, whereby the suction pad 28 may be pressed against the jet outlet sides of the electrodes 6 through 8.
The control installation 23, pursuant to FIG. 2 includes seven impulse generators 31 through 37, which are synchronized by means of a pulse generator 38. Each of the impulse generators 31 through 37 delivers an impulse sequence whose frequency and impulse amplitude is constant, and whose sensing ratio corresponds to one of seven color increments or steps. The through-connection of the high-voltage impulse generators 31 through 37 to the electrodes 6 through 8 is carried out through the intermediary of a distributor 39, which is controlled by signals in three conductors 40 through 42. The conductor 40 is thereby, for example, associated with the image color blue, the conductor 41 with the image color red, and the conductor 42 with the image color yellow. The intensity of the three colors of an image point is characterized through binary signals in the conductors 40 through 42. Through these signals there may thus be characterized the percentual composition of an image point based on these three image colors. Thus, if there is to be sprayed on an image point 43 proportion of, for example, 20% yellow, 30% red, and 50% blue, then in the illustrated position of the drum 1, first the signal in the conductor 40 characterizes the blue proportion. Those of the impulse generator 31 through 37 which provide this blue component are connected for a predetermined time period to the control electrode 6, and the blue component is sprayed. If the image point 43 has moved to the location 43', then the signal in the conductor 41 characterizes the red component of the image point 43, and the respective impulse generator 31 through 37 is connected with the control electrode 7. The recording of the red proportion is carried out during the same time interval as the recording of the blue component. If the image point has moved further to the location 43", then the signal in the conductor 42 characterizes the yellow portion of the image point 43, and the respective impulse generator 31 through 37 is connected with the control electrode 8. Also in this instance the recording of the yellow proportion is carried out during the same time period as the recording of the blue and red components.
The signals associated with an image point in conductors 40 through 42 must, in conformance with the sequential recording of the three image colors, timewise offset appear in the conductors 40 through 42. This can be effectuated, when the signals are presented initially at the same time, through corresponding delays of the signal in the conduit 41 with respect to the signal in conduit 40, and the signal in conduit 42 with respect to the signal in the conduit 41. The delay can be effected by means of, for example, slide registers.
In the embodiment according to FIG. 2 it is possible to provide seven color increments for each image color. Furthermore, it is possible to attain a further color increment (color white) in response to continual application of a high-voltage to a control electrode during the recording time for an image point.
If no image color is to be obtained for a particular image point, than for this image point the high-voltage should be constantly maintained at the electrode.
FIG. 3 illustrates three impulse sequences which may, for example, be applied to the control electrodes 6 through 8 for the recording of an image point. The t is thereby this particular time period during which the information associated with an image point is applied to the control electrode, namely, the above-mentioned recording time. FIG. 3 has the basic assumption that an image point is to contain 0% of yellow color. In accordance therewith, the impulse sequence 44 is applied to the control electrode 6, and the impulse sequence 45 to the control electrode 7, whereas to the control electrode 8 during the time period t there is applied a constant high-voltage pursuant to line 46. The impulse sequences 44 and 45 represent high-voltage impulses which are applied to the control electrodes during the times t min and which are small in comparison to the intervening impulse pauses. The sensing ratio has its minimum value for the impulse sequences 44 and 45. In accordance therewith, the colors blue and red, which are associated with the impulse sequences 44 and 45, are recorded on an image point at the greatest intensity. Since during the time period t a continuous high-voltage is applied to the control electrode 8, the color yellow is not at all applied to this image point. The sensing of the liquid jet is carried out also during recording of the greatest intensity so as to facilitate monitoring of the function of the recording, as is described in greater detail hereinbelow.
If an image point is to be constituted of the three image colors in another way, then the sensing ratio of the impulse sequences 44 and 45 are correspondingly varied with respect to the desired proportion of the image color. If required, at the locations of the impulse sequences 44 and 45 there may be applied a constant high-voltage during the time period t. Further, the constant high-voltage 56 may be replaced by an impulse sequence.
It is important for the present invention that through a number of impulse generators 31 through 37 corresponding to the number of the desired color increments for each image point, each of the image colors can be reproduced on an image point in the required intensity.
From FIG. 3 there may be ascertained that, during a minimum time period t min, at all three electrodes 6 through 8 there is present a high-voltage and therein the time periods t min of the impulse sequence frequency of the generators 31 through 37 correspondingly follow each other (timewise coincidence). From the foregoing there is ascertained that, when a signal is generated, which corresponds to the sum of the voltages at the three electrodes 6 through 8, this signal possesses an impulse shape in which the impulse amplitude exceeds a predetermined value at undisturbed operation during a minimum time period, and the pauses between two impulses do not exceed a maximum value. This fact can be utilized for monitoring disturbances of the liquid jet recorder, in accordance with FIG. 4.
In FIG. 4 there are illustrated three resistances 47 through 49 to which there are transmitted signals through conductors 50 through 52, which correspond to the voltages at the control electrodes 6 through 8. The resistances 47 through 49 are high-ohmic in comparison with the summing resistance 53, so that a voltage is applied to location 54 which corresponds to the sum of the three voltages in the conductors 50 through 52. This voltage is transmitted to threshold sensor 55 which connects a transistor 56 through a coupling resistance 57 for as long as the voltage at its input, in effect, at location 54, exceeds a predetermined reference value. During an undisturbed operation the voltage at input location 54 of the threshold sensor is, at least during the times t min, above the reference value and the spacing between the voltage impulses does not exceed the time period t 1 . The connected transistor 56 effects the charging of a condenser 58. As soon as the high-voltage is lacking at one of the electrodes 6 through 8, the impulses at the input of the threshold sensor 55 no longer reach the required magnitude for effecting a reversal. The condenser 58 may then be discharged through the resistance 59 more strongly than for undisturbed operation, so that after completion of a predetermined time period, which is characteristic of the presence of a disturbance (for example, 2xt 1 , there reverses a Schmitt-trigger 60, since then the voltage at the condenser 58 drops below a predetermined value. This will control a switch-off device 61, which deactivates the liquid jet recorder. During undisturbed operation, the condenser 58 is always again timely recharged before the level of the Schmitt-trigger is reached.
The circuit arrangement according to FIG. 4, in a simple manner, facilitates the monitoring of the operation of the liquid jet recorder since there is tested if a high-voltage is applied to all three electrodes 6 through 8 within predetermined time spacings. In this manner it can be prevented that, due to the lack of a high-voltage as a result of disturbance, the recording liquid can be sprayed in the apparatus or onto the drum in an undesired manner.
The invention is described in connection with a color recorder in which a color image is constituted of three basic colors. However, it is also applicable for use with one jet nozzle for the creation of black-white image. Also in this instance the intensity control of the liquid jet is provided through selection of the particular suitable impulse generator 31 through 37.
The construction of the control installation 23 may be more closely ascertained from FIG. 5. Thus, FIG. 5 illustrates the impulse generators 31 through 37, which are monostable stepping oscillators or flip-flop circuits. These flip-flop circuits are jointly reversed by a beat generator 38. They possess varied time constants and thereby reverse back in accordance with different times, as measured from the end of a beat impulse. Thereby, at the outputs 62 through 68 of the flip-flop circuits 31 through 37 there are obtained impulse sequences which possess the same frequence but different sensing ratios.
In FIG. 5 there is illustrated the control passageway for only the basic color blue. The control passageways for the basic colors red and yellow are constructed in the indentical manner as this illustrated passageway. The output impulses of the flip-flop circuits or stepping oscillators 62 through 68 are transmitted to the inputs of AND-gates 69 through 75. The other inputs of these AND-gates are connected to a binary-decimal converter 76 which possesses three input conductors 77 through 79, to which there is applied the 3-bit information for a basic color. The three input conductors 77 through 79 correspond to the conductor 40 in FIG. 2. At the inputs 77 through 79 there is applied a 3-bit signal which characterizes the intensity of the basic color blue for an image point. This signal is so processed in the binary-decimal decoder 76 so that a signal appears at one of the seven outputs of the binary-decimal decoder 76. The seven outputs of the binary-decimal decoder 76, in effect, correspond to the seven intensity increments for an image and a basic color.
The AND-gates 69 through 75 have an OR-gate 80 connected thereto, which controls a high-voltage switch 81, the latter of which is connected to the electrode 6.
It is assumed that the 3-bit information at the inputs 77 through 79 corresponds to the output signal at the output 82. In accordance therewith, the AND-gate 73 is opened and the impulse sequence of the flip-flop or stepping oscillator 35 is transmitted through the OR-gate 80 to the high-voltage switch 81. During the time period t (FIG. 3) the impulse sequence delivered by the flip-flop or stepping oscillator 35 is applied to the high-voltage or high-tension switch 81, and the color blue is recorded on an image point with an intensity which is determined through the sensing ratio of the impulse sequence of the flip-flop circuit 35.
Also the basic colors red and yellow each have a binary-decimal decoder associated therewith, which is connected together with AND-gates and OR-gate in the above described manner. Each of the further OR-gates has, respectively, connected thereto a high-voltage or tension switch. Each of the two further high-voltage conductors controls one of the electrodes 7 and 8. The output conductors 62 through 68 are, in effect, conveyed in parallel to the inputs of two further groups of, respectively, seven AND-gates, whose other inputs each lead to a further binary-decimal decoder.
While there has been shown what is considered to be the preferred embodiment of the invention, it will be obvious that modifications may be made which come within the scope of the disclosure of the specification. | A liquid jet recorder which includes at least one jet nozzle which is connected to a pressure medium conduit for the ejection of an electrically-conductive recording liquid onto a recording carrier, and which includes at least one control electrode connected to a signal source for modulation of the liquid jet in the context of carrying out spot or point wise recording. The liquid jet recorder of the above-mentioned type, which in a simple manner facilitates that the intensity of a recording color may be controlled within a predetermined range of accuracy. The signal source comprises a number of impulse generators which correspond to the number of desired color steps for each image point, whose impulse sequences are in synchronism, which possess equal impulse amplitudes and may be differentiated from each other with respect to the sensing relationship of the color steps; and including means for connecting the required impulse generator required for the recording of a desired color step on an image point to the associated electrode, while providing an identical recording time for all image points. | 7 |
PRIOR APPLICATION
This application is a U.S. national phase application based on International Application No. PCT/SE2006/050531, filed 30 Nov. 2006, claiming priority from Swedish Patent Application No. 0502667-9, filed 2 Dec. 2005.
BACKGROUND AND SUMMARY OF THE INVENTION
When manufacturing chemical cellulose pulp from chopped chips, it is desired to expel air and moisture from the chips. It is at the same time desired to heat the chips to the desired process temperature, suitably to a level around 100° C., since the chips are finally to reach a temperature of approximately 130-160° C. during the cooking process. This requires large volumes of steam, since not only is the correct chip temperature to be achieved with the aid of the steam, not only is the bound air to be expelled by the steam, but also the bound chip moisture is to be heated.
In certain older conventional systems, atmospheric chip bins have been used in which the chips are pre-heated with steam in order to expel the air. Very large volumes of withdrawn air are obtained from these systems, which volumes are contaminated with turpentine, methanol and other explosive gases that have been expelled from the chips, the latter being denoted by the term “NCGs” (where “NCG” is an abbreviation of “non-condensable gas”). If steam is used that has been obtained from the release of pressure of black liquor, this steam contains also large quantities of sulphides, known as TRS gases (where “TRS” is an abbreviation of “total reduced sulphur”), which are very malodorous. These TRS gases contain, among other compounds, hydrogen sulphide (H 2 S), methyl mercaptan (CH 3 SH), dimethyl sulphide (CH 3 SCH 3 ), dimethyl disulphide (CH 3 SSCH 3 ), and other strongly malodorous gases. Hydrogen sulphide and methyl mercaptan, which principally come from the steaming of black liquor, have boiling points of −60° C. and +6° C., respectively, and it will thus be difficult to condense these compounds out from the gases.
Pure steam is often used for heating in the chip bin in order to minimise the release of TRS gases, and black liquor steam is used first in the subsequent steam-treatment step that follows the chip bin. Even if black liquor steam is used only in a subsequent steam-treatment step, it is still possible that these TRS gases leak up into the chip bin or are deliberately allowed to escape up into this chip bin during, for example, interruptions in operation.
Systems are revealed in U.S. Pat. No. 6,375,795 and in U.S. Pat. No. 6,284,095 in which it is attempted to disperse TRS gases from a pressure isolation device arranged between a chip bin and a steam-treatment vessel, where the TRS gases are withdrawn from the pressure isolation device and reintroduced at a position that lies downstream in the input sequence, at the outlet end of the steam-treatment vessel. The system has a chip bin arranged upstream, and a ventilation system is arranged at this bin in order to deal with weak gases. The system also provides possibilities for the dispersion of the TRS gases on certain occasions, either at a standpipe into the atmosphere, or to lead these TRS gases to the superior chip bin. Both of these alternatives involve the risk that TRS gases leak into the surroundings and create odour problems. The dispersal of pressurised TRS gases from the pressure isolation device, however, is combined with problems, since chips and fragments of chips can readily become stuck in the system, resulting is malodorous TRS gases being released up into the chip bin.
The prior art technology has identified the problem that it is desired to minimise leakage of harmful and toxic gases that arise during the steam pre-treatment with hot steam. It is normal to allow removal of weak gases from the chip bin to a destruction system, and to allow a further dispersal of gases from the steam pre-treatment vessel, the latter often being considered to be strong gases. It is attempted to maintain the concentration of the weak gases at well under 4% by volume, and the concentration of the strong gases at well over 40% by volume.
In the previously known chip bins in which steam is blown into the bed of chips, large volumes of weak gases are formed, and either pure steam or special systems that manage to deal with these weak gases are required. It is a property of weak gases that they very readily obtain a very explosive composition. As long as the concentration of NCGs lies lower than approximately 4% by volume or well over 40% by volume, there is no risk of explosion. For this reason, weak gas systems that maintain the concentration below under 4% by volume, typically below 1-2% by volume, or strong gas systems that maintain the concentration well over 40% by volume are used. It is thus ensured that the concentration in weak gas systems is held well below 4% by volume, and this entails the transport of large volumes of air: as soon as the volume of NCGs is set to increase, an equivalent increase in the fraction of air must be carried out in order to maintain the concentration below the critical limit.
If, for example, 1 kg/min of NCGs are steamed off in a chip bin, the air amount must lie around approximately 50 kg/min in order to maintain the concentration at approximately 2% by volume. If an increase in the NCGs to 2 or 3 kg/min takes place, as may occur in certain interruptions in the process, it is necessary temporarily to increase the amount of air to 100 or 150 kg/min. This results in the system being normally dimensioned such that it can deal with the normal flow, and that excess gases are vented directly into the atmosphere through the vent pipe when interruptions in operation occur.
Another solution to minimise the volumes of weak gases is to control the flow of chips through the chip bin such that a stable plug flow through the chip bin is obtained, and the supply of steam to the chip bin is in this case controlled such that only the chips in the lower part of the bin are heated. This technique is known as “cold-top” control and is applied in systems that are marketed by Kvaerner Pulping AB under the name DUALSTEAM™ bin.
A number of very expensive solutions have been developed in order to reduce the explosiveness and toxicity of the weak gases. Different systems are revealed in, for example, WO 96/32531 and in U.S. Pat. No. 6,176,971, in which cooking fluid withdrawn from the digester generates pure steam from ordinary water. The use of totally pure steam for the steam pre-treatment of the chips reduces the TRS content in the weak gases, since the steam used is totally free from any TRS content.
These systems, however, inevitably give rise to energy losses and additional expensive process equipment.
The principal aim of the invention is to obtain a chip bin or similar vessel for the steam pre-treatment of chips in which the risks of leakage of weak gases are minimised and that is not associated with the disadvantages of the prior art.
A second aim is to obtain a safe system with simple regulation in which it is ensured that the weak gases that are drawn from the chip bin always maintain a concentration of TRS gases (or of NCGs) that lies well below the level at which the mixture of gases becomes explosive.
The system uses a simple temperature regulation, in which, with increasing temperature of the weak gases, a gradually increasing amount of dilution air is added at the ventilation channel in which the weak gases are transferred to the destruction system or the DNCG system (where “DNCG” is an abbreviation for “diluted NCG”).
A further aim is to use a condensation arrangement in the weak gas system such that the gas volumes can be reduced early in the weak gas system, in which way an effective reduction in the volumes of weak gases can be achieved if large flows of steam are suddenly emitted from the top of the chip bin, and to avoid in this manner the customary venting to atmosphere. Current weak gas system are normally dimensioned such that they are able to deal with a nominally interruption-free flow of exhaust gases, and not to be able to deal with the increased volume of NCGs that may temporarily arise in the event of an interruption in operation. The volumes of gases obtained during such interruptions of operation are much larger than those that the weak gas system can manage, and the extra gas volume has, in general, been emitted to the surrounding air, through a dispersal standpipe of the roof of the mill, which has had as a consequence that the pulp mill has been compelled to emit malodorous gases.
A further aim is that the safety system is preferably used during what is known as “cold-top”-regulation of the heating of the chips, in which the chips are heated in such a manner that a temperature gradient is formed in the volume of chips, where the chips at the top of the chip bin maintain a temperature of approximately 40° C., and successively higher temperatures down towards the bottom of the chip bin are established with an advantageous temperature of approximately 90-110° C. established at the bottom of the chip bin. This system ensures that the volumes of gases that are expelled from the chips in the chip bin are very low, and the load on the weak gas system will be minimal during continuous routine operation. The system does, however, possess the property that NCGs tend to accumulate in a condensation layer in the chip bin, and in the event of steam break-through, when the chips reach a temperature of well over 40° C. at the top of the chip bin as a result of interruptions in the system, large amounts of NCGs are expelled from the bed of chips, which amounts must be dealt with by the weak gas system.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows schematically a system for the steam pre-treatment of chips according to the invention;
FIG. 2 shows a variant of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows schematically a suitable vessel, shown here as a chip bin 1 , into which chopped chips are fed in to the top of the chip bin through a flow feed or input feed 34 . A upper level of chips is normally established at the top of the chip bin such that this level is established between a lowest and a highest level. Gas phase is established in the vessel between this upper chip level and the top of the vessel.
The vessel may also be a vessel in which impregnation of the chips takes place in the lower part of the vessel, according to, for example, a technology sold by Kvaerner Pulping AB under the name IMPBIN™.
Steam ST is added at the lower part of the chip bin well below the established upper chip level through suitable addition nozzles, where the amount of steam is regulated by detecting the temperature in the column of chips. A measurement probe 32 is used in the drawing, which probe establishes a mean value along a long stretch of the measurement probe, and its output signal is led to a control unit 31 that regulates the valves 33 on the steam supply line.
The steam may preferably be pure steam totally free of any NCG and TRS content, or it may be black liquor steam, which contains TRS.
The chips are pre-treated in the embodiment shown according to the “cold-top” concept, in which it is attempted to establish a temperature gradient in the chip bin, shown schematically, where different levels of temperature: 80° C., 60° C., and 40° C., are established upwards in the column of chips. In the ideal case, the chips at the upper surface of the column of chips are to maintain a temperature in the interval 20-40° C.
A ventilation channel 2 A- 2 B for venting of the weak gases that are formed is arranged at the upper part of the vessel and connected to a weak gas system NCG in which these weak gases are evacuated with a suitable fan 6 (or pump).
In the embodiment shown in FIG. 1 , also a temperature sensor 3 installed for the weak gas system is used to detect the temperature in the upper part of the vessel. The temperature sensor here is located in the ventilation channel 2 A close to the upper part of the vessel, typically less than 1 metre from the vessel 1 , but it is possible to use also a temperature sensor that is located within the top of the vessel, or to use the temperature sensor 32 .
The ventilation channel 2 A- 2 B is according to the invention connected to at least one diluting air input line 5 a , 5 b , 5 c , 5 d , that is connected to the surrounding atmosphere ATM at one end and connected at its other end to the ventilation channel 2 B through a valve 4 a , 4 b , 4 c and 4 d.
A control unit CPU is connected to the temperature sensor 3 and to the relevant valves 4 a , 4 b , 4 c and 4 d in the dilution lines 5 a , 5 b , 5 c and 5 d , which control unit CPU opens and closes the relevant valves when the temperature exceeds pre-determined threshold values that are set and stored in the control unit.
Four dilution lines 5 a - 5 d are shown in the drawing, but it is preferable that at least two dilution lines 5 a , 5 b are connected to the ventilation channel 2 B, with first 4 a and second 4 b valves in the associated dilution lines 5 a and 5 b , and where the control unit opens the relevant valve when a first or second threshold value is exceeded. The first threshold value is a pre-determined first temperature T level1 and the second threshold value is a pre-determined second temperature T level2 , where T level1 <T level2 .
The system can be extended with a suitable number of dilution lines where a third dilution line 5 c with a third valve 4 c is connected to the ventilation channel 2 B, and where the control unit opens the third valve 4 c when a third threshold value T level3 , where T level1 <T level2 <T level3 , is exceeded, etc.
In order to limit the volumes of weak gases in the subsequent handling, the system is provided with a suitable condensation arrangement 10 connected to the ventilation channel 2 A, 2 B between the vessel 1 and the connections of the ventilation lines to the ventilation channel 2 B. A condensate is withdrawn from the condensation arrangement in a condensation line with a pump 15 . This condensation arrangement can comprise condensation technology in which cold process fluid LIQ (typically condensate from the pulp mill) or cold water is sprayed into the gas flow through a suitable distribution nozzle 11 . The amount of added cold fluid for the condensation is controlled, by use of the valve 12 , depending on the temperature detected in the gas outlet from the condensation arrangement. Typically, it is attempted to maintain this temperature at the outlet at approximately 40-45° C., and for this reason essentially all water vapour can be separated, and a certain amount of other readily condensable gases that are malodorous (although not the more malodorous TRS gases to any major extent). The condensation technology means that the complete channel system that lies downstream of the condensation arrangement can adapt to much lower volumes of gas, something that is important from an economic point of view since these weak gases are often led along large distances either to a soda boiler or to another destruction plant at a considerable distance from the chip bin.
The condensation arrangement is important in order to remove steam from the air flow that is withdrawn, such that there is no risk that steam condenses in lines or vessels that are located downstream, something that can involve the flow of gases achieving a raised concentration of NCGs in the remaining gas flow, i.e. that the gas concentration comes to lie within the interval where a risk for explosion arises: 4-40% by volume.
The condensation arrangement in the drawing has a pressure lock 13 for condensate in its outlet, appropriately a simple water lock, from which condensate is led to a buffer tank 14 , from which the malodorous condensate can be pumped by the pump 15 onwards to destruction, the pump typically being controlled by the level in the buffer tank 14 .
The valves 4 a - 4 d on the air dilution lines 5 a - 5 d are preferably valves of a binary type that switch from a fully open condition to a fully closed condition, where the fully open condition is selected if the control signal from the control unit disappears, to give a “fail-safe mode”.
FIG. 2 shows a variant of the system according to FIG. 1 , where the valve in the dilution line 5 a is a proportional valve, instead, whose degree of opening can be set proportionally between a fully open condition and a fully closed condition, proportional to the control signal from the control unit, where the fully open condition is selected if the control signal from the control unit disappears. It is also suggested in this drawing that it is possible to have a pressurising fan 40 in the dilution lines in order to feed in dilution air. The fan 40 must, in this case, have a capacity that lies well under the suction capacity of the fan 6 in order to avoid the risk of pressurising the chip bin.
The system according to FIG. 1 functions in the following manner. When the air withdrawn from the chip bin maintains a temperature of up to 60° C., measured by the sensor 3 , this air maintains a maximum of 20% by volume of water vapour, and a concentration of approximately 2% by volume of NCGs is maintained in the remaining 80% by volume, i.e. the fraction of NCGs in the total volume (including steam) is approximately 1.6% by volume. Even if the water vapour were to be condensed out, the concentration of NCGs would not exceed 2% by volume during normal interruption-free operation, and this is well under the critical level of 4% by volume. This condition is the one that is normally established during “cold-top” regulation of the steam pre-treatment, and there is normally no risk of explosion.
However, in order to ensure a low concentration in the weak gases, the system opens a first valve 4 a when the temperature lies within the interval 40-60° C. Operational conditions may arise in which NCGs, or even TRS gases, force their way up through the chip bin, and it is for this reason desired to establish a safety margin to prevent the establishment of a critical concentration.
When the temperature reaches 80° C., the air that has been withdrawn from the chip bin (the undiluted air) maintains a maximum of approximately 48% by volume water vapour. This means that the fraction or concentration of NCGs in the remaining volume of gas, excluding the water vapour, increases from 2% by volume to just over 3% by volume, on the condition that the total fraction of NCGs is constant. However, since more NCGs are expelled from the chips by through-ventilation of steam, it has proved to be the case that the fraction of NCGs in the volume of gas, excluding the water vapour, lies rather close to the critical level of 4% by volume.
In order to prevent this critical level from being reached at a temperature of up to 80° C., the system opens a second valve 4 b when the temperature reaches 60° C., such that the critical concentration cannot be established in the temperature interval 60-80° C.
When the temperature reaches 95° C., the air that is withdrawn from the chip bin, if no diluting air has been added, contains a maximum of approximately 85% by volume water vapour. This means that the fraction or concentration of NCGs in the remaining volume of gas, excluding water vapour, increases from 2% by volume to just over 10% by volume, on the condition that the total fraction of NCGs is constant. In order to prevent this level being reached at a temperature of up to 95° C., the system opens also a third valve 4 c when the temperature reaches 80° C., such that the critical concentration cannot be established in the temperature interval 80-95° C.
If the temperature exceeds 95° C. and reaches 100° C., the air that is withdrawn from the chip bin, if no diluting air has been added, contains a maximum of approximately 100% by volume water vapour (at 100° C. and at atmospheric pressure). In order to prevent the critical concentration from being reached at a temperature of over 95° C., the system opens also a fourth valve 4 d when the temperature exceeds 95° C., such that the critical concentration cannot be established in the temperature interval 95-100° C.
The activation of the various valves by the system can be seen in the following table:
TC1 Valve 4a Valve 4b Valve 4c Valve 4d TC2 40° C. open closed closed closed 40° C. 60° C. open open closed closed 45° C. 80° C. open open open closed 45° C. 95° C. open open open open 45° C.
where TC1 is the temperature measured by sensor 3 , and where TC2 is the temperature that the condensation arrangement 11 uses to control the cooling flow.
A calibrated flow of dilution air is established at each stepwise opening of the valves 4 a - 4 d , appropriately through a calibrated throttle, or through the design of the relevant valve, such that given falls in pressure and flow are established that ensure a sufficient supply of dilution air, such that the concentration is held at a low value. The negative pressure in the ventilation channel 2 B is maintained at a given level by the fan 6 in a conventional manner (pressure control).
This example of temperature-controlled activation of the valves enables it to be realised that the system as an alternative or as a complement, may have direct measurement of the moisture content of the gases. Moisture sensors, however, are more liable to disturbance and are not in any way as stable as a simple temperature sensor. The concept of “gas sensor” in this application applies to both a temperature sensor and a moisture sensor.
The system and the method can be supplemented also with measurement of the level of chips in the vessel, detected by means of a level sensor 40 , also which signal from the level is led to the control unit CPU. In addition to the controlled regulation of the added dilution air as a function of moisture level or temperature, the amount of dilution air that is added can be regulated also by the current level of chips. It is appropriate that this regulation starts to apply when the level falls below a certain pre-determined minimum level, where the risk of penetration of, primarily, TRS gases can arise if the volume of chips becomes too low. As the chip level successively falls under this minimum level, successively increasing amounts of dilution air can be added in a similar manner as that which occurs with an increasing fraction of moisture or an increasing temperature in the gas phase of the vessel.
For example, a valve can be opened in the system if the level lies below this minimum level, and a further valve can be opened if the level subsequently falls even further, for example to 90% of the minimum level, etc.
If both the level of chips and the level of moisture or temperature indicate that addition of dilution air is necessary, the current level of added dilution air may be larger than that that would be added if only one of these parameters controlled the degree of opening of the valves.
The system displayed in FIG. 2 can be regulated in a similar manner, where the valve 4 a′ is used as a proportional valve with a fall in pressure that can be regulated, where the degree of opening of the valve provides a proportional flow of dilution air, either through the dilution air being supplied at an amount that is proportional to the current temperatures or in stepwise addition corresponding to the functionality of the system shown in FIG. 1 .
The invention can be varied in several ways within the scope of the attached patent claims. For example, the valves in the embodiment shown in FIG. 1 can be opened at different temperature levels, and there may be a greater or lesser number than the four that are shown in this embodiment.
The first valve 4 a can be also a fixed throttle that is held always open, in the same way as the valve 30 or the valve 35 , and where only valves 4 b , 4 c and 4 d are regulated by the control unit between their closed and open conditions depending on the current temperature.
The condensation arrangement may be also of another type than one that functions through directly condensing fluid; one with, for example, indirect cooling in a heat exchanger or with electrical cooling elements (Peltier elements, etc).
One alternative is that the valves 4 a - 4 d are instead proportional valves whose degree of opening can be proportionally set between a fully open position and a fully closed position, the proportionality being to the control signal from the control unit, where the fully open condition is selected in the event that the control signal from the control unit disappears.
The system and the method can, naturally, be used also in steam pre-treatment systems using what is known as “hot-top” regulation, in which the steam is added in such an amount that steam continuously blows through the complete volume of chips in the vessel.
The feed arrangement of the vessel may be of different types, such as a simple chip feed with rotating bins (shown schematically in the drawing), or various feed screws that are often placed into a horizontal housing, with or without reverse valve means in the inlet.
While the present invention has been described in accordance with preferred compositions and embodiments, it is to be understood that certain substitutions and alterations may be made thereto without departing from the spirit and scope of the following claims. | The vessel in which the chips are pre-treated with steam (ST) is provided with a ventilation channel at the top of the vessel for the leading away of weak gases to a weak gas system (NCG). A simple safety system has been installed with the aim of guaranteeing that these weak gases do not reach a level of concentration at which these weak gases become explosive. The safety system has a control unit (CPU) that detects a process parameter that is indicative of the fraction of moisture in the weak gases and opens dilution lines that supply air for the dilution of the weak gases in the ventilation channel. It is appropriate that the dilution take place in stages, where the dilution lines are opened in stages with successively increasing temperature of the weak gases. | 3 |
[0001] This application hereby incorporates by reference U.S. Provisional Patent Application No. 61/636,549, filed Apr. 20, 2012, entitled “DISPLAY POWER REDUCTION USING EXTEND NAL UNIT HEADER INFORMATION,” U.S. Provisional Patent Application No. 61/636,543, filed Apr. 20, 2012, entitled “DISPLAY POWER REDUCTION USING EXTEND SEI INFORMATION,” AND U.S. Provisional Patent Application No. 61/636,561, filed Apr. 20, 2012, entitled “PERCEPTUAL LOSSLESS DISPLAY POWER REDUCTION.”
TECHNICAL FIELD
[0002] The present disclosure relates generally to reduction of energy consumption in wireless mobile communication devices and, more specifically, to content-based display adaptation control for video content displayed on a wireless mobile communication device.
BACKGROUND
[0003] In recent years, display resolution on mobile devices has advanced significantly, to where 720p or even higher super liquid crystal display (LCD) or OLED organic light emitting diode (OLED) displays are or soon will be mainstream for smart phones and tablets. However, such high display resolution requires much more energy for rendering, especially for video where high frequency frame buffering and display panel refresh are indispensable.
[0004] For LCD displays, power consumption is a monotonic function of the backlighting brightness level; for OLED displays, power consumption is controlled by the supply voltage as well as the display content itself. While a brightness control is already implemented on some mobile devices, those controls typically must be adjusted prior to issuing a new job—that is, before starting playback of a video. For example, brightness may be set at 100%, 50%, or even 25% prior to watching a video, but cannot be changed dynamically without interrupting playback of the video. In addition, since power consumption is determined by the supply voltage and input image for OLED displays, current implementations do not provide a mechanism for adapting the voltage.
[0005] There is, therefore, a need in the art to improve mobile device displays by allowing either LCD display backlighting brightness or OLED supply voltage to be adapted according to the content being displayed, saving significant display energy.
SUMMARY
[0006] Segments for a video are transmitted in payload units with a supplemental enhancement information (SEI) message within which is embedded display adaptation information that may be employed to control display brightness and thereby reduce power consumption during display of the respective segment. The display adaptation information includes at least a maximum pixel brightness that may be used to scale pixel brightness to maximum and correspondingly reduce backlighting for liquid crystal displays, or to adjust the supply voltage for OLED displays. The display adaptation information may optionally include a minimum pixel brightness, a pixel histogram step size, and an indicator of scaling method.
[0007] Before undertaking the DETAILED DESCRIPTION below, it may be advantageous to set forth definitions of certain words and phrases used throughout this patent document: the terms “include” and “comprise,” as well as derivatives thereof, mean inclusion without limitation; the term “or,” is inclusive, meaning and/or; the phrases “associated with” and “associated therewith,” as well as derivatives thereof, may mean to include, be included within, interconnect with, contain, be contained within, connect to or with, couple to or with, be communicable with, cooperate with, interleave, juxtapose, be proximate to, be bound to or with, have, have a property of, or the like; and the term “controller” means any device, system or part thereof that controls at least one operation, where such a device, system or part may be implemented in hardware that is programmable by firmware or software. It should be noted that the functionality associated with any particular controller may be centralized or distributed, whether locally or remotely. Definitions for certain words and phrases are provided throughout this patent document, those of ordinary skill in the art should understand that in many, if not most instances, such definitions apply to prior, as well as future uses of such defined words and phrases.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] For a more complete understanding of the present disclosure and its advantages, reference is now made to the following description taken in conjunction with the accompanying drawings, in which like reference numerals represent like parts:
[0009] FIG. 1 is a high level diagram illustrating a network within which devices may implement dynamic, content-based display power reduction according to one or more embodiments of the present disclosure;
[0010] FIG. 1A is a front view of wireless device from the network of FIG. 1 within which dynamic, content-based display adaptation and corresponding power reduction may be implemented according to one embodiment of the present disclosure;
[0011] FIG. 1B is a high level block diagram of the functional components of the wireless device illustrated in FIG. 1A ;
[0012] FIGS. 2A and 2B illustrate display adaptation preserving brightness using display adaptation information embedded within SEI messages for dynamic, content-based display adaptation and corresponding power reduction according to one embodiment of the present disclosure;
[0013] FIGS. 3A and 3B illustrate SEI message insertion within a video data bitstream for dynamic, content-based display adaptation and corresponding power reduction according to one embodiment of the present disclosure;
[0014] FIG. 4 is a high level flow diagram for a process of encoding video using SEI message insertion for dynamic, content-based display adaptation and corresponding power reduction according to one embodiment of the present disclosure; and
[0015] FIG. 5 is a high level flow diagram for a process of video decoding and display based on SEI messages inserted for dynamic, content-based display adaptation and corresponding power reduction according to one embodiment of the present disclosure.
DETAILED DESCRIPTION
[0016] FIGS. 1 through 5 , discussed below, and the various embodiments used to describe the principles of the present disclosure in this patent document are by way of illustration only and should not be construed in any way to limit the scope of the disclosure. Those skilled in the art will understand that the principles of the present disclosure may be implemented in any suitably arranged wireless communication system.
[0017] The metadata used for display adaptation can be embedded into the video stream as the supplemental enhancement information (SEI) message.
[0018] In the present disclosure, display adaptation is embedded within the video content information using a Supplemental Enhancement Information (SEI) message, which is then parsed at the decoder to help with display power reduction. For LCD displays, the display brightness is adjusted, while for OLED displays, the display supply voltage is adapted. Elements in this extended SEI message can be derived at the encoder during video encoding.
[0019] Display adaptation is defined by enabling an SEI message (i.e., display_adaptation( )) that can be inserted into stream frame by frame, or group of pictures (GOP) by GOP, scene by scene, or even time interval by time interval, depending on the underlying applications and the hardware capability. By comparison with a frame-level solution, GOP, a scene or time interval based approach requires less overhead for message insertion. For processors that do not support high-frequency display adaptation, e.g., every 33 millisecond (ms) for a 30 Hertz (Hz) video, GOP, scene or time interval based schemes are better than a frame based solution. Nonetheless, the concept is explained herein primarily using a frame level solution.
[0020] FIG. 1 is a high level diagram illustrating a network within which devices may implement dynamic, content-based display adaptation and corresponding power reduction according to one or more embodiments of the present disclosure. The network 100 includes a content encoder data processing system 101 including an encoder controller configured to encode video content in accordance existing procedures, but with display adaptation information embedded within NALU header(s) as described in further detail below. The content encoder 101 is communicably coupled to (or alternatively integrated with) a content server data processing system 102 , which delivers video content to user devices. The content server 102 is coupled by a communications network, such as the Internet 103 and a wireless communications system including a base station (BS) 104 , for delivery of the video content to a user device 105 , which may also be referred to as user equipment (UE) or a mobile station (MS). As noted above, the user device 105 may be a “smart” phone or tablet device capable of functions other than wireless voice communications, including at least playing video content. Alternatively, the user device 105 may be a laptop computer or other wireless device having an LCD or OLED display and benefitting from dynamic, content-based display power reduction during playback of videos, such as any device that is primarily battery-powered during at least periods of typical operation.
[0021] FIG. 1A is a front view of wireless device from the network of FIG. 1 within which dynamic, content-based display adaptation and corresponding power reduction may be implemented according to one embodiment of the present disclosure, and FIG. 1B is a high level block diagram of the functional components of that wireless device. User device 105 is a mobile phone and includes a backlit LCD (which includes the optional luminance source depicted in FIG. 1B ) or OLED display 106 . A processor 107 coupled to the display 106 controls content displayed on the display. The processor 107 and other components within the user device 105 are powered by a battery (not shown), which may be recharged by an external power source (also not shown), or alternatively may be powered by the external power source. A memory 108 coupled to the processor 107 may store or buffer video content for playback by the processor 107 and display on the display 106 , and may also store a video player application (or “app”) 109 for performing such video playback. The video content being played may be received, either contemporaneously (e.g., overlapping in time) with the playback of the video content or prior to the playback, via transceiver 110 connected to antenna 111 . As described above, the video content may be received in wireless communications from a base station 104 . In the exemplary embodiment, the video content received by mobile device 105 for playback therein and display on display 106 includes display adaptation information embedded within SEI message(s). The display adaptation information is employed by processor 107 to set display controls 112 for the optional luminance source and display 106 .
[0022] In International Telecommunication Union (ITU) Telecommunication Standardization Section (ITU-T) Video Coding Experts Group (VCEG) standard H.264 Advanced Video Coding (AVC, also referred to as Motion Picture Experts Group 4 Part 10 or “MPEG-4 Part 10”) and its extensions, each SEI message(s) are inserted in the payload bitstream as described in further detail below. A new SEI message with payloadType=47 as shown in TABLE I below. (The choice of payloadType=47 is merely for the purposes of illustration in this example; any previously unspecified payloadType value could be used instead). Each time the SEI message is encountered in the bitstream, the decoder parses that SEI message and enables the frame-level, GOP-level, scene-level or time interval-level display adaptation as defined in TABLE II.
[0023] The current definition of the SEI message is modified by extension to support embedding of display adaptation related information. TABLE I shows the extended SEI message for H.264/AVC and its extensions (modifications shown in italics in TABLE I):
[0000] TABLE I De- scrip- C tor sei_payload( payloadType, payloadSize ) { if( payloadType = = 0 ) buffering_period( payloadSize ) 5 else if( payloadType = = 1 ) pic_timing( payloadSize ) 5 else if( payloadType = = 2 ) pan_scan_rect( payloadSize ) 5 else if( payloadType = = 3 ) filler_payload( payloadSize ) 5 else if( payloadType = = 4 ) user_data_registered_itu_t_t35( 5 payloadSize ) else if( payloadType = = 5 ) user_data_unregistered( payloadSize ) 5 else if( payloadType = = 6 ) recovery_point( payloadSize ) 5 else if( payloadType = = 7 ) dec_ref_pic_marking_repetition( 5 payloadSize ) else if( payloadType = = 8 ) spare_pic( payloadSize ) 5 else if( payloadType = = 9 ) scene_info( payloadSize ) 5 else if( payloadType = = 10 ) sub_seq_info( payloadSize ) 5 else if( payloadType = = 11 ) sub_seq_layer_characteristics( 5 payloadSize ) else if( payloadType = = 12 ) sub_seq_characteristics( payloadSize ) 5 else if( payloadType = = 13 ) full_frame_freeze( payloadSize ) 5 else if( payloadType = = 14 ) full_frame_freeze_release( payloadSize ) 5 else if( payloadType = = 15 ) full_frame_snapshot( payloadSize ) 5 else if( payloadType = = 16 ) progressive_refinement_segment_start( 5 payloadSize ) else if( payloadType = = 17 ) progressive_refinement_segment_end( 5 payloadSize ) else if( payloadType = = 18 ) motion_constrained_slice_group_set( 5 payloadSize ) else if( payloadType = = 19 ) film grain characteristics( payloadSize ) 5 else if( payloadType = = 20 ) deblocking_filter_display_preference( 5 payloadSize ) else if( payloadType = = 21 ) stereo_video_info( payloadSize ) 5 else if( payloadType = = 22 ) post_filter_hint( payloadSize ) 5 else if( payloadType = = 23 ) tone_mapping_info( payloadSize ) 5 else if( payloadType = = 24 ) scalability_info( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 25 ) sub_pic_scalable_layer( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 26 ) non_required_layer_rep( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 27 ) priority_layer_info( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 28 ) layers_not_present( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 29 ) layer_dependency_change( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 30 ) scalable_nesting( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 31 ) base_layer_temporal_hrd( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 32 ) quality_layer_integrity_check( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 33 ) redundant_pic_property( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 34 ) tl0_dep_rep_index( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 35 ) tl_switching_point( payloadSize ) /* 5 specified in Annex G */ else if( payloadType = = 36 ) parallel_decoding_info( payloadSize ) /* 5 specified in Annex H */ else if( payloadType = = 37 ) mvc_scalable_nesting( payloadSize ) /* 5 specified in Annex H */ else if( payloadType = = 38 ) view_scalability_info( payloadSize ) /* 5 specified in Annex H */ else if( payloadType = = 39 ) multiview_scene_info( payloadSize ) /* 5 specified in Annex H */ else if( payloadType = = 40 ) multiview_acquisition_info( payloadSize ) /* 5 specified in Annex H */ else if( payloadType = = 41 ) non_required_view_component( payloadSize ) /* 5 specified in Annex H */ else if( payloadType = = 42 ) view_dependency_change( payloadSize ) /* 5 specified in Annex H */ else if( payloadType = = 43 ) operation_points_not_present( payloadSize ) /* 5 specified in Annex H */ else if( payloadType = = 44 ) base_view_temporal_hrd( payloadSize ) /* 5 specified in Annex H */ else if( payloadType = = 45 ) frame_packing_arrangement( payloadSize ) 5 else if ( payloadType = = 47 ) display — adaptation ( payloadSize ) /* 5 specified for display adaptation */ Else reserved_sei_message( payloadSize ) 5 if( !byte_aligned( ) ) { bit_equal_to_one /* equal to 1 */ 5 f(1) while( !byte_aligned( ) ) bit_equal_to_zero /* equal to 0 */ 5 f(1) } }
TABLE II shows the display adaptation SEI message syntax in H.264/AVC (modifications shown in italics in TABLE II):
[0000]
TABLE II
C
Descriptor
display — adaptation ( payloadSize ) {
display
—
scaling
—
method
5
f(4)
distortion
—
percentage
5
f(7)
if ( display=scaling — method ==
BRIGHTNESS — PRESERVED ) {
max
—
pixel
—
value
5
f(8)
} else if ( display=scaling — method ==
CONTRAST — PRESERVED ) {
max
—
pixel
—
value
5
f(8)
min
—
pixel
—
value
5
f(8)
} else if ( display=scaling — method ==
PERCEPTUAL — LOSSLESS ) {
pixel
—
hist
—
stepsize
5
f(8)
max
—
pixel
—
value
5
f(8)
min
—
pixel
—
value
5
f(8)
}
[0024] As evident from TABLE II, three different types of display adaptation (“display_scaling_method”) are contemplated: display adaptation preserving brightness of the pixels (“BRIGHTNESS_PRESERVED”); display adaptation preserving contrast (“CONTRAST_PRESERVED”); and perceptually lossless display adaptation (“PERCEPTUAL_LOSSLESS”). Display adaptation preserving brightness takes a single value as a parameter: the maximum pixel brightness value (“max_pixel_value”) within a histogram of pixel brightness values for a reconstructed frame encoded with the respective NALU header. Display adaptation preserving contrast rightness takes as parameter both the maximum pixel brightness value and the minimum pixel brightness value (“min_pixel_value”) within the histogram of pixel brightness values for the reconstructed frame. Perceptually lossless display adaptation, preserving both brightness and contrast, takes three parameters: the maximum and minimum pixel brightness values (“max_pixel_value”) within the histogram and the step size (“pixel_hist_stepsize”) of pixel brightness values used in generating the histogram.
[0025] In ITU VCEG and International Standards Organization (ISO)/International Electro-technical Commission (IEC) Motion Pictures Expert Group (MPEG) Joint Collaborative Team on Video Coding (JCT-VC) standard H.265 High Efficiency Video Coding (HVEC), both SEI and video usability information (VUI) metadata are permitted. Accordingly, those skilled in the art will understand how the above-described techniques may be readily adapted for use with HVEC streams.
[0026] FIGS. 2A and 2B illustrate display adaptation preserving brightness using display adaptation information embedded within SEI messages for dynamic, content-based display adaptation and corresponding power reduction according to one embodiment of the present disclosure. Before decoding every frame, the SEI message is parsed to extract the maximum pixel value used to scale up a current reconstructed frame by (255/max_pixel_value). Let p(i) indicate the original brightness of an i-th pixel value (in raster scan order) in a histogram of pixel brightness for a reconstructed frame as illustrated in FIG. 2A , then the scaled pixel brightness pnew(i) for that pixel in the scaled frame histogram illustrated in FIG. 2B is (for 8-bit pixel brightness values):
[0000] p new( i )= p ( i )* Y, (1)
[0000] where Y=(255/max_pixel_value) and max_pixel_value is the parameter specified in the SEI message as described above. As apparent by comparison on FIGS. 2A and 2B , the histogram is shifted by linear scaling.
[0027] Meanwhile, by increasing the pixel brightness, a lower brightness backlighting (for LCD displays) or a lower supply voltage (for OLED displays) may be used for a net reduction in energy. That is, for LCD displays the scaled pixel brightness is employed together with a reduced backlighting brightness. The scaled value may be set at the ratio (max_pixel_value/255)*100%. That is, the scaled backlighting brightness bnew is:
[0000] b new= b/Y, (2)
[0000] where b is the original backlighting brightness, and the scaled supply voltage is:
[0000] V new= V/Y, (3)
[0000] where V is the original supply voltage. To further reduce energy, the maximum pixel value may be further altered to allow some pixel distortion (i.e., saturated after scaling), but without any perceptual difference, i.e.,
[0000] max_pixel_value=(1−distortion_percentage)*max_pixel_value. (4)
[0000] The parameter min_pixel_value may be similarly employed, together with max_pixel_value, for adaptation when scaling in CONTRAST_PRESERVED mode. The range between maximum and minimum pixel brightness may both be adjusted to maintain contrast. Likewise, the parameters min_pixel_value and pixel_hist_stepsize, together with max_pixel_value, for adaptation when scaling in CONTRAST_PRESERVED mode. The range between maximum and minimum pixel brightness and the distribution of pixel brightness may all be adjusted. While linear scaling of backlight brightness and supply voltage are assumed above, in actual implementations the scaling could be non-linear. Either linear or non-linear adjustment may be implemented through a look-up table, which may be constructed by measuring the display power at different levels of the backlight brightness or supply voltage.
[0028] FIGS. 3A and 3B illustrate SEI message insertion within a video data bitstream for dynamic, content-based display adaptation and corresponding power reduction according to one embodiment of the present disclosure. FIG. 3A illustrates frame-based SEI message insertion, while FIG. 3B illustrates GOP-based SEI message insertion. Similar insertion schemes may be employed for scene-based or time interval-based SEI message insertion.
[0029] For LCD displays with separate backlighting of each of the red (R), green (G) and blue (B) color channels, pixel brightness scaling and backlighting brightness reduction as described above may be implemented separately for the pixel and backlighting brightness of each of the RGB colors individually. To the extent that separate supply voltages are employed for red, green and blue LEDs within an OLED display, pixel brightness scaling and supply voltage reduction as described above may be implemented separately for each RGB color. In that manner, different color components may be individually adapted.
[0030] FIG. 4 is a high level flow diagram for a process of encoding video using SEI message insertion for dynamic, content-based display adaptation and corresponding power reduction according to one embodiment of the present disclosure. The process is performed by the encoder controller within encoder 101 . The same process may be employed for encoding video regardless of whether intended for delivery to a device supporting display adaptation, since devices not supporting display adaptation may simply ignore display adaptation information embedded in the SEI messages. The process 400 begins with receiving pixel data for a frame, GOP, scene or time interval segment of the video being encoded (step 401 ).
[0031] The histogram of pixel brightness is determined for the video data of the segment being processed (step 402 ), including determination of at least max_pixel_value, and optionally also min_pixel_value and pixel_hist_stepsize. An SEI message is generated for the segment of video data being processed (step 403 ), with the scaling method and appropriate parameters included. The SEI message is then inserted into the payload stream in association with the corresponding segment data, and the encoded video data is transmitted (step 404 ). If the video encoding is incomplete (step 405 ), another iteration of the process is performed for the pixel data for the next frame, GOP, scene or time interval segment of the video being encoded.
[0032] FIG. 5 is a high level flow diagram for a process of video decoding and display based on SEI messages inserted for dynamic, content-based display adaptation and corresponding power reduction according to one embodiment of the present disclosure. The process is performed by user equipment 105 . The process 500 begins with receiving an SEI message and associated payload for a frame, GOP, scene or time interval segment of the video being decoded (step 501 ). The scaling method and parameter(s) are extracted from the SEI message (step 502 ), and the pixel brightness and the supply voltage is adapted (for an OLED display) or the pixel and backlighting brightness are adapted (for an LCD display) based on the scaling method and parameter(s) (step 503 ). The video content decoded from the payload for the corresponding frame, GOP, scene or time interval segment is displayed with the adapted display settings (step 504 ). If the video decoding is incomplete (step 505 ), another iteration of the process is performed for the next frame, GOP, scene or time interval segment of the video being decoded.
[0033] Display adaptation using an SEI message based on a brightness preserved algorithm is exemplified in the above disclosure. Such an algorithm requires the maximum pixel value to remain the same as in the embedded information. However, the principles disclosed are not limited to only such implementation. In another embodiment, any information derived from the video encoder may be embedded as part of the SEI message to help the display adaptation, such as both minimum and maximum pixel brightness values, or even the histogram distribution.
[0034] The present disclosure will make products, such as smartphones and tablets, much more power efficient while reducing the data cost, thus improving the user experience for mobile streaming applications.
[0035] While each process flow and/or signal sequence depicted in the figures and described above depicts a sequence of steps and/or signals, either in series or in tandem, unless explicitly stated or otherwise self-evident (e.g., a signal cannot be received before being transmitted) no inference should be drawn from that sequence regarding specific order of performance, performance of steps or portions or transmission of signals thereof serially rather than concurrently or in an overlapping manner, or performance the steps or transmission of signals depicted exclusively without the occurrence of intervening or intermediate steps or signals. Moreover, those skilled in the art will recognize that complete processes and signal sequences are not illustrated or described. Instead, for simplicity and clarity, only so much of the respective processes and signal sequences as is unique to the present disclosure or necessary for an understanding of the present disclosure is depicted and described.
[0036] Although the present disclosure has been described with exemplary embodiments, various changes and modifications may be suggested to one skilled in the art. It is intended that the present disclosure encompass such changes and modifications as fall within the scope of the appended claims. | Segments for a video are transmitted in payload units with a supplemental enhancement information (SEI) message within which is embedded display adaptation information that may be employed to control display brightness and thereby reduce power consumption during display of the respective segment. The display adaptation information includes at least a maximum pixel brightness that may be used to scale pixel brightness to maximum and correspondingly reduce backlighting for liquid crystal displays, or to adjust the supply voltage for OLED displays. The display adaptation information may optionally include a minimum pixel brightness, a pixel histogram step size, and an indicator of scaling method. | 6 |
RELATED U.S. APPLICATION DATA
This is a Continuation-in-Part of Ser. No. 08/620,510 filed Mar. 22, 1996 U.S. Pat. No. 5,567,745 which is a Divisional of application Ser. No. 08/392,650, filed Feb. 23, 1995, U.S. Pat. No. 5,521,243, which is a Continuation-in-Part of Ser. No. 08/157,253, Nov. 26, 1993, abandoned.
TECHNICAL FIELD
This invention relates to poly (methyl methacrylate) ("PMMA") containing compositions useful in the manufacture of sheets or slabs, and methods of manufacturing said sheets. These sheets find use in such applications as kitchen countertops. In addition to PMMA, the above compositions comprise at least one crosslinking agent and at least one chain transfer agent. The concentration of said transfer agent is independent on said crosslinking agent. In the present invention, the amount of chain transfer agent is lower than prior art compositions due to the addition of a small amount of plasticizer. The sheets also contain a significant amount of flame retardant minerals such as alumina trihydrate, and typically contain colorants. These colorants are often used for imitation of natural minerals such as onyx, marble, or other solid color or patterned types having no visibly distinguishable particles. The sheets of the present invention can be heat bent, or thermoformed at an angle as sharp as ninety degrees and/or can be vacuum thermoformed into shapes such as sinks and bowls. shapes such as sinks and bowls.
BACKGROUND OF THE INVENTION
Sheets (used herein interchangeably with slabs) of synthetic mineral appearing material are commonly used as kitchen countertops and interior and/or exterior decorative coverings for buildings and the like. Often the design specifications require sheets to be fitted together or otherwise abut another surface at ninety degree angles.
The fabrication process required under these conditions is both time consuming and expensive. Often there are color differences between abutting surfaces, and the point of contact may be esthetically unappealing. The sheets of the present invention can provide a complex finished part by simple thermoforming operations. For example, to form a vanity top having a ninety degree back splash wall and a front end bull nose of 1.0 inch radius. After forming, cooling and trimming, the part can be installed directly without additional fabrication.
U.S. Pat. No. 3,563,939 and Canadian Patent 916,337 disclose the use of alumina trihydrate ("ATH") in poly (methyl methacrylate) ("PMMA") articles. In U.S. Pat. No. 3,847,865 Duggins discloses the construction of synthetic mineral products. Duggins also discloses the use of crosslinking and mold release agents as well as viscosity reducers such as aliphatic acids.
Buser et al, in U.S. Pat. Nos. 4,085,246 and 4,159,301, discloses the phenomena of particle settling rates suitable for making synthetic granite having a polymerizable methyl methacrylate ("MMA") matrix and PMMA dissolved therein. The PMMA is used to adjust the viscosity which in turn controls the settling rates of the larger particles. The patents further disclose the use of chain-transfer agents as accelerators for polymerization (see '301 at col. 8, lines 58-68). The drawback to these patents is that the sheets cannot be thermoformed to the same extent as the sheets of the present invention.
In Gavin et al, U.S. Pat. No. 4,413,089; uniformity of color is disclosed as an objective. Iron oxide pigment of ten microns or less is uniformly distributed in a syrup of MMA/PMMA. The syrup is then cured.
More recently, Minghetti et al, in U.S. Pat. No. 5,521,243, disclose a composition for making thermoformable sheets. A reference point one-half inch sheet is disclosed as having a minimum bending radius of less than three inches. However, that composition is limited in that when the amount of crosslinking agent "x" is 0.5 pph or more, the amount of chain terminator is no less than 0.58x-0.28 pph. In contrast, the composition of the present invention is drawn to a thermoformable sheet wherein the composition is such that the amount of chain terminator is less than 0.58x-0.28 pph. The composition, and thus the sheets manufactured therefrom, have the unexpected feature of performing almost identically to the '243 composition, but at ratios of crosslinker to chain terminator not thought possible in the '243 invention. The difference is attributable to the addition of at least on plasticizer to the instant composition.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a more or less hypothetical illustration of a prior art bending of a one-half inch thick sheet of a contemporary commercial product "Corian" (by DuPont).
FIG. 1B is a similar illustration of the bending of a one-half inch thick sheet of the present invention.
SUMMARY OF THE INVENTION
The present invention is drawn to compositions, thermoformable sheets and thermoformed articles made therefrom. As used herein, by MMA and PMMA is meant a mixture comprising mainly methymethacrylate monomer or polymethylmethacrylate polymer respectively. Other co-monomers or co-polymers such as butyl acrylate, ethyl acrylate may be present in total amounts up to about twenty percent of the polymerizable portion of the composition. The weight average molecular weight of the PMMA is typically 30,000 to 600,000 and having little or no crosslinked polymer chains to maintain its solubility in MMA. The MMA is typically at least 60 to 80% monomer having about 20 to 40% polymer dissolved therein. However, the monomer content can be in excess of 90%.
The sheets can be heat bent at relatively sharp angles and can be thermoformed into shaped articles without losing the uniform appearance and properties of the top surface. The sheets undergo only minor tolerable color changes across the entire finished part, either less than Delta E=2.0 by Cielab, or not easily discernible by the human eye. The thermoforming temperature is low enough to avoid any significant loss of water from the ATH filler during thermoforming, as is often the case with other thermoplastic materials. The sheet will have a Flame Spread Index, by the ASTM E-84 Tunnel Test lower than 75 and a Smoke Index of 350 or less. The sheet will also have a relatively equal impact resistance, as measured by a falling weight method, as measured from both the top and bottom side.
The present invention provides for the stability of the suspension of alumina trihydrate in a syrup of MMA having PMMA dissolved therein as follows (by weight):
(a) Content of PMMA dissolved in MMA: 0-30 wt %, preferably 10-25 wt %;
(b) ATH in the entire composition: 20-60 wt %, preferably 25-40 wt %;
(c) thixotropic agent (preferably fumed silica) in the monomer/syrup fraction: 0.10-3.5 wt %, or as much as necessary to obtain a viscosity of 1,000-10,000 cps (preferably 2,000-5,000 cps) after mixing, as measured by Brookfield Viscometer Model RVTDV-II, Spindle No. 2, 10RPM;
(d) crosslinking agent as wt % of the total monomer content: greater than 0.5 up to about 1.0 wt % for ethylene glycol dimethacrylate, equivalent content for other crosslinking agents, preferably 0.5 to 1.0 wt %;
(e) chain-transfer agent as wt % of total monomer content up to 0.58x-0.28, where x is the amount of crosslinking agent in pph of ethylene glycol dimethacrylate equivalents, and wherein the amount is based on n-dodecyl mercaptan (other agents may vary the exact content slightly to give results equivalent to n-dodecyl mercaptan);
(f) about 0.1 to about 8 phr (parts per hundred of resin composition) of at least one plasticizer.
As shown above, the crosslinking and chain-transfer agents' concentration will vary slightly depending on the exact agents selected. One way to compare the effects of chain transfer agents is to polymerize MMA in the presence of said agents and in the absence of crosslinkers. The MWw and MWn should be similar to that obtained by n-dodecyl mercaptan. In addition to the above, other ingredients such as dyes, pigments, polymerization initiators may be present. These additional ingredients are well known in the art.
The particulates of the present invention will not be visibly distinguishable in the finished product. Most synthetic granites will contain visibly distinguishable particles of various compositions and colors ranging from 150 to 500 microns. That is, passing through a sieve having openings of 500 microns, but retained on a sieve of openings less than 150 microns. However, larger particles are also used in the art. In the present invention, the use of larger particles can inhibit the even distribution of said particles. In the context of the present invention the majority of particles will be less than about 90 microns, and preferably are mostly less than about 60 microns. The particles' composition is preferably ATH, but may be any composition having similar properties, in particular the flame retardant properties of ATH, it should comprise 25 to 50 weight percent.
The solid surface material of the present invention will typically have a somewhat glossy appearance attributable to the acrylic surface. The particulates will not be discernable, as with simulated granite surfaces, and the appearance can be described as substantially fine grained.
Any number of crosslinking agents, di-functional or tri-functional, may be used. Examples include, but are not limited to the following: ethylene glycol dimethacrylate, propylene dimethacrylate, polyethylene-glycol dimethacrylate, divinyl benzene, diallyl phthalate, 1,3-butanediolmethacrylate, 1,4-butane ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethacrylate, triallyl cyanurate, pentaerythritol tetramethacrylate, allylmethacrylate, hydroxypropylmethacrylate and hydroxyethyl methacrylate. Preferably, ethylene glycol dimethacrylate is used. Preferably, the amount of crosslink will be at least 0.01% to about 10%.
Chain terminator or chain-transfer agents include, but are not limited to the following: octyl mercaptan, iso-dodecyl mercaptan, thiurams, dithiocarbarumates, dipentene dimercaptan, 2-mercapts ethanol, allyl mercapts-acetates, ethylene glycol dimercapts-acetate, trimethylolethane trithioglycolate, and pentaerythritol tetrathioglycolate. In the present invention the chain terminator serves to regulate the length of the polymer chains and thus to obtain a suitable polymer matrix for thermoforming. Preferably the amount of chain transfer agent used will be at least 0.01% n-dodecyl mercaptan.
The present invention is not limited to a particular subclass of plasticizer provided said plasticizer is compatible with an MMA/PMMA syrup. Any compatible plasticizer known in the art is contemplated by the present invention. The plasticizers included in the present invention will have the feature of lowering the Heat Distortion Temperature (ASTM D-648) of the base formulation. The plasticizers selected can be either monomeric or polymeric. Monomeric plasticizers include phthalates, epoxies, adipates, azelates, trimellitates, glutarates, and citrate esters. These plasticizers are commonly used due to their low cost and suitability to typical applications. Polymeric plasticizers generally consist of polyesters of dibasic fatty acids and polyfunctional alcohols. Extensive lists of MMA/PMMA compatible plasticizers exist in the art. Also, liquid fire retardants containing P, Cl, Br, and the like are understood in the art to plasticize polymeric compositions, and are therefore incorporated in the context of the present invention. At least one plasticizer is added in an amount of about 0.1 to about 8 phr. Preferably, in the amount of about 2 to about 8 phr.
Conventional thickening agents as well as thixotropic agents are particularly suited to the present invention. They are believed to enhance the inertial tendency of a particle to remain stationary in the matrix suspension. Preferably, fumed silica is used. By fumed silica is meant the product formed by the hydrolysis of silicon tetrachloride vapor in a flame of hydrogen and oxygen, to produce solid particles in the range of about seven to 30 millimicrons. Several commercial types of fumed silica are available. The majority of experimentation for the present invention was conducted with CAB-O-Sil M5, which has a surface area of 200 square meters per gram. However, the present invention is not limited to any one particular type.
The surface of fumed silica is hydrophilic due to an abundance of hydroxyl groups. Absorbed moisture in the silica, or in the other components has a gross effect on the final viscosity of the suspension, and normally lowers the viscosity. The same effect can be achieved with other substances which are more or less capable of developing hydrogen bonding.
If the fumed silica and/or ATH are dried to eliminate the absorbed moisture, the final viscosity of the suspension will be higher. However, drying the ATH above 200° F. may hinder its utility as a flame retardant by depleting its water content.
In our preferred compositions, the amount of fumed silica is selected so that the preferred viscosity is obtained, regardless of variations in the other ingredients.
The preferred method of obtaining a desired viscosity is the following:
(A) Mix all the ingredients (MMA, PMMA, ATH, pigments, other additives, catalysts, chain-transfer agent, crosslinking agent, and plasticizer) of the formulation except the fumed silica and measure the viscosity as indicated below. If necessary, adjust the MMA (monomer) content of the syrup to obtain a viscosity of 800 to 1,500 centipoise.
(B) Repeat step A including an amount of fumed silica and measure the viscosity.
(C) Repeat step B to bring the viscosity to a level between 1,000 and 10,000 centipoise, preferably between 2,000 and 5,000 centipoise.
Hellsund's U.S. Pat. No. 3,371,383 and Opel's U.S. Pat. No. 3,376,371, are incorporated herein by reference in their entireties, as these references represent our preferred procedure for formation of sheet material or a continuous cast operation. While the forming of sheets between two moving continuous steel belts is the preferred procedure, it is important to realize that such machines are necessarily prone to vibration and microadjustments which tend to result in an almost unavoidable jostling of the particulates in the syrup; the concentrations of crosslinker, chain terminator, fumed silica, and PMMA prepolymer factor in stabilizing the ATH and/or other solids contributing to an evenly distributed fine-grained appearance.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIG. 1A, the recommended (DuPont "Corian" Technical Bulletin CTDC-110, October, 1987) minimum bending radius of three inches for a prior art one-half inch thick flat sheet is illustrated as the radius of the bend in the inside curve from vertical extension point A to horizontal extension point B. Applying the simple formula C=πD, the circumference of a hypothetical three-inch circle would be 18.8496 inches, and the quarter circle AB would measure 4.7124 inches. Applying the same formula to the outside curve for a sheet 0.5 inch thick, i.e. using a radius of 3.5, yields a quarter circle of 5.4953, a difference of 16.6% from the inside curvature. Such a distortion will tend to cause a flow of heated ingredients from the compressed inside curve to the expanded outside, and lengthwise toward points A and B from the curved portion. The flow of ingredients has a tendency to distort the visual or decorative pattern; accordingly, the prior art has minimized the disruptions of the material by using a relatively large radius for the curvature, eg. 3 inches.
FIG. 1B illustrates the achievable curvature of a sheet of the present invention, wherein the radius of the curve is one-half inch rather than the three inches of the section of FIG. 1A. In this case, the theoretical circumference of the outside of the curved section CD is 100% greater than that of the inside of the curve. It is readily seen that by enabling such a forming ability, the present invention overcomes a more severe displacement of material in relatively less volume. The relatively more severe displacement of material means a greater potential for distortion of the esthetic pattern, but we avoid or neutralize such distortion and so achieve a continuity of pattern heretofore not achievable under the stress of thermoforming.
A test has been devised to evaluate thermoformability, which is a primary object of the present invention. The test consists of clamping a flat test specimen 4 7/8 square having the desired thickness onto a steel plate in which has been drilled a 3-inch diameter hole; then a polished stainless steel plunger having a one-inch radius is lowered at a rate of five inches per minute regardless of the resistance. The apparatus and sample are heated prior to the test to the desired temperature. As the plunger moves, a load cell generates a signal representing the amount of resistance in pounds, which may be recorded. At the moment the specimen ruptures, the plunger is stopped and the distance it has traveled is measured. Averaging of tests from four specimens of each sample is recommended. This test may be referred to herein as TP-0085.
The invention is illustrated by, but not limited to the following example:
EXAMPLE 1
Sheet samples of 0.500" thickness were prepared as described in Example 3 of U.S. Pat. No. 5,521,243, from a basic formulation consisting of:
______________________________________ % Weight______________________________________ATH (Solem OE-431) 40MMA/PMMA (20%) Syrup 59.75BYK 1142 .25n-dodecyl mercaptan 0.119 phr.sup.( *.sup.)Ethylene glycol dimetharcylate 0.135 phr.sup.( *.sup.)Catalysts As neededpigments As neededother additives As needed______________________________________ .sup.(*.sup.) These amounts correspond to .249% and .282%, respectively, of the MMA present in the formulation.
The samples were poured between two casting plates made of stainless steel, to produce 12"×12" sheets of 0.500" thickness after curing. The curing was obtained by dipping the stainless steel plate assembly into a water tank kept at 180° F. For one hour and then into an air circulating oven, kept at 250° F., for one hour. This was done to evaluate laboratory prepared formulations in which variations of the amount of chain transfer (n-dodecyl mercaptan) and crosslinking agents (ethylene glycol dimethacrylate were made.
Samples 1A, 1B, and 1C were made from the formulation above, with Epoxol 9.5 (epoxidized linseed oil produced by ACS, Inc.) Added as indicated in the table below.
Samples 1G and 1H contained 2 and 4 phr, respectively, of Fyrol RDP, a flame retardant additive containing phosphorus and sold by AKZO. The samples were tested by the thermoforming test method TP-0085, 40 minutes at 340° F. The details of the compositions and the results are listed below:
______________________________________ TP-0085 Inches Lbs. ForceSample ID HDT at Break at BreakThickness Added phr of °F.(*) At 320° F./40 min.______________________________________1A/.500" 4.2 of Exoxol 9.5 164.5 13.1 721B/.500" 3.0 of Epoxol 9.5 183.9 11.5 991C/.500" 1.8 of Epoxol 9.5 192.9 10.7 1221G/.500" 2 of Fyrol RDP Not 4.4 46 determined1H/.500" 4 of Fyrol RDP Not 4.6 40 determined______________________________________ (*)Heat Distortion Temperature, at 264 psi, per ASTM D648
Examples 1A, 1B and 1C show a higher degree of stretch of the sheet at a lower force.
In Examples 1G, 1H a commercial flame retardant added to the formulation shows how the termoforming parameters can be modified while adding flame retardant additives which might be categorized as plasticizers.
Epoxol 9.5 is an epoxidized linseed oil, sold by Swift Chemical Company. Fyrol RDP is a bis-phosphate ester, containing 11% of phosphorus and it is sold by AKZO.
EXAMPLE 2
A syrup was made by partial polymerization of MMA to obtain a viscosity of 3 Poise and a PMMA content about of 20% weight. Butyl Acrylate, Cab-O-Sil M5, Aluminum Trihydrate (ATH) we added to the syrup under agitation. Their proportions are indicated below, together with the chemicals necessary to obtain a complete polymerization and a good release from the call casting plates:
______________________________________ % Weight______________________________________1-3 syrup (20% PMMA) 57.20Butyl Acrylate 2.00Cab-O-Sil M5 0.53ATH 39.92Wetting Agents 0.35______________________________________ phr______________________________________Pigment Paste As neededRelease Agents As neededCatalysts As neededChain Transfer Agent See Table ACrosslinker See Table APlasticizer See Table A______________________________________
The mixture of ingredients was handled and polymerized as described in Example 1.
Table A shows the combinations of chain transfer agent, crosslinker and plasticizer used and the test results:
TABLE A______________________________________phr on TotalMonomers Heat Dist. TP-0085(*)Chain Temp. Inches Lbs. ForceTransfer Crosslinker Plasticizer (°F.) at Break at Break______________________________________PL-0 .1 .9 -- 200.1 3.3 301PL-1 .1 .9 4 168.8 3.2 250PL-2 .1 .7 -- 195.2 3.7 258PL-4 .1 .7 6 155.5 3.8 206______________________________________ (*)Tested at 340° F./40 minutes heating time.
The data of Table A shows how a certain amount of plasticizer reduces the force needed for thermoforming, see lbs. force of test PL-1 and PL-4 against PL-0 and PL-2, 250 and 206 lbs. against 301 and 258 lbs. respectively. The PL-0 and PL-2 points are outside the region of compositions claimed in U.S. Pat. No. 5,521,243. If a plasticizer is added to them, the performance of the sheet changes and it becomes a candidate for thermoforming, since a lower force is necessary to change its shape and obtain acceptable details in the molded sheet. | A composition suitable for making thermoformable sheets and the like. The composition comprises a crosslinked poly (methyl methacrylate) typically having uncrosslinked poly (methyl methacrylate) dispersed therein. The composition a comprises 0.5 to about 1.0 pph of at least one crosslinking agent x, and up to about 0.58x-0.28 pph of a at least one chain terminator. The composition also comprises about 0.1 to 8 pph poly (methyl methacrylate) compatible plasticizer, and has about 20 to 60 wt % solid particle dispersed therein. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a generic-type steam iron.
2. Description of the Related Art
A steam iron is known from DE-PS 42 14 564 which comprises an electric pump, which conveys water from the water tank via a pressure reservoir to the individual consumers, such as the evaporation chamber, the auxiliary evaporation chamber and the spray device. In order to spray the material which is to be ironed in the region in front of the iron and for steam production, corresponding cut-off valves are actuated from outside the iron by way of manual actuating members. The valves are coupled for the production of steam to control electronics via electric switches.
This known steam iron has the disadvantage that an additional electric switch is required for the production of additional steam. This additional switch interrupts the electric circuit of the pump via the control electronics during actuation of the corresponding cut-off valve in order to prevent the auxiliary evaporation chamber from flooding. Consequently, this known steam iron is still too complicated with regard to its control technology.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a steam iron which can be manufactured in a simpler fashion with respect to control technology and can therefore be produced in a more assembly-friendly, reliable and cost-effective manner.
Pursuant to this object, and others which will become apparent hereafter, one aspect of the present invention resides in a steam iron having a water tank, individual water consumers, an electric pump for conveying water from the water tank via supply lines to the individual water consumers, a pressure reservoir arranged between the pump and the water consumers, which pressure reservoir includes switch means for signaling a maximum water level in the pressure reservoir, a plurality of manually actuable cut-off valves, a switch associated with one of the cut-off valves, and control electronics operatively connected with the switch, the switch means and the pump for controlling different operating modes of the pump and permitting unlimited pump operation time as a function of actuation of the cut-off valves, the switch and the switch means. The control electronics are further operative to recognize and control different operating modes of the pump associated with the individual water consumers as a function of pressure changes in a pressure control circuit. The control electronics limit the operating time of the pump to a maximum time in accordance with the respective operating mode.
As a result of the different dimensioning--as regards flow resistance--of the outlet for the additional steam, comprising a cut-off valve, water hose and metal pipe on the one hand, and the outlet for the spray device, comprising a cut-off valve, water hose and spray nozzle on the other hand, the switch which is coupled to the pressure reservoir carries out different switching cycles, which can be differentiated by the control electronics as an additional steam operation or a spraying operation. The usual spraying operation and the capacity-restricted operation of the electric pump required for this process is actuated by a second switch coupled to the steam valve and the control electronics. In an advantageous manner, the fact that the pump is switched off after a predetermined response time during steam jet mode prevents the auxiliary evaporation chamber from being flooded and the electric pump is prevented from running dry--which would cause damage--when the water tank is empty.
As a result of the invention, there is no need for the additional electric switch which is required in the state of the art for generating additional steam and which interrupts the electric circuit via the control electronics upon actuation of the corresponding cut-off valve. Consequently, the invention offers a substantial simplification of the control technology and assembly whilst improving the reliability of the iron.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of the disclosure. For a better understanding of the invention, its operating advantages, and specific objects attained by its use, reference should be had to the drawing and descriptive matter in which there are illustrated and described preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of the steam iron according to the present invention;
FIG. 2 is a circuit diagram of a steam iron according to FIG. 1;
FIG. 3 is a circuit diagram of a steam iron according to the prior art;
FIG. 4 is a graph illustrating spraying operation; and
FIG. 5 is a graph illustrating steam jet operation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The steam iron schematically illustrated in FIGS. 1 and 2 comprises a water tank 1, an electric pump 2, a pressure reservoir 3 and a spray device 4. The cylindrical pressure reservoir 3 is constructed as a pressure-loaded water reservoir. A piston 6 that is displaceable by the pressure of a spring 5 is arranged inside the pressure reservoir 3. The piston rod 7 of the piston 6 is in operative connection with an electric switch 8. The pump 2 and the pressure reservoir 3 are connected via supply lines 9 and cut-off valves 10, 11 and 12 to water consumers, namely an evaporation chamber 13, an auxiliary evaporation chamber 14 and the spray device 4. The actuation of the cut-off valves 10, 11 and 12 is effected manually via manual actuation members 17, 18 and 19. The valve 11 is in operative connection with control electronics 20 via an electric switch 16 connected to the valve 11. Once the maximum water level of the pressure reservoir 3 is reached, the switch 8 is actuated by the piston rod 7 and the pump 2 is switched off. In contrast, if the water level in the pressure reservoir 3 falls below a certain level, the pump 2 is switched on again via the switch 8. The pump 2 and the pressure reservoir 3 thus form a control circuit which ensures that there is always sufficient water at the outlet of the supply line 9 and that the water always has the required water pressure, since the water withdrawn from the pressure reservoir 3 is immediately replaced. The optimum operating pressure for the entire water storage system is adjustable in the pressure reservoir 3.
FIG. 3 illustrates the prior art in a schematic drawing similar to FIG. 2. It can be seen that a further switch 21 is required for generating additional steam, the further switch 21 switching off the pump 2 via the control electronics when the valve 12 is actuated, thereby preventing the auxiliary evaporation chamber 14 from flooding.
In the operating condition, the iron is switched on and the pump 2 conveys water into the pressure reservoir 3. Once the maximum water level is reached, the pump 2 is switched off and the water is ready for use at the optimum operating pressure upstream of the valves 10, 11 and 12.
In order to spray the material which is to be ironed with cold water, the valve 10 is opened via the manual actuating member 17. The water pressure then falls until the reconnection level is reached in the pressure reservoir 3 and the pump 2 conveys more water into the reservoir. The relationship between the conveying rate of the pump 2 and the withdrawal rate of the valve 10 and the spray nozzle 4 is measured in such a manner that water volume in the pressure reservoir 3 can increase even though water is being withdrawn via the open valve 10, so that the maximum water level is quickly reached again and the pump 2 is switched off. The cycle then begins again, as illustrated in FIG. 4. As a result of this cycle, the control electronics 20 recognizes that the spraying operation is activated and allows this function without imposing any time limit on the pump operation. The withdrawal of water is effected at a system pressure which varies throughout the cycle and with intermittent pump operation.
In order to generate additional steam, the valve 12 is opened via the manual actuating member 19. As a result of the large quantity of water which is withdrawn, the water level in the pressure reservoir 3 and therefore the system pressure falls extremely rapidly on account of the low flow resistance, so that the pump 2, the switch 8 and the control electronics 20 are actuated. However, the maximum water level in the pressure reservoir 3 cannot be attained due to the large quantity of water which is being withdrawn. When the switch 8 on the pressure reservoir 3 fails to transmit a signal within a given period of time, the control electronics 20 recognize active additional steam operation and restrict the duration of the pump operation to a given maximum time t max . This prevents flooding of the auxiliary evaporation chamber 14. A lack of water also advantageously results in an absence of the signal from the switch 8, since the maximum water level in the pressure reservoir 3 cannot be attained when the tank 1 is empty. As with the additional steam generation, the control electronics 20 then restrict the operating time of the pump 2, which is now running dry, to the maximum time t max . This is shown in FIG. 5.
To produce normal steam, the valve 11 is opened by the user via the manual actuating member 18 and the coupled switch 16 is simultaneously actuated. The signal from the switch 16 causes the control electronics 20 to render the pressure control and the time restriction t max inoperative and to set the pump 2 to pulsed half-wave operation, the cycle time being adjustable by the user, e.g. with the aid of a potentiometer on the control electronics 20.
The invention is not limited by the embodiments described above which are presented as examples only but can be modified in various ways within the scope of protection defined by the appended patent claims. | A steam iron with an electric pump for conveying water from a water tank to individual water consumers and control electronics, which control the pump as a function of actuated cut-off valves. The control electronics recognize and control the different operating modes associated with the respective water consumers as a function of pressure changes in the pressure control circuit. The operating duration of the pump is restricted to a maximum time in accordance with the respective operating mode. | 3 |
BACKGROUND OF THE INVENTION
It is well known in the art how to extract coal from deeply buried coal deposits. One method widely practiced is the so called "room and pillar" technique wherein the coal is extracted from the rooms and is left in place in the pillars. Size of each remnant coal pillar is dictated in part by the weight of the overburden which in itself may vary widely over the coal deposit in mountainous terrain. Lengths and widths of the various rooms are dictated in part by the hazards of roof fall, while the height of the room is generally controlled by the thickness of the coal seam. In some cases the thickness of the coal seam is greater than the efficient capacity of existing mining equipment and a portion of the coal seam is left unmined in the roof and in the floor. In such cases it is not uncommon to find examples where less than 50% of the coal in place has been removed when mining is completed and the mine abandoned.
The creation of void spaces underground induces significant stresses in the overburden and concentrates vertical loads in the remnant pillars. Coal, being a non-homogenous rock, inherently introduces uncertainties as to its vertical load carrying capabilities in any given location. Further, vertical load distribution is uneven among massive barrier pillars on the periphery of the mine (or around mine shafts) and each remnant pillar. It is not uncommon to find cases where the vertical load imposed on a particular remnant pillar exceeds the compressive strength of the coal, resulting in bursting of the pillar and shifting additional vertical loads to adjacent remnant pillars which also may burst. The result is a downwarping of the overburden, which in severe cases can cause tension cracks opening up from the mine workings through the overburden on to the surface of the ground above the mine.
While the tensional cracks tend to be in a near vertical alignment on the periphery of the downwarped overburden, compressive forces are predominent near the upper center of the downwarped area and normally cause buckling of the earth's crust. Any man-made structures in the path of these shifts in the earth's surface will be substantially damaged. Such shifting is commonly called subsidence.
Subsidence effects at the surface of the ground may be noticable during the course of mining. In other cases the subsidence effects may not be apparent for many years after the mine is abandoned. Subsidence cracks can be several feet wide at the surface and pose grave hazards if left unattended. Hazards to people and animals are obvious. If the abandoned mine happens to be above the normal water table, a potential fire hazard also exists if one crack serves as an air intake and another crack serves as a chimney. Filling the cracks with inert material may correct the hazardous situation although there is no assurance that another crack will not appear without warning. The potential threat of additional subsidence can be eliminated by filling the void space underground, a practice that generally is more costly than the value of the coal originally removed. Or the mine may be reopened, if it is safe to do so, and the remnant pillars removed by further mining. Generally, abandoned mines fall far short of meeting modern day safety requirements and the cost of upgrading the old mine may be disproportionate to expected revenues from the coal recovered from the remnant pillars.
In many cases the lingering perils of subsidence over the years can be substantially foreshortened and effectively controlled by consuming the remnant pillars in situ, using methods disclosed in the instant invention together with methods taught in U.S. Pat. Nos. 3,987,852; 3,952,802 and 3,948,320; U.S. patent application Ser. Nos. 6l9,562 filed Oct. 6, 1975, now U.S. Pat. Nos. 4,010,801, and 665,128 filed Mar. 8, 1976, now U.S. Pat. No. 4,018,481; all of the instant inventor.
By consuming the remnant pillars in situ the roof of the mine can be lowered in a reasonably uniform manner until the roof and the floor substantially coincide, thereby ending the threat of further subsidence. The necessity of subjecting personnel to the hazards of old underground workings also is eliminated. Further, much of the coal remaining in place, including that in the roof and in the floor, can be converted to useful products such as low BTU fuel gas, synthesis gas, mixed coal chemicals and the like.
To accomplish the planned results the old mine workings must be sealed and remain sealed so that the underground chambers can be converted into pressurized reaction zones. Then the in situ techniques of gasification, liquefaction and pyrolysis can be employed to convert remaining coal into commercial products.
OBJECTS OF THE INVENTION
It is an objective of the instant invention to teach methods of applying pressure tight seals to an underground coal deposit.
It is an objective of the instant invention to teach methods of control of in situ reactions so that underground coal can be consumed in accordance with a predetermined plan.
Other objectives, capabilities and advantages of the instant invention will become apparent as the description proceeds and in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic vertical section taken through a portion of the earth, showing the arrangement of apparatus used in the methods of the instant invention.
FIG. 2 is a diagrammatic plan view of an underground remnant coal deposit that is considered ideal to the practice of the instant invention.
FIG. 3 is a diagrammatic vertical section of a production well.
SUMMARY OF INVENTION
Referring to FIG. 1, an underground coal deposit is overlain by overburden 11. The coal deposit has been previously mined to economic depletion by room and pillar techniques. Coal remains in place in the remnant pillars 12, barrier pillar 13, in the roof 14 and in the floor 15. Remnant pillar 16 has failed in compression causing downwarping of the overburden 11 with resultant subsidence cracks 17 & 22. The original mining operations had entry 19 and ventilation shaft 20, and barricades 21 were erected at the close of operations to seal the mine. Due to subsidence the seal has been altered by cracks 17 and 22, and the damage to shaft 20 when crack 22 intersected the shaft. Mud slurry injection well 23 has been drilled into crack 17 and mud slurry injection well 24 has been drilled into crack 22. Injector-production wells 25 and 26 are two of a series of wells that are drilled into the coal deposit with bottoms of the holes located preferably in the top of the void space or rooms within the coal. A slush mud slurry is prepared in surface facilities (not shown) and the slurry is injected into wells 23 and 24 and into shaft 20. Slurry injection is continued until a static head is established of sufficient height to contain the expected mine pressure when in situ production is undertaken, for example 50 psig. The slurry serves not only as a gas tight sealant but also to lubricate cracks 17 and 22 so that overburden 11 may be lowered reasonably uniformly as the remnant pillars are consumed. Should additional subsidence cracks develop during the period of planned subsidence, these cracks also should be mudded off similar to cracks 17 and 22.
A multiplicity of injector-production wells 25 and 26 is drilled into the coal formation and the coal is set afire using techniques common in the production of coal in situ. The fire is sustained by injection of oxidizer, preferably compressed air. Products of combustion are withdrawn through appropriate injector-producer wells, with proper back pressure maintained on the withdrawal wells to maintain desired mine pressure, for example 50 psig. Initially there will be considerable void space volume within the coal underground and the fire of necessity will be located in a relatively small portion of the mine. As the burning proceeds the temperature of the gases underground will gradually increase to the point where the temperature is above the ignition temperature of the exposed coal. It is during this phase that propagation of the fire is easiest to attain in the coal making up the roof of the underground workings. In time all of the exposed coal will be heated to a temperature above its ignition temperature and fire propagation becomes a function of oxidizer distribution underground.
As the burning proceeds the process of subsidence accelerates. It is necessary to maintain sufficient mud slurry capacity to deliver mud to subsidence cracks at sufficient volumes to maintain the mud slurry seal and thus contain the mine pressure. With continuing subsidence the void space underground is significantly diminished and the efficiency of the in situ production processes is significantly increased. Near the end of the production program when substantially all of the coal available for reaction has been consumed, the project is terminated by injecting copious quantities of water into the residual void space until the remnants of coal and the surrounding rock is below the ignition temperature of the coal.
Thus it may be seen that abandoned coal mines may be further produced to resource exhaustion using in situ production techniques thereby utilizing wasted resources and terminating the threat of subsidence damages.
DESCRIPTION OF THE PREFERRED EMBODIMENT
For illustration purposes the methods taught herein are directed to the special case of an abandoned underground coal mine that was produced by room and pillar techniques. Those skilled in the art will recognize that these methods also may be applied to underground coal deposits partially recovered by other techniques and in some cases to virgin coal deposits.
The coal deposit as illustrated in FIG. 1 has been mined by driving an entry 19 into the side of a hill that is underlain by a coal deposit. The economically recoverable coal has been extracted by room and pillar techniques with ventilation provided by shaft 20. Barrier pillar of coal 13 has been left in place at the property limit line. Upon completion of mining barricades 21 were installed to seal the mine. In time after abandonment, remnant pillar 16 failed in compression causing partial failure of nearby remnant pillars. Downwarping of the overburden 11 induced tension cracks 17 and 22. Open cracks 17 and 22 sometimes called subsidence cracks, presented hazards to wild animals and hikers and provided conduits from the surface of the ground into the old workings. For safety purposes the area of cracks in the surface may be contained within a barrier fence to prevent accidental falls.
The process begins by drilling mud injection wells 23 and 24 to their intersection with cracks 17 and 22 respectively, with the well bores suitably cased to prevent slumping of the well bore. A suitable sealant fluid is prepared in surface facilities (not shown), such fluid in its simplest form being a mud slurry composed of water and approximately 40% solids such as native clay. Other "muds" commonly used in the drilling of petroleum wells may also be used together with various mud additives commonly used in the petroleum industry. It is important that the sealant fluid be non flammable and preferably non toxic. It is further preferable that the sealant fluid be composed in part of solid materials that remain within the fluid at high fluid velocities and tend to settle out of the fluid at low velocities. For example, upon injection of the sealant fluid into well 23, the fluid should remain as a slurry as it rapidly descends into crack 17 and into the void space 27 between the barricades 21 immediately below crack 17. Then as the fluid velocity is diminished the solids in the slurry should settle out and fill the void space 27 with solids. Any leaks around barracades will also result in low fluid velocities with the solids settling out to plug the leaks.
Sealant fluid injection is continued through well 23 until a proper fluid head pressure is established in crack 17, for example a fluid head pressure that will provide a seal against a mine pressure of 50 psig. Once the fluid head pressure is stabilized at the desired level it is important that the fluid head pressure be maintained at that level. It is preferable to install a liquid level sensor (not shown) in crack 17 so that further injection of fluid is automatically initiated when the liquid level descends below the desired level.
Crack 22 is similarly treated with sealant fluid after sealant fluid injection well 24, sometimes called mud injection well, is drilled and completed. The void space 28 is filled with solids settling out of the slurry and the injection of the slurry is continued until the proper fluid head pressure is attained in crack 22 and shaft 20. Should the sealant action in crack 22 be such that an insufficient fluid head is attained in shaft 20, injection of the mud slurry should be undertaken into shaft 20 until the desired fluid head pressure is attained also in shaft 20.
In this mode the underground workings are now sealed so that the mine may be pressurized to the desired level, for example 50 psig. In some cases the fluid seal may not be completely effective, resulting in the slurry carrier liquid continuously leaking at slow rates into the mine workings. In these cases a fluid removal well (not shown) can be drilled into the underground workings, preferably located at the lowest point in the underground workings, and the migrant carrier liquid can be pumped to the surface for recycling. Later in the production cycle the pumping of the carrier liquid may be terminated and the carrier liquid utilized in situ as a part of the production process. The well, previously used for withdrawing accumulated liquids then may be converted and used as an injector-producer well for the in situ processes.
Referring to FIG. 3, with the underground workings sealed to withstand the desired mine pressure, for example 50 psig, injector-production wells 26 are drilled from the surface of the earth through the overburden 11 and through the roof of the underground workings 14. Each well is lined with a surface casing 31 with the bottom of the casing located at a convenient depth, for example 50 feet below the surface of the ground. The casing is cemented in place. The bore hole is then deepened to a point 33 in the overburden near the top of the coal. Point 33 is located in a competent rock strata in the overburden, preferably sandstone. A liner 35, for example 9 inches in diameter, is installed from the surface of the ground through retaining bracket 36, with the bottom of the liner landed at point 33. The bottom of liner 35 is cemented 34 in place for a vertical distance for example of 10 feet. Retaining bracket 36 serves the purpose of positioning liner 35 within casing 31 so that liner 35 may elongate without restraint. The well bore is then deepened from point 33 through coal 14.
It is important that the lower cement seal 34 be positioned with due regard for competent rock strata in the lower part of the overburden in order to provide a proper seal. Preferably the remainder of the annulus 37 between the bore hole and the liner 35 above the lower cement seal 34 is filled with mud slurry to complete the hermetic seal of the injector-producer well. Such an arrangement provides a cushion around liner 35 so that damage to the liner is minimized when further earth shifts occur as a result of continuing subsidence. Also this arrangement permits the liner 35 to elongate and contact with varying temperatures expected to be encountered in the production cycle.
In some cases the mud slurry or sealant material used in the well bore should be composed of a liquid carrier fluid other than water, preferably a liquid with a boiling point temperature higher than that of water. In other cases, particularly those in which the casing is subjected to gas temperatures in excess of 1000° F., it may be desirable to install a slurry injection tubing 38 in the well bore annulus 37 from the surface of the ground to a point near the lower cement seal 34 so that the slurry may be circulated within annulus 37 to provide cooling for liner 35.
At the top of liner 35 suitable wellhead fixtures are installed to permit injection and withdrawal of fluids in the production cycle. Such fixtures are sealed to complete the hermetic seal between the underground workings and surface facilities. As shown in FIG. 3 tubing 40 contains valve 39 and tubing 42 contains valve 41. Tubing 40 could be connected to a compressor delivering oxidizer to well 26 when well 26 is programmed to be an injector well, and in this mode valve 41 would remain closed. Tubing 42 could be connected to gas clean-up facilities when well 26 is programmed to be a producer well, and in this mode valve 39 would remain closed.
In commercial practice a multiplicity of injector-producer wells would be drilled into the underground workings. For purposes of illustration, the bottom hole locations of four such wells are shown on FIG. 2. Wells 25, 26 and 29 are drilled into the "rooms" around remnant pillar 30, and well 18 is drilled into remnant pillar 44. These wells, together with other injector-producer wells not shown, provide numerous alternatives for fluid flow directions underground both for oxidizer injection and for withdrawal of products of combustion. Some of these alternatives are described herein, and those skilled in the art will be able to envision numerous other alternatives within the scope of the disclosure.
Looking first to well 18, this well is drilled and hermetically sealed as described in the foregoing description of well 26. The well bore is then deepened into the coal within remnant pillar 44. In one alternate explosives, for example an ammonium nitrate fuel oil mixture, may be positioned in the lower part of the well bore within remnant pillar 44 and the charge detonated to create communication passages between well 18 and the void space of the underground workings. In another alternate, the well bore within remnant pillar 44 may be ignited, for example by dropping hot charcoal briquettes into the well bore, and the coal in remnant pillar 44 set afire by continuous injection of oxidizer through well 18, with an injection pressure of for example 200 psig. The second alternate is preferable when well 18 is selected as the site for the initial production of the underground coal deposit. If well 18 is used to initiate the in situ production of the coal, the underground workings will be at relatively low gas pressure, for example 14.7 psia, and the fire in remnant pillar 44 will proceed as a forward burn from well bore 18. Due to differential pressure the products of combustion will migrate through the natural permeability in the coal and into the void space of the underground workings. This method may be continued if desired until the mine pressure reaches the planned level, for example 50 psig, before it is necessary to engage a production well.
Preferably, however, the coal deposit is ignited in several locations early in the production sequence. For example, shortly after well 18 is ignited well 26 can be ignited, for example by dropping hot charcoal briquettes onto the coal in the mine floor underneath well 26. Oxidizer injection continues, for example at a pressure of 100 psig, in well 26 and when the mine pressure reaches the desired level, for example 50 psig, well 29 is engaged as a production well for withdrawing the products of combustion to surface facilities. Sufficient backpressure is maintained in well 29 to maintain the desired level of mine pressure, for example 50 psig. In this mode the two fire locations are propagating as forward burns toward well 29. Similarly the coal near well 25 may be ignited for the third fire location with propagation in a forward mode toward well 29.
Generally after the various underground fires are well established, the temperature of the underground gases is significantly higher than the temperature of the injected oxidizer, for example compressed air. Thus the oxidizer will tend to sink and spread until the oxygen content is consumed. The differential temperatures and pressures underground create considerable turbulence which is generally beneficial to the in situ production processes, particularly in converting virgin coal into low BTU fuel gas. In some cases an oxidizer bypass situation may occur such as the air injected into well 25 proceeding along the roof of the mine workings and on to well 29. In this case the low BTU gas generated between wells 26 and 18 enroute to production well 29 may be further burned by the excess oxidizer supply from well 25, and thus the gases will arrive at the surface with no calorific content except for sensible heat. Corrective action may be taken by installing an oxidizer injection line (not shown) within well 25 so that the oxidizer release point is near the floor of the mine workings. An alternate corrective action would be to reduce the oxidizer injection pressure into well 25 to for example 65 psig.
In time, with the initiation of numerous fire points in the underground workings, the mine temperature will increase to the point where all exposed coal is at a temperature above its ignition point. When this occurs the in situ production techniques reach maximum flexibility, because the fire areas may be propagated by selective control of oxidizer distribution. In areas of the underground workings where there is an insufficiency of oxygen for combustion, the coal is at a temperature well within the range of pyrolysis temperatures and medium BTU fuel gases are being expelled for collection by a nearby production well. Steam may be injected into the hottest areas resulting in a reaction with coal to generate carbon monoxide and hydrogen for collection by a nearby production well, and the like. Also the residual coal can be consumed in patterns that induce subsidence in a reasonably uniform manner.
Thus it may be seen that an underground coal deposit of no apparent economic value can be converted to commercial products and that the perils of subsidence can be foreshortened and controlled.
While the instant invention has been described with a certain degree of particularity it is recognized that changes in details of structure may be made without departing from the spirit thereof. | A previously mined underground coal deposit is sealed so that the underground void space can be pressurized for production by in situ techniques. Excavated communication passages are sealed by barricades which are further sealed by applying hydrostatic head pressure. Subsidence cracks are sealed by injection of mud slurry with additional sealing effected by maintaining hydrostatic head pressure with a column of the slurry. In situ production wells are drilled into the coal with hermetic seal accomplished in part by cementing a portion of the liner to the well bore and in part by the hydrostatic head pressure of a mud slurry positioned above the cement seal. Coal is ignited and burn patterns are established to cause reasonably uniform subsidence. | 4 |
This is a continuation, of application Ser. No. 09/109,515, filed Jul. 2, 1998, which is a continuation of prior application Ser. No. 08/798,896, filed Feb. 11, 1997, now U.S. Pat. No. 5,907,897, which is a continuation-in-part of U.S. Ser. No. 08/761,730, filed Dec. 5, 1996, U.S. Pat. No. 5,870,938.
FIELD OF THE INVENTION
The present invention relates to compound miter saws or other power operated equipment or machinery utilizing a cutter for performing working operations on a workpiece. More particularly, the present invention relates to improvements in the bevel stop mechanism for the bevel adjustment for such power operated equipment.
BACKGROUND OF THE INVENTION
Saws and other apparatuses designed for cutting or performing other working operations on a workpiece typically require adjustment mechanisms for moving the saw blade or cutting tool into an angular relationship to the workpiece. Examples of such equipment include cross-cut compound miter saws which are adapted for allowing the user to selectively move the saw blade into any of a number of positions or modes for square cutting, miter cutting, bevel cutting, or compound miter cutting where a combination miter angle and bevel angle are cut. In addition, some operations, such as dado cutting or shaping operations, for example, require the use of saw blades or other cutting or working devices of different shapes or sizes to be substituted for one another in order to perform the desired operation on the workpiece, whether the workpiece is composed of wood, plastic, metal other materials.
In order to allow for the adjustment in the miter and the bevel angle, the saw blade, cutter or other working device is angularly adjustable with respect to a horizontal base and a vertical fence against which the workpiece is positioned. The miter adjustment allows the saw blade, cutter or other working device to move angularly with respect to the vertical fence while maintaining perpendicularity with the horizontal base. The bevel adjustment allows the saw blade, cutter or other working device to move angularly with respect to the horizontal base while maintaining perpendicularity with the vertical fence. At times it may be desirable to cut a combination miter angle and bevel angle by simultaneously adjusting the angularity of the blade with respect to both the horizontal base and the vertical fence.
Once the saw blade, cutter or other working device has been adjusted to the desired position with respect to the horizontal base and the vertical fence, locking mechanisms for the miter and bevel adjustment must be activated in order to prohibit movement of the saw blade, cutter or other working device with respect to the base and fence while the cutting operation is performed. These locking mechanisms need to be easily activated, adjustable and quick acting in order to optimize the efficiency of the cutting apparatus and provide convenience to the operator of the apparatus.
It is also advantageous to provide bevel stop mechanisms so that operators can change and easily locate common bevel angles. These bevel stop mechanisms need to be easily engaged and disengaged, adjustable and quick acting in order to optimize the efficiency of the cutting apparatus and provide convenience to the operator of the apparatus.
SUMMARY OF THE INVENTION
In accordance with the present invention, an improved bevel stop is employed in a miter saw. The miter saw includes a table on which a workpiece is placed, a miter saw unit supporting a saw blade and having a motor for rotatably driving the saw blade, and a housing pivotally supporting the miter saw unit related to the table in such a manner that the miter saw unit is at least laterally pivotable. Further, the miter saw includes a bevel mechanism for selectively determining the lateral position of the miter saw unit at any of a plurality of pivoted positions including a vertical position where the saw blade is positioned substantially vertically relative to the table, and leftward and rightward pivoted positions where the blade is inclined laterally leftwardly and laterally rightwardly from the vertical position.
The bevel mechanism includes a movable rod and three fixed stop members, the rod being operable to move between a first rod position abutting one of the fixed stop members and a second rod position not abutting the one of the fixed stop members so as to permit the lateral pivotal movement of the miter saw unit. The first fixed stop member is disposed so that the rod abuts the first fixed stop member when the miter saw unit is at the vertical position. Similarly, the second fixed stop member is disposed so that the rod abuts the second fixed stop member when the miter saw unit is leftwardly pivoted at a first predetermined angle from the vertical position. Further, the third fixed stop member is disposed so that the rod abuts the third fixed stop member when the miter saw unit is rightwardly pivoted at a second predetermined angle from the vertical position.
Other advantages and objects of the present invention will become apparent to those skilled in the art from the subsequent detailed description, appended claims and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings which illustrate the best mode presently contemplated for carrying out the present invention:
FIG. 1 is a front perspective view of a sliding compound miter saw in accordance with the present invention;
FIG. 2 is a front elevational view of the sliding compound miter saw shown in FIG. 1;
FIG. 3 is a rear elevational view of the sliding compound miter saw shown in FIGS. 1 and 2;
FIG. 4 is a side elevational view of the sliding compound miter saw shown in FIGS. 1 through 3;
FIG. 5 is an exploded perspective view of a first embodiment of the bevel stop mechanism in accordance with the present invention;
FIG. 6 is an assembled perspective view, partially in cross-section of the first embodiment of the bevel stop mechanism shown in FIG. 5;
FIG. 7 is a cross-sectional side view of the first embodiment of the bevel stop mechanism shown in FIG. 5;
FIG. 8 is an end view of the base or table assembly illustrating a first embodiment of the adjustment feature provided for the bevel stop mechanism shown in FIG. 5;
FIG. 9 is an end view of the base or table assembly illustrating a second embodiment of the adjustment feature provided for the bevel stop mechanism shown in FIG. 5;
FIG. 10 is an end view of the base or table assembly illustrating a third embodiment of the adjustment feature provided for the bevel stop mechanism shown in FIG. 5;
FIG. 11 is a partial cross-section perspective view of a second embodiment of the bevel stop mechanism;
FIG. 12 is a cross-sectional side view of the second embodiment of the bevel stop mechanism shown in FIG. 11;
FIG. 13 is a partial cross-section perspective view of a third embodiment of the bevel stop mechanism;
FIG. 14 is a cross-sectional side view of the third embodiment of the bevel stop mechanism shown in FIG. 13;
FIG. 15 is a partial cross-section perspective view of a fourth embodiment of the bevel stop mechanism;
FIG. 16 is a cross-sectional side view of the fourth embodiment of the bevel stop mechanism shown in FIG. 15;
FIG. 17 is a partial cross-section perspective view of a fifth embodiment of the bevel stop mechanism;
FIG. 18 is a cross-sectional side view of the fifth embodiment of the bevel stop mechanism shown in FIG. 17;
FIG. 19 is an end view of the base or table assembly illustrating the adjustment feature provided for the bevel stop mechanism shown in FIGS. 17 and 18;
FIG. 20 is a partial cross-section perspective view of a sixth embodiment of the bevel stop mechanism;
FIG. 21 is a cross-sectional side view of the sixth embodiment of the bevel stop mechanism shown in FIG. 20;
FIG. 22 is a partial cross-section perspective view of a seventh embodiment of the bevel stop mechanism;
FIG. 23 is a cross-sectional side view of the seventh embodiment of the bevel stop mechanism shown in FIG. 22;
FIG. 24 is a partial cross-section perspective view of an eighth second embodiment of the bevel stop mechanism;
FIG. 25 is a cross-sectional side view of the eighth embodiment of the bevel stop mechanism shown in FIG. 24;
FIG. 26 is an end view of the base or table assembly illustrating a ninth embodiment of the bevel stop mechanism;
FIG. 27 is an exploded side view of the pin assembly used in the ninth embodiment of the bevel stop mechanism shown in FIG. 26;
FIG. 28 is an exploded perspective view of the pin assembly used in the ninth embodiment of the bevel stop mechanism shown in FIG. 26;
FIG. 29 is a side view of the pin assembly used in the ninth embodiment of the bevel stop mechanism shown in FIG. 26, where FIG. 29 a shows the pin assembly in the expanded position and FIG. 29 b shows the pin assembly in the retracted position;
FIG. 30 is a cross-sectional side view of the rod assembly used in conjunction with the ninth embodiment of the bevel stop mechanism shown in FIG. 26;
FIG. 31 is a partial cross-section perspective view of a tenth embodiment of the bevel stop mechanism;
FIG. 32 is a cross-sectional side view of the tenth embodiment of the bevel stop mechanism shown in FIG. 31;
FIG. 33 is a cross-sectional view of the tenth embodiment of the bevel stop mechanism shown in FIGS. 31 and 32, along a line D—D shown in FIG. 32;
FIG. 34 is a partial cross-section perspective view of a eleventh embodiment of the bevel stop mechanism;
FIG. 35 is a cross-sectional side view of the eleventh embodiment of the bevel stop mechanism shown in FIG. 34; and
FIG. 36 is a cross-sectional view of the tenth embodiment of the bevel stop mechanism shown in FIGS. 34 and 35, along a line E—E shown in FIG. 35 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings in which like reference numerals designate like or corresponding parts throughout the several views, there is shown in FIGS. 1 through 4 an exemplary sliding compound miter saw incorporating a bevel stop mechanism according to the present invention, shown merely for the purposes of illustration, and designated generally by the reference numeral 10 . One skilled in the art will readily recognize from the following description, taken in conjunction with the accompanying drawings and claims, that the principles of the present invention are equally applicable to sliding compound miter saws, compound miter saws, chop saws, radial arm saws, table saws, jigsaws, scroll saws, or other saws of types other than that shown for purposes of illustration in the drawings. Similarly, one skilled in the art will readily recognize that the principles of the bevel stop mechanism according to the present invention are also applicable to other types of powered or unpowered equipment for performing an operation on a workpiece. Such equipment includes, but is not limited to, dado saws, spindle shapers or sanders, or other types of powered or unpowered devices that would benefit from the cam locking mechanism of the present invention.
Referring primarily to FIGS. 1 through 4, sliding compound miter saw 10 comprises a base assembly 12 , a table assembly 14 , a unique housing assembly 16 , a saw blade 18 , a blade guard 20 , a motor 22 drivingly connected to saw blade 18 , a handle 24 and a fence assembly 26 . Table assembly 14 is secured to base assembly 12 such that it can be rotated in order to provide adjustment for miter cutting. The rotation of table assembly 14 changes the angle of saw blade 18 relative to fence assembly 26 but maintains the perpendicularity of saw blade 18 with table assembly 14 . A locking mechanism 28 can be activated in order to lock table assembly 14 to base assembly 12 .
Housing assembly 16 is secured to table assembly 14 such that it can be pivoted with respect to table assembly 14 in order to provide adjustment for bevel cutting. As can be appreciated by one skilled in the art, the adjustments for mitering and beveling can be separate or they can be adjusted simultaneously in order to provide a compound miter and bevel cut. The pivoting of housing assembly 16 changes the angle of saw blade 18 relative to table assembly 14 but maintains the perpendicularity of saw blade 18 with respect fence assembly 26 . A locking mechanism 30 can be activated in order to lock housing assembly 16 to table assembly 14 at any desired bevel angle.
Referring to FIGS. 1 through 5, housing assembly 16 includes support housing 32 , which mounts a pair of support arms 34 for sliding movement with respect to housing 32 . Saw blade 18 , blade guard 20 , motor 22 and handle 24 are all mounted to a drive housing 36 which is pivotably secured to support arms 34 . The pivoting of drive housing 36 downward towards table assembly 14 operates to open blade guard 20 and cut a workpiece which is supported by table assembly 14 and fence assembly 26 . The sliding movement of support arm 34 relative to housing 32 permits drive housing 36 and thus saw blade 18 to be pulled through the workpiece when the size of the workpiece exceeds the cutting width of saw blade 18 .
Referring now to FIGS. 5 through 8, support housing 32 is pivotably supported with respect to table assembly 14 on a steel shaft 40 which is secured to table assembly 14 and extends rearwardly from table assembly 14 to define a pivot axis 42 for support housing 32 . Shaft 40 is inserted into a complimentary bore 44 located within table assembly 14 and is secured in place using a cross pin 46 which extends through a bore 47 extending through shaft 40 and a corresponding set of bores 48 located within table assembly 14 and being generally perpendicular to and extending into bore 44 . The end of shaft 40 opposite to the end defining bore 46 includes a threaded stub 50 for retaining and adjusting locking mechanism 30 as will be described later herein.
Locking mechanism 30 comprises a cam 52 , a handle 54 , a thrust bearing 55 , a plurality of washers 56 and a locknut 58 . Once support housing 32 is slidingly and pivotably received on shaft 40 , cam 52 is slidingly positioned on shaft 40 adjacent support housing 32 . Cam 52 includes a D-shaped through bore 60 which mates with a corresponding D-shaped portion 62 of shaft 40 such that cam 52 is allowed to move axially along portion 62 of shaft 40 but rotation of cam 52 with respect to shaft 40 is prohibited. Cam 52 further includes an angular camming surface 64 having a plurality of ramps which is located on the radial surface of cam 52 which is opposite to support housing 32 . Camming surface 64 is designed to mate with handle 54 as will be described later herein.
Handle 54 is slidingly and rotatably positioned on shaft 40 adjacent to and outboard of cam 52 . Handle 54 includes an angular camming surface 66 having a plurality of ramps which mates with angular camming surface 64 on cam 52 . Support housing 32 , cam 52 and handle 54 are retained on shaft 40 by thrust washer 55 , the plurality of washers 56 and locknut 58 which is threadingly received on stub 50 of shaft 40 .
When angular camming surface 64 and angular camming surface 66 are in full contact with each other as shown in FIG. 7, support housing 32 is free to pivot on shaft 40 to change the bevel angle of saw blade 18 . Once the desired bevel angle has been set, handle 54 is rotated with respect to shaft 40 . Rotation of handle 54 mis-aligns camming surfaces 64 and 66 pushing support housing 32 and cam 52 axially along shaft 40 . Support housing 32 contacts table assembly 14 and continued rotation of handle 54 forces support housing 32 into table assembly 14 locking the two components together. The locking of the two components together can be accomplished by rotating handle 54 in either a clockwise or a counter clockwise direction on order to misalign camming surfaces 64 and 66 . This bi-directional locking ability of handle 54 simplifies the adjustment of the bevel angle on opposite sides of center. An indicator plate 68 is bolted to support housing 32 to allow the user to set a specific bevel angle. Indicator plate 68 is provided with a pair of slots which allow for the zero adjustment of plate 68 as is well known in the art.
The present miter saw 10 also incorporates two additional features within housing assembly 16 . These two features are a detent system 70 and a positive stop system 72 . Detent system 70 includes a biasing spring 74 and a ball 76 . Biasing spring 74 and ball 76 are inserted into a blind aperture 78 located within support housing 32 . The ends of aperture 78 are formed over ball 76 such that ball 76 is retained within aperture 78 while being biased by spring 74 against the formed ends of aperture 78 . Table assembly 14 includes a pair of detents 80 , FIG. 8, which are formed into the face of table assembly 14 . The position of detents 80 are selected such that ball 76 will drop into detent 80 when the bevel angle for support housing 32 reaches 31.62° either side of center. A bevel angle of 31.62° is desired when miter saw 10 is being set to cut cove molding. While the present invention is illustrated as having only one pair of detents 80 , it is within the scope of the present invention to provide additional detents located at additional bevel angles which are commonly used if desired.
Referring to FIGS. 5 through 8, positive stop system 72 comprises a biasing spring 82 , a stop rod 84 , an override button 86 and an adjustable stop system 88 . Biasing spring 82 is inserted into a stepped aperture 90 extending through support housing 32 such that it abuts the step formed within aperture 90 . Stop rod 84 is then inserted through spring 82 and through aperture 90 trapping spring 82 between rod 84 and stepped aperture 90 . A reduced diameter portion 92 of rod 84 extends through housing 32 and is inserted into a slot 94 formed within override button 86 . Override button 86 is pivotably secured to a pair of posts 96 formed as a part of housing 32 by a pair of bolts 98 . Once secured to posts 96 , pivoting movement of button 86 moves stop rod 84 axially within housing 32 between a stop position and a release position with spring 82 biasing stop rod 84 into its stopped position.
Persons skilled in the art will recognize that the spring 82 shown in FIGS. 6 and 7 is a compression spring. Additionally, such persons will recognize that the same function, i.e., biasing stop rod 84 into its stopped position, can be achieved by springs disposed on the button 86 which bias the button towards the stopped position. Further, persons skilled in the art will recognize that other means, such as elastomeric materials and structures, can be utilized to bias the stop rod 84 into its stopped position.
Additionally, persons skilled in the art will recognize that the stop rod 84 moves axially in a direction parallel to the axis of rotation 42 . However, such persons will also recognize that the stop rod 84 can be inclined in any manner, so long as it can contact the bolt 100 .
When located in its stopped position, stop rod 84 extends out of housing 32 and into table assembly 14 such that it can engage one of the plurality of adjustable stops 88 a shown in FIG. 8 . Table assembly 14 is shown having an adjustable stop 88 a located at a 0° bevel angle and at a bevel angle of 45° on both sides of center. Each adjustable stop 88 a includes a housing 98 and a threaded stop bolt 100 . Each housing 98 is shown as an integral part of table assembly 14 but it is within the scope of the present invention to manufacture individual housings 98 and secure them to table assembly 14 if desired. Each housing 98 defines a threaded through bore 102 into which stop bolt 100 is threadably received. Threaded stop bolt 100 provides a surface for stop rod 84 to contact when the bevel angle of housing 32 is located at about 0° or about ±45° from the 0° bevel angle as is shown in the preferred embodiment. The adjustability of each stop 88 a is provided by the threaded connection between bolt 100 and housing 98 and this adjustability allows the operator to accurately set these specific bevel angles. When the bevel angle needs to be changed, handle 54 is rotated to release housing 32 from table assembly 14 and override button 86 is pivoted on posts 96 to withdraw stop rod 84 from within table assembly 14 to a position at which stop rod 84 does not contact bolt 100 or housing 98 when housing 32 is pivoted on shaft 40 .
Persons skilled in the art will recognize that the adjustable stops 88 a may be replaced with fixed castings on the table assembly 14 . This will provide a mechanism to stop the stop rod 84 at a lower manufacturing cost.
The table assembly 14 may further be provided with a ramp 150 . The ramp 150 contacts the stop rod 84 when the miter saw is beveled in a clockwise direction M, i.e., from the −45° bevel angle towards the +45° bevel angle, so that the stop rod 84 retracts and bypasses the 0° bolt.
FIG. 9 illustrates a different adjustable stop system 88 , which can be used in conjunction with the other elements of the positive stop system 72 . Table assembly 14 is shown having an adjustable stop 88 a located at about a bevel angle of 45° on both sides of center, having the same function and adjustability as described above. In addition, an adjustable guide plate 113 is provided to stop the stop rod 84 when the bevel angle of the housing 32 is located at about 0°. The guide plate 113 is preferably connected to an adjustment bolt 110 .
The adjustment bolt 110 includes a housing 112 . Each housing 112 is shown as an integral part of table assembly 14 but it is within the scope of the present invention to manufacture individual housings 112 and secure them to table assembly 14 if desired. Each housing 112 defines a threaded through bore 111 into which bolt 110 is threadably received. The adjustability of the adjustment bolt 110 (and thus of the guide plate 113 ) is provided by the threaded connection between bolt 100 and housing 98 . This adjustability allows the operator to accurately set the position of the guide plate 113 , and thus the specific bevel angle.
The table assembly 14 may further be provided with ramps 150 a . The ramps 150 a contact the stop rod 84 when the miter saw is beveled back to the vertical position, i.e., from the ±45° bevel angles to the 0° bevel angle, so that the stop rod 84 retracts and slides onto guide plate 113 . The stop rod 84 then engages the guide plate 113 by extending into hole 113 a . When the bevel angles needs to be changed, handle 54 is rotated to release housing 32 from table assembly 14 and override button 86 is pivoted on posts 96 to withdraw stop rod 84 from within table assembly 14 to a position at which stop rod 84 does not engage guide plate 113 via hole 113 a when housing 32 is pivoted on shaft 40 .
FIG. 10 illustrates yet another adjustable stop system 88 , which can be used in conjunction with the other elements of the positive stop system 72 . Like the stop system shown in FIG. 9, this system has an adjustable guide plate 115 . The guide plate 115 is preferably connected to at least one adjustment bolt 110 . Unlike the guide plate 113 , the guide plate 115 has a plurality of holes 115 a, for the stop rod 84 to contact when the bevel angle of housing 32 is located at about 0° or about ±45° from the 0° bevel angle. Nevertheless, operation of the system is substantially similar to the stop system of FIG. 9 .
Referring to FIGS. 11 and 12, a second embodiment of positive stop system 72 comprises a biasing spring 82 , a stop rod 84 , an override handle 114 and a stop system, preferably one of the stop systems shown in FIGS. 8 through 10. Biasing spring 82 is inserted into a stepped aperture 90 extending through the housing 32 such that it abuts the step formed within aperture 90 . Stop rod 84 is then inserted through spring 82 and through aperture 90 . The housing 32 has a plaque 117 , which may be built separate to or integrated with the housing 32 . Spring 82 is trapped between plaque 117 and the stop rod 84 .
A reduced diameter portion 92 of rod 84 extends through housing 32 and is inserted through a slot in plaque 117 . An override handle 114 is then attached to the portion of rod. 84 extending through plaque 117 .
Further, stop rod 84 has a helical groove 116 disposed on its body, that engages a stop 115 in housing 32 . Accordingly, rotational movement of handle 114 , for example,in a clockwise direction, i.e., along direction A, rotates stop rod 84 . Because of the engagement between the stop 115 and the rod groove 116 , stop rod 84 moves axially while rotating, as in a screwing action, within housing 32 between a stop position and a release position with spring 82 biasing stop rod 84 into its stopped position.
Persons skilled in the art will recognize that the spring 82 shown in FIGS. 11 and 12 is a compression spring. Additionally, such persons will recognize that the same function, i.e., biasing stop rod 84 into its stopped position, can be achieved by rotational springs disposed on the stop rod 84 and/or handle 114 , which force the rod 84 to rotate towards the stopped position. Further, persons skilled in the art will recognize that other means, such as elastomeric materials and structures, can be utilized to bias the stop rod 84 into its stopped position.
Referring to FIGS. 13 and 14, a third embodiment of positive stop system 72 comprises, like the embodiment illustrated in FIGS. 11 and 12, a biasing spring 82 , a stop rod 84 , an override handle 114 and a stop system, preferably one of the stop systems shown in FIGS. 8 through 10. The arrangement and operation of the third embodiment is similar to the one illustrated in FIGS. 11 and 12. Accordingly, the description of the second embodiment should be referred to when studying this embodiment.
Unlike in the second embodiment, a separate stop 119 is preferably disposed in the housing 32 . Spring 82 is then trapped between stop 119 and the stop rod 84 . Further, the helical groove 116 is disposed towards the rear of stop rod 84 , so that it can engage a stop 118 disposed in plaque 117 . Nevertheless, operation of the third embodiment is similar to that of the embodiment shown in FIGS. 11 and 12.
Referring to FIGS. 15 and 16, a fourth embodiment of positive stop system 72 comprises, like the embodiment illustrated in FIGS. 11 and 12, a biasing spring 82 , a stop rod 84 , an override handle 114 and a stop system, preferably one of the stop systems shown in FIGS. 8 through 10. The arrangement and operation of the fourth embodiment is similar to the one illustrated in FIGS. 11 and 12. Accordingly, the description of the second embodiment should be referred to when studying this embodiment.
Unlike in the second embodiment, plaque 117 is provided with guide 120 . Furthermore, stop rod 84 is provided with two pins 121 , which form a channel, or thread, that engages guide 120 . The combination of the pins 121 and guide 120 provide the same function as the combination of the helical groove 116 and stop 115 , i.e., convert rotational handle movement into axial stop rod movement. Accordingly, operation of the fourth embodiment is similar to that of the embodiment shown in FIGS. 11 and 12.
Referring to FIGS. 17 through 19, a fifth embodiment of positive stop system 72 comprises a biasing spring 182 , a stop rod 84 , an override handle 114 and a stop system 88 , preferably the stop system shown in FIG. 8 . Biasing spring 182 is attached to stop rod 84 at one end and to the housing 32 at another end.
The housing 32 has a plaque 117 , which may be built separate to or integrated with the housing 32 . A reduced diameter portion 92 of rod 84 extends through housing 32 and is inserted through a slot in plaque 117 . A handle 114 is then attached to the portion of rod 84 extending through plaque 117 .
Further, stop rod 84 has a radial groove 123 disposed on its body, that engages a stop 115 in housing 32 . The combination of the groove 123 and the stop 115 ensure that the rod 84 moves rotationally, rather than axially. Persons skilled in the art will recognize other means to achieve the same function.
Stop rod 84 has a step 122 at its distal end. As shown in FIG. 19, the step 122 is provided so that, upon rotation of rod 84 , the step 122 will either bypass or contact the stop 88 a . The spring 182 biases the rod 84 towards a contacting position.
Accordingly, when the bevel angle needs to be changed, handle 54 is rotated to release housing 32 from table assembly 14 and override handle 114 is rotated, for example, in a counter-clockwise direction, i.e., along direction B, to rotate step 122 to a position at which step 122 does not contact bolt 100 or housing 98 when housing 32 is pivoted on shaft 40 .
Persons skilled in the art will recognize that the spring 182 shown in FIGS. 17 and 18 is a rotational spring. Additionally, such persons will recognize that the same function, i.e., biasing stop rod into its stopped position, can be achieved by rotational springs disposed on the handle 114 , which force the step 122 to rotate into contact with the stops 88 a . Further, persons skilled in the art will recognize that other means, such as elastomeric materials and structures, can be utilized to bias the stop rod 84 into its contacting position.
Referring to FIGS. 20 and 21, a sixth embodiment of positive stop system 72 comprises a biasing spring 123 , a stop rod 84 , an override lever 186 and a stop system 88 , preferably the stop system shown in FIG. 8 . The stop rod 84 is disposed between pivot points 124 and 125 . As shown in FIGS. 20 and 21, the housing includes two inclined surfaces 90 a and 90 b, which in conjunction with pivot points 124 and 125 , allow radial movement of the stop rod 84 about the pivot points. Biasing spring 123 is attached to stop rod 84 at one end and to the housing 32 at another end.
A reduced diameter portion 92 of rod 84 extends through housing 32 and is inserted through a slot 94 in override lever 186 . The lever 186 has a lower lip 186 a, which contacts the portion 92 . In addition, the lever 186 is slidably attached to posts 96 .
Accordingly, when the bevel angle needs to be changed, handle 54 is rotated to release housing 32 from table assembly 14 and override lever 186 is pulled in an upward direction, i.e., along direction Z, to rotate rod 84 about pivot points 124 and 125 to a position at which rod does not contact bolt 100 or housing 98 when housing 32 is pivoted on shaft 40 .
Persons skilled in the art will recognize that the spring 182 shown in FIGS. 17 and 18 is a compression spring. Additionally, such persons will recognize that the same function, i.e., biasing stop rod 84 into its stopped position, can be achieved by linear spring pushing or pulling lever 186 . Further, persons skilled in the art will recognize that other means, such as elastomeric materials and structures, can be utilized to bias the stop rod 84 into its stopping position.
Referring to FIGS. 22 and 23, a seventh embodiment of positive stop system 72 comprises, like the embodiment illustrated in FIGS. 20 and 21, a biasing spring 123 , a stop rod 84 , an override lever 186 and a stop system, preferably the stop system shown in FIG. 8 . The arrangement and operation of the seventh embodiment is similar to the one illustrated in FIGS. 20 and 21. Accordingly, the description of the sixth embodiment should be referred to when studying this embodiment.
Unlike in the sixth embodiment, pivot points 124 and 125 are not present. Instead, the stop rod 84 has a pivot pin 126 about which the stop rod 84 rotates. Accordingly, operation of the seventh embodiment is similar to that of the embodiment shown in FIGS. 20 and 21.
Referring to FIGS. 24 and 25, an eighth embodiment of positive stop system 72 comprises a biasing spring 123 , a stop rod 84 , an override lever 127 and a stop system 88 , preferably the stop system shown in FIG. 8 . The stop rod 84 is connected to the override lever 127 at a pivot axis 127 a. As shown in FIGS. 20 and 21, the housing includes an inclined surface 90 b , which in conjunction with radial movement of override lever 127 about pivot axis 127 a, allows radial movement of the stop rod 84 about the pivot axis 127 a . Biasing spring 123 is attached to stop rod 84 at one end and to the housing 32 at another end.
Accordingly, when the bevel angle needs to be changed, handle 54 is rotated to release housing 32 from table assembly 14 and override lever 127 is rotated, for example, in a clockwise direction, i.e., along direction Y, to rotate rod 84 about pivot axis 127 a to a position at which rod does not contact bolt 100 or housing 98 when housing 32 is pivoted on shaft 40 .
Persons skilled in the art will recognize that the spring 123 shown in FIGS. 24 and 25 is a compression spring. Additionally, such persons will recognize that the same function, i.e., biasing stop rod 84 into its stopped position, can be achieved by a rotational spring pushing or pulling lever 127 . Further, persons skilled in the art will recognize that other means, such as elastomeric materials and structures, can be utilized to bias the stop rod 84 into its stopping position.
Referring to FIGS. 26 through 30, positive stop system 72 comprises a biasing spring 82 , a stop rod 84 , and an overridable, adjustable stop system 88 ′. Biasing spring 82 is inserted into a stepped aperture 90 extending through support housing 32 such that it abuts the step formed within aperture 90 . Stop rod 84 is then inserted through spring 82 and through aperture 90 trapping spring 82 between rod 84 and stepped aperture 90 .
The housing 32 has a plaque 117 , which may be built separate to or integrated with the housing 32 . A reduced diameter portion 92 of rod 84 extends through housing 32 and is inserted through a slot in plaque 117 .
When located in its stopped position, stop rod 84 extends out of housing 32 and into table assembly 14 such that it can engage one of the plurality of adjustable stops 88 c shown in FIG. 26 . Table assembly 14 is shown having an adjustable stop 88 c located at about a 0° bevel angle and at a bevel angle of about 45° on both sides of center.
Each adjustable stop 88 c preferably has a threaded body 131 , a stop pin 128 disposed within the threaded body 131 , and a pin 129 at a distal end of the stop pin 128 . In addition, the adjustable stop 88 c preferably has a spring 130 disposed between the stop pin 128 and the threaded body 131 . The threaded body 131 preferably has a long channel 132 , along which the pin 129 can slide.
As shown in FIG. 29 b , the stop pin 128 can be retracted by pulling out the stop pin 128 from the threaded body 131 , until the pin 129 contacts the end of the channel 132 . In order to put the stop pin 128 in the stopping position, the stop pin 128 is pushed into the threaded body 131 . The pin 129 will maintain the stop pin in the stopping position by riding along the edge of the threaded body 131 . However, it may be preferable to provide a short channel 134 on the threaded body 131 , where the pin 129 can lock into, as shown in FIG. 29 a . The spring 130 will ensure that the pin 129 is kept at the end of the respective channel.
In addition, each adjustable stop 88 c includes a housing 136 . Each housing 136 is shown as an integral part of table assembly 14 but it is within the scope of the present invention to manufacture individual housings 136 and secure them to table assembly 14 if desired. Each housing 136 defines a threaded through bore 135 into which the threaded body 131 is threadably received. The stop pin 128 provides a surface for stop rod 84 to contact when the bevel angle of housing 32 is located at about 0° or about ±45° from the 0° bevel angle as is shown in the preferred embodiment.
The adjustability of each stop 88 c is provided by the threaded connection between the threaded body 131 and housing 98 and this adjustability allows the operator to accurately set these specific bevel angles. An operator need only to lock the stop pin 128 in either channel, and lodge a wrench into cavity 133 to adjust the bevel angles.
When the bevel angle needs to be changed, handle 54 is rotated to release housing 32 from table assembly 14 and stop pin 128 is rotated so that pin 129 leaves the channel 134 and slides along channel 132 . Stop pin 128 is pulled out until the pin 129 hits the end of channel 132 . The stop rod 84 thus does not contact stop pin 128 or housing 98 when housing 32 is pivoted on shaft 40 . If the operator wants to return the stop pin 128 into the stopping position, the operator needs only to push and rotate the stop pin 128 so that pin 129 lodges itself within channel 134 .
The table assembly 14 may further be provided with a ramp 150 . The ramp 150 contacts the stop rod 84 when the miter saw is beveled in a clockwise direction M; i.e., from the −45° bevel angle towards the +45° bevel angle, so that the stop rod 84 retracts and bypasses the 0° bolt.
Persons skilled in the art will recognize that the present embodiment may be implemented with the override button 86 illustrated in FIGS. 6 and 7, instead of plaque 117 . This would allow the operator to withdraw the stop rod 84 to bypass the adjustable stops 88 c and/or to disable the adjustable stops 88 c. Furthermore, if the override button 86 is used, the adjustable stops 88 c may be replaced with the adjustable stops 88 a.
Persons skilled in the art will also recognize that spring 130 need not be disposed between stop pin 128 and threaded body 131 . Instead, the spring 130 may be disposed between the stop pin 128 and the table 14 .
Persons skilled in the art may also recognize that the stop rod 84 may be fixed or may even be a casting in the housing 32 which extends into the table 14 .
Referring to FIGS. 31 through 33, a tenth embodiment of positive stop system 72 comprises a biasing spring 82 , a stop rod 84 and a stop system, preferably one of the stop systems shown in FIGS. 8 through 10. Biasing spring 82 is inserted into a stepped aperture 90 extending through the housing 32 such that it abuts the step formed within aperture 90 . Stop rod 84 is then inserted through spring 82 and through aperture 90 .
The housing 32 has a plaque 117 , which may be built separate to or integrated with the housing 32 . Spring 82 is trapped between plaque 117 and the stop rod 84 . A reduced diameter portion 92 of rod 84 extends through housing 32 and is inserted through a slot in plaque 117 .
An override rod 138 is provided through the housing 32 . The axis of the override rod 138 is preferably substantially perpendicular to the axis of the stop rod 84 . As shown in FIG. 33, the override rod 138 is provided with a rack 140 of teeth, which engage a pinion section 139 of the stop rod 84 .
Further, stop rod 84 has a helical groove 116 disposed on its body, that engages a stop 115 in housing 32 . Accordingly, linear movement of the override rod 138 , for example, along direction X, will cause the rotation of stop rod 84 . Because of the engagement between the stop 115 and the rod groove 116 , stop rod 84 moves axially while rotating, as in a screwing action, within housing 32 between a stop position and a release position with spring 82 biasing stop rod 84 into its stopped position.
Persons skilled in the art will recognize that the spring 82 shown in FIGS. 31 and 32 is a compression spring. Additionally, such persons will recognize that the same function, i.e., biasing stop rod 84 into its stopped position, can be achieved by rotational springs disposed on the stop rod 84 , or linear springs which bias the override rod 138 in the direction opposite to direction X, which force the rod 84 to rotate. Further, persons skilled in the art will recognize that other means, such as elastomeric materials and structures, can be utilized to bias the stop rod 84 into its stopped position.
Referring to FIGS. 34 through 36, an eleventh embodiment of positive stop system 72 comprises a biasing spring 82 , a stop rod 84 and a stop system, preferably one of the stop systems shown in FIGS. 8 through 10. Biasing spring 82 is inserted into a stepped aperture 90 extending through the housing 32 such that it abuts the step formed within aperture 90 . Stop rod 84 is then inserted through spring 82 and through aperture 90 .
The housing 32 has a plaque 117 , which may be built separate to or integrated with the housing 32 . Spring 82 is trapped between plaque 117 and the stop rod 84 . A reduced diameter portion 92 of rod 84 extends through housing 32 and is inserted through a slot in plaque 117 .
An override lever 141 is provided through the housing 32 . The rotational axis of the override lever 141 is preferably substantially perpendicular to the axis of the stop rod 84 . As shown in FIG. 36, the override lever 141 is provided with a pinion section 143 , which engages a rack 142 of teeth disposed on the stop rod 84 .
Accordingly, because of the engagement of the rack 142 and pinion 143 , rotational movement of the override lever 138 , for example, along direction W, is converted into linear movement of stop rod 84 . Thus, stop rod 84 moves axially within housing 32 between a stop position and a release position with spring 82 biasing stop rod 84 into its stopped position.
Persons skilled in the art will recognize that the spring 82 shown in FIGS. 34 and 35 is a compression spring. Additionally, such persons will recognize that the same function, i.e., biasing stop rod 84 into its stopped position, can be achieved by rotational springs disposed on the stop rod 84 and/or on the override lever 141 . Further, persons skilled in the art will recognize that other means, such as elastomeric materials and structures, can be utilized to bias the stop rod 84 into its stopped position.
The above detailed description describes different embodiments of the present invention. Persons skilled in the art may recognize other alternatives to the means disclosed herein, such as using non-adjustable fixed castings instead of the adjustable stops 88 a , or placing the adjustable stops 88 a on the housing 32 , while placing the stop rod 84 , and/or the means to retract the rod, on the table 14 . Similarly, persons skilled in the art will recognize that a knob can be placed on the stop rod 84 to manually withdraw it from the stopping position. However, all these additions and/or alterations are considered to be equivalents of the present invention. | A compound miter saw includes a table on which a workpiece is placed, a miter saw unit supporting a saw blade, and a housing pivotally supporting the miter saw unit related to the table in such a manner that the miter saws unit is at least laterally pivotable. Further, the miter saw includes a bevel mechanism for selectively determining the lateral position of the miter saw unit at any of a plurality of pivoted positions, including a vertical position where the saw blade is positioned substantially vertically relative to the table, and leftward and rightward pivoted positions where the blade is inclined laterally leftwardly and laterally rightwardly from the vertical position. The bevel mechanism includes a movable rod and three fixed stop members, the rod being operable to move between a first rod position abutting one of the fixed stop members and a second rod position not abutting the one of the fixed stop members so as to permit the lateral pivotal movement of the miter saw unit. The first fixed stop member is disposed so that the rod abuts the first fixed stop member when the miter saw unit is at the vertical position. Similarly, the second fixed stop member is disposed so that the rod abuts the second fixed stop member when the miter saw unit is leftwardly pivoted at a first predetermined angle from the vertical position. Further, the third fixed stop member is disposed so that the rod abuts the third fixed stop member when the miter saw unit is rightwardly pivoted at a second predetermined angle from the vertical position. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of U.S. patent application No. 09/109,911, filed Jul. 2, 1998, the disclosure of which is incorporate
FIELD OF THE INVENTION
[0002] This application relates to a headband or a fastening device for applying pressure to the back of a human head for therapeutic effects, and more particularly to a device that applies bilateral pressure to the occipital region to improve the circulation of cerebrospinal fluid.
BACKGROUND OF THE INVENTION
[0003] It is believed that the human body is continually subjected to physical and other forms of stress that can stimulate the occurrence of a variety of ailments or otherwise cause detrimental effects to one's physical health or well-being. It is believed that these physical stresses can include injuries stemming from birth trauma, automotive accidents, athletic exertions, or postural problems. It is further believed that other forms of stress can occur from psychological tension or emotional disturbances, which may be caused by depression or anxiety. The occurrence of stress is believed to manifest as muscle tension, which in turn may tighten the muscles around the head and neck. It is believed that severe or prolonged muscle tension in the area surrounding the cranium may distort the alignment of cranial bones.
[0004] Within the human cranium, it is believed that cerebrospinal fluid fills the ventricles of the brain and occupies the subarachnoid space. It is believed that cerebrospinal fluid is a clear watery fluid that remains in constant circulation throughout the brain and the spinal cord. It is further believed that cerebrospinal fluid acts as both a protective cushion against injury and a carrier of nutrients and proteins that provide nourishment to the brain for normal functioning.
[0005] It is believed that cerebrospinal fluid drains from the lateral ventricles through the interventricular foramina of Monro into the third ventricle. This fluid is then believed to combine with fluid produced by the choroid plexus of the third ventricle, and then pass through the cerebral aqueduct of Sylvius into the fourth ventricle. The fluid is then believed to escape through openings in the roof of the fourth ventricle, the median foramen of Magendie, and the two lateral foramina of Luschka. From the foramina of the fourth ventricle, it is believed that the fluid enters the subarachnoid space. Henry Gray and Charles Goss, Gray's Anatomy, Lea & Febiger, 1973.
[0006] It is believed that there are four major rhythmic pulsations from fluid circulation within the cranium. It is believed that blood flows from cardiovascular circulation between 60 to 72 times per minute to provide circulation throughout the brain and the entire body. It is also believed that oxygen is provided to the vascular system through respiratory circulation at 14 to 19 times per minute. And it is further believed that there are sutural pulsations at 14 to 19 times per minute and dural pulsations at 6 to 8 times per minute, which are measured as a cranial rhythm index. These rhythmic pulsations are believed to affect the circulation of cerebrospinal fluid.
[0007] With regard to rhythmic dural pulsation, it is believed that flexion/extension movement provides tension changes to the membrane within the dural system. Dural flexion is believed to occur when the distance from the internal margin of the lamboid and the superior posterior margin of the sphenobasilar articulation decrease in distance. This decrease in distance is believed to produce a slight tension to the external margin of the falx cerebrum, falx cerebellum, and the falx tentorium. The internal margin of the membrane is believed to produce a slight relaxation of the falx cerebrum, falx cerebellum, and the falx tentorium. It is believed that this membrane tension change allows the external cisterns and superior sagital sinus to decrease in volume and size. When this takes place, it is also believed that the ventricles of the brain increase in volume and size. It is believed that the cerebrospinal fluid moves with the fluctuations of this rhythmic cycle.
[0008] It is believed that if the skeletal structure in the cranium is improperly aligned, the cerebrospinal fluid cannot provide optimal circulation throughout the cerebrum. By applying pressure to the cranium, it is believe to be possible to stimulate greater circulation to reverse, or at least reduce the harmful effects of sub-optimal cerebrospinal fluid flow. It is believed that in 1939, Dr. William Garner Sutherland, DO, experimented with a technique of applying pressure to the occipital region of the head to cause a compression of the fourth ventricle, adjacent to the cerebellum. Traditionally called a “CV-4” technique, it is believed that a therapist can press against the occiput and thus apply resistance against movement to modify the activity of the craniosacral system. It is believed that this induces a “still-point” that can enhance the flow of cerebrospinal fluid throughout the cerebrum. Upon reaching a “still-point,” it is believed that a patient can enjoy a sense of relaxation.
[0009] It is believed that a patient must remain immobile in order to induce a “still-point.” Thus, it is believed that previous methods or devices applying pressure to the occipital region require the assistance of a therapist, or devices that require a patient to remain immobile while receiving treatment. The inconvenience of relying upon another to provide treatment and remaining in a still position during a treatment process is believed to greatly reduce the benefits of the treatment and limit the opportunities for achieving a state of relaxation from the application of occipital pressure.
[0010] It is believed that there is a need for an apparatus and a method of applying occipital pressure that overcomes the problems and limitations of the previous methods and devices.
SUMMARY OF THE INVENTION
[0011] The present invention provides an apparatus for applying occiputal pressure to a human head. The human head has frontal, parietal, and occipital bones. The frontal bones generally are on a front portion of the head, the occiputal bones generally are on a back portion of the head, and the parietal bones generally extend between the frontal and parietal bones. The apparatus comprises a harness adapted to overlie the frontal bones, and a pad adapted to apply a therapeutic force to the occiputal bones. The pad has first and second ends attached to the harness. And the pad has first and second protrusions that extend generally toward the harness and that are adapted to overlie respective ones of the occipital bones.
[0012] The present invention also provides an apparatus for applying occiputal pressure to a human head. The human head has frontal, parietal, and occipital bones. The frontal bones generally are on a front portion of the head, the occiputal bones generally are on a back portion of the head, and the parietal bones generally extend between the frontal and parietal bones. The apparatus comprises a band adapted to surround the human head, at least one protrusion, and a cushion. The band has a first portion adapted to overly the occipital bones, a second portion adapted to overly the frontal bones, and connecting portions that extend between the first and second portions. The at least one protrusion extends inwardly from the first portion and is adapted to apply a therapeutic force to the occipital bones. The cushion extends inwardly from the second portion and is adapted to apply a reaction force to the frontal bones. The reaction force opposes the therapeutic force.
[0013] The present invention further provides a method of applying theraputic forces to a human head. The human head has frontal, parietal, and occipital bones. The frontal bones generally are on a front portion of the head, the occiputal bones generally are on a back portion of the head, and the parietal bones generally extend between the frontal and parietal bones. The method comprises surrounding the human head with a band, the band having at least one inwardly directed protrusion and a cushion; orienting the cushion to overly the frontal bones; orienting the at least one inwardly directed protrusion so as to overly the occipital bones; and adjusting the band so as to enhance a flow of cerebrospinal fluid within the human head
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The accompanying drawings, which are incorporated herein and constitute part of this specification, illustrate presently preferred embodiments of the invention, and, together with the general description given above and the detailed description given below, serve to explain features of the invention.
[0015] [0015]FIG. 1 is a perspective view of a preferred embodiment of an apparatus for applying cranial occipital pressure.
[0016] [0016]FIG. 2A is a perspective view of a plate with attached protrusions to apply occipital pressure.
[0017] [0017]FIG. 2B is a perspective view of a curvilinear plate with integral protrusions to apply occipital pressure.
[0018] [0018]FIG. 3 is a top view illustrating a placement on a head of the apparatus shown in FIG. 1.
[0019] [0019]FIG. 4 is a rear view illustrating the placement on a head of the apparatus shown in FIG. 1.
[0020] [0020]FIG. 5 is a profile view illustrating the placement on a head of the apparatus shown in FIG. 1.
[0021] [0021]FIG. 6 is a perspective view of another preferred embodiment of an apparatus for applying cranial occipital pressure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0022] Reference will now be made in detail to the preferred embodiments that are illustrated in the accompanying drawings, wherein like numerals indicate like elements throughout. Certain terminology is used in the following description to facilitate the description only and is not intended to be limiting in its use.
[0023] Referring to FIG. 1, a headband 100 preferably comprises a band 102 connected to a forehead pad 104 . The illustrated headband 100 is example of many types and styles of devices that can be used to surround a head. The band 102 preferably includes a strap 106 and a buckle 108 . The strap 106 interlinks within the buckle 108 to form the band 102 that connects the forehead pad 104 to a therapeutic pad 110 . In the preferred embodiment shown in FIG. 1, there is a second band composed of a second strap and a second buckle for forming a symmetrical harness attached to the therapeutic pad 110 . The strap 106 can be secured with respect to the buckle 108 by a hook and loop fastener, e.g., on an outer strap surface disposed away from the head. The strap 106 can also comprise materials such as leather or cotton, and may be secured by other means, such as by buttons or snaps.
[0024] The preferred therapeutic pad 110 is configured to apply bilateral pressure at the back of the head when worn. The therapeutic pad 110 can be made of any material suitable for maintaining a force against the head, including nylon, rayon, cotton, leather, etc. As shown in FIG. 1, the therapeutic pad 110 can be sewn closed around the sides and an upper portion, and can contain an inner material shaped to form two protrusions 112 appearing along the inner surface. The protrusions are symmetrical about the center of the pad to apply the desired bilateral pressure when worn.
[0025] Referring also to FIG. 2A, the two protrusions 112 can be two generally semispherical objects placed within the therapeutic pad 110 . The semispheres can be made of rubber, foam, metal, plastic, or any other material sufficient to apply pressure against the occiput. The semispheres can also be filled with a fluid that be heated or chilled. In FIG. 2A, the two semispherical protrusions 112 are connected through an attachment plate 114 , which can be made of metal, plastic, cloth, etc., that is placed within the pad 110 . The spheres can also be sewn directly into the pad 110 .
[0026] In an alternative embodiment shown in FIG. 2B, the protrusions 112 can be formed within the therapeutic pad 110 by a single curved structure, such as a piece of metal formed to provide the symmetrical protrusions. In FIG. 2B, a curved portion 116 serves to apply bilateral pressure to the occiput. The curved portion 116 can be sewn directly into the pad 110 . The pressure points for applying occipital pressure can be adjusted by bending the curvilinear structure.
[0027] FIGS. 3 - 5 illustrate how the therapeutic pad relates to the frontal F, parietal P, and occipital O bones. In particular, FIGS. 3 and 4 illustrate how the therapeutic pad contacts the occiput in relation to the primary cranial bones. Although the headband in FIG. 3 is shown making contact with the parietal bones, i.e., the sides of the cranium, the therapeutic pad 110 can be of sufficient width such that, when the band is attached about the ends of the pad, the bands do not contact the head when worn.
[0028] The forehead pad 104 can provide cushioning to the forehead to facilitate the comfort when wearing the mounting apparatus. Additionally, the forehead pad 104 can position the therapeutic pad on the cranium such that the force applied to the occiput is at the proper angle and placement. In accordance with the preferred embodiment, the forehead pad 104 should be slightly superior to the frontal eminence. The force of the protrusions 112 that is applied to the occiput can depend on the adjustments to each band 102 . The resulting effective pressure upon the head should be approximately one to five pounds.
[0029] In FIG. 4, the two protrusions 112 , which are shown with hidden lines, are located at the proper position for applying pressure to the occiput. Preferably, the two protrusions 112 should be equidistant from the midline to the right and to the left on the occiput. The protrusions 112 should be superior to the external occipital nucal ridge, and inferior to the lamboidal suture.
[0030] [0030]FIG. 5 also illustrates the proper positioning of the headband 100 according to a preferred embodiment. The headband 100 can be worn while standing, sitting, or exercising. With the headband 100 properly in place, a constant pressure can be exerted against the occiput for applying resistance to the dural rhythmic pulsations. The wearer can then experience a relaxing, therapeutic effect while remaining mobile and capable of continuing normal, daily activities.
[0031] A variety of other designs and modifications can aid to make the device more fashionable or comfortable while still applying occipital pressure. The therapeutic pad can be positioned with respect to the occiput by means of a hat or a cap, which serves to cover the head and disguise the apparatus from public view.
[0032] As shown in FIG. 6, the therapeutic pad 110 can be provided in combination with a visor to cover or shade the face while wearing the apparatus. For example, a bill 118 can be attached to the outer surface of the forehead pad 104 .
[0033] As can be readily understood, the hat or cap would include a harness as part of its structure for holding the therapeutic pad against the occiput. This hat or cap, which can be a modified conventional baseball cap, can include side straps for adjusting the size of the cap for different head sizes or different desired tension levels at the sides of the cap. A conventional hat or cap can also be modified to apply bilateral occipital pressure by inserting therapeutic padding within an inner portion at the back of the cap. The back padding can be temporarily inserted and attachable to the inner portion of the cap by Velcro hook-and-loop fasteners.
[0034] When wearing one of the preferred embodiments, the applied bilateral occipital pressure puts the cranium in a state of flexion. In an alternative embodiment, additional pressure points can be applied to the frontal bone in the cranium to enhance the relaxing and therapeutic effects induced by applying occipital pressure. In particular, by supplementing the forehead pad 104 with two projections (not shown), the wearer can also benefit from bilateral frontal compression. Optional removable pads can be added to the inside of a front cushion, or a front portion of a visor or hat to apply bilateral frontal pressure as desired. The frontal pads can be attached (e.g., glued or sewn) onto a removable hook-and-loop Velcro strap that can be affixed to the inner side of the forehead cushion 104 . Alternatively, the frontal pads can be directly attached to the inner side of the forehead cushion 104 by Velcro attachments. The frontal pads can be made removable because it may not be desirable in some cases to apply both frontal and occipital pressures.
[0035] It is also possible to wear one of the preferred embodiments, e.g., as shown in shown in FIG. 5, in reverse. As such, bilateral pressure would be applied to the frontal bone, and lateral, uniform pressure would be applied to the occiput.
[0036] While the present invention has been disclosed with reference to certain preferred embodiments, numerous modifications, alterations, and changes to the described embodiments are possible without departing from the sphere and scope of the present invention, as defined in the appended claims. Accordingly, it is intended that the present invention not be limited to the described embodiments, but that it have the full scope defined by the language of the following claims, and equivalents thereof. | An apparatus and method for applying occiputal pressure to a human head. The human head has frontal, parietal, and occipital bones. The frontal bones generally are on a front portion of the head, the occiputal bones generally are on a back portion of the head, and the parietal bones generally extend between the frontal and parietal bones. The apparatus comprises a harness adapted to overlie the frontal bones, and a pad adapted to apply a therapeutic force to the occiputal bones. The pad has first and second ends attached to the harness. And the pad has first and second protrusions that extend generally toward the harness and that are adapted to overlie respective ones of the occipital bones. | 0 |
BACKGROUND OF THE INVENTION
This invention generally relates to guiding members for vascular catheters useful in such procedures as angiography, angioplasty, valvuloplasty and the like.
In typical percutaneous transluminal coronary angioplasty (PTCA) procedures, a guiding catheter having a preformed distal tip is percutaneously introduced into the cardiovascular system of a patient through the brachial or femoral arteries and advanced therein until the distal tip thereof is in the ostium of the desired coronary artery. A guidewire and a dilatation catheter having a balloon on the distal end thereof are introduced through the guiding catheter with the guidewire slidably disposed within an inner lumen of the dilatation catheter. The guidewire is first advanced into the patient's coronary vasculature until the distal end thereof crosses the lesion to be dilated and then the dilatation catheter is advanced over the previously introduced guidewire until the dilatation balloon is properly positioned across the lesion. Once in position across the lesion, the flexible, relatively inelastic balloon is inflated to radially compress atherosclerotic plaque against the inside of the artery wall to thereby dilate the lumen of the artery. The balloon is then deflated so that the dilatation catheter and the guidewire can be removed and blood flow resumed through the dilated artery.
Guidewires for vascular use usually comprise an elongated core member which is tapered toward the distal end, a helical coil disposed about and secured to the tapered distal end of the core member and a rounded plug provided on the distal tip of the coil. Preferably, the plug and at least part of the coil are formed of highly radiopaque materials to facilitate fluoroscopic observation thereof. There are two general types of guidewire constructions. In the first type, the core member extends through the coil to the plug in the distal tip thereof. In the second type, the core member extends into the interior of the helical coil, but terminates short of the plug in the distal tip. A shaping ribbon is secured directly or indirectly to the core member and the ribbon is secured to the radiopaque plug as shown.
Steerable dilatation catheters with built-in or fixed guidewires or guiding elements are used with greater frequency because the deflated profile of such catheters is generally smaller than conventional dilatation catheters with movable guidewires or elements having the same inflated balloon size.
Further details of angioplasty procedures and the devices used in such procedures can be found in U.S. Pat. No. 4,332,254 (Lundquist); U.S. Pat. No. 4,323,071 (Simpson-Robert); U.S. Pat. No. 4,439,185 (Lundquist); U.S. Pat. No. 4,468,224 (Enzmann et al.) U.S. Pat. No. 4,516,972 (Samson); U.S. Pat. No. 4,538,622 (Samson et al.); U.S. Pat. No. 4,554,929 (Samson et al.); and U.S. Pat. No. 4,616,652 (Simpson). Each of the above references is incorporated herein in their entirety.
Further details about guidewires can be found in U.S. Pat. No. 4,538,622 (Samson et al.); U.S. Pat. No. 4,554,929 (Samson et al.) U.S. Pat. No. 4,619,274 (Morrison); and U.S. Pat. No. 4,721,117 (Mar et al.).
Further details of low-profile steerable dilatation catheters may be found in U.S. Pat. No. 4,582,181 (Samson); U.S. Pat. No. 4,619,263 (Frisbie et al.); U.S. Pat. No. 4,641,654 (Samson et al.); and U.S. Pat. No. 4,664,113 (Frisbie et al.).
While the prior guidewires and guide members have for the most part performed well, there was always a need for increased flexibility and the increased torquability and pushability of the distal tip of the guidewire. With the prior devices, improvements in flexibility usually involved some loss of torquability and improvements in torquability usually involved some loss in flexibility. What has been needed and heretofore unavailable is some means to improve both the flexibility and torquability of the distal tip of the guidewire. The present invention satisfies that need.
SUMMARY OF THE INVENTION
This invention is directed to a guidewire or guiding member design having both improved flexibility and torquability, particularly in the distal portion thereof.
The guiding member of the invention generally includes an elongated core member which preferably tapers toward the distal end thereof. A plurality of interfitting links are provided on the distal portion of the core member to facilitate improvements in flexibility and torquability. Means are provided on the proximal end of the core member to apply torque thereto which is transmitted through the core member to the distal portion thereof having a section of loosely interfitting links.
In a presently preferred embodiment, the links comprise a relatively flat base and a plurality of vertically extending arms which fold inwardly in the upper portion thereof to engage the upper surface of the flat base of the adjacent link, with the length of the upwardly extending portion of the arms being chosen to provide a desirable amount of axial movement between the links. An opening, preferably centered, may be provided in the flat base of the link to receive the distal portion of the core member or a shaping ribbon which extends from the distal end of the core member to the distal tip of the flexible link section with a rounded plug formed in the distal end thereof.
The ends of the arms which extend upwardly from the flat base and are bent inwardly between the arms of the adjacent link are preferably provided with an enlargement on the end thereof for interlocking the links and to thereby prevent their separation, particularly during vascular procedures. Lost motion or winding between the individual links can be minimized by minimizing the spacing between the interfitting arms of the links.
The length of the interfitting links generally will assume the shape imposed on the shaping member or the distal end of the core which passes through the opening provided in the flat bases of the links.
These and other advantages of the invention will become more apparent from the following detailed description thereof when taken in conjunction with the accompanying exemplary drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevation view partially in section of a steerable, fixed wire dilatation catheter embodying features of the invention;
FIG. 2 is a perspective view of the distal portion of the dilatation catheter shown in FIG. 1;
FIG. 3 is a perspective view of a link of a preferred embodiment;
FIGS. 4 and 5 illustrate the interfitting of the links, such as shown in FIG. 3 to form the distal portion of the guiding member shown in FIGS. 1 and 2;
FIG. 6 is a side elevation view of a guidewire embodying features of the invention;
FIG. 7 is a plan view of an alternative link preform;
FIG. 8 is a perspective view of the link preform shown in FIG. 7 finally formed;
FIG. 9 is an elevation view of several links as shown in FIGS. 7 and 8 in an assembled condition;
FIG. 10 is a plan view of an alternative link preform;
FIG. 11 is a perspective view of the link preform shown in FIG. 10; and
FIG. 12 is an elevation view of several links in an assembled condition.
DETAILED DESCRIPTION OF THE INVENTION
Reference is made to FIGS. 1 and 2 which illustrate a steerable dilatation catheter assembly 10 having a fixed guidewire or guiding member 11 therein embodying features of the invention. The catheter assembly 10 generally comprises an elongated tubular body 12 having a balloon member 13 on the distal portion thereof adjacent the distal end and a multi-arm adapter 14 on the proximal end of the tubular body 12. A core member 15 is disposed within an inner lumen 16 provided within the tubular body 12 with a tapered distal portion 17.
A flexible section 20 of the catheter 10 includes a plurality of interfitting links 21 and is secured to the core member 15 at location 22 by means of welding, brazing, soldering, adhesives or the like. A shaping member or ribbon 23 extends through aperture 24 provided in the links 21 from the bond location 22 which secures the proximal end of the shaping member 23 to the core member 15 to the rounded plug 25 provided on the distal tip of the flexible link section 20.
A torquing knob 26 is provided on the proximal end of the core member 15 in a conventional fashion to allow the manual rotation of the guiding member or guidewire 11 in a desired manner to guide the catheter assembly 10 through a patient's vasculature. The two-arm adapter 27 on the proximal end of tubular member 12 has an arm 28 for injecting inflation fluid through the lumen 16 to the interior of balloon 13.
A preform 30 from which an individual link 21 can be made is shown in FIG. 3. As indicated, the preform 30 includes a base 31, preferably flat, having an aperture 24 and a plurality of projecting arms 32 extending radially outwardly from the base 31. However, as shown in FIGS. 4 and 5, the individual links 21 are interfitted by first placing one preform 30 on top of another, radially offsetting the upper preform so that the arms 32 of one of the preforms extend between the arms of the adjacent preform, as shown. The arms 32 of the lower preform 30 are folded upwardly at the junction thereof with the base 31 and then are folded inwardly again at an intermediate location 33, as shown in FIG. 5, so that the inwardly folded section 34 of the arms 32 limits the maximum axial displacement between adjacent links. Additional preforms are added in the same manner in order to form the flexible link section 20. The ends 35 of the inwardly folded arm section 32 are enlarged, preferably flaring outwardly, as shown, so that when the arm sections 34 are folded inwardly the links 21 interlock to thereby prevent the separation thereof during vascular procedures. The transverse dimension (i.e., the width) of the arms 32 controls the amount of relative axial rotation between adjacent links. The larger the width dimension, the less relative axial rotation is allowed between links 21 and thus the less lost motion from the proximal to the distal end of the flexible link section 20. The length of the shaping ribbon 23 extending between the bonding location 22 and the plug 25 at the distal tip of the flexible section 20 can determine the relative axial placement of the individual links 21 within the displacement allowed by the arms 32 of each link 21.
FIG. 6 illustrates another embodiment of the invention involving a movable guidewire 40 for use within the inner lumen of a dilatation catheter, not shown. The guidewire 40 generally comprises a relatively thin core 41 with a short tapered distal portion 42. All or a substantial part of the guidewire 40 may be provided with a thin Teflon coating (not shown) of about 0.0005 to about 0.001 inch (0.013 to 0.025 mm) to facilitate the passage thereof through the central lumen of the dilatation catheter. The tapered distal portion 42 has two sections 43-45 of progressively smaller cross-sectional dimensions with gentle tapers 46-48 between the progressively smaller sections. This embodiment has a standard design wherein section 45 extends to the plug 52 and is flattened to allow shaping. A flexible link section 53 is disposed about the short tapered distal portion 42 of the guidewire 40. The proximal end of the section 53 is secured to the distal portion 42 by welding, brazing, soldering, or adhesive at location 51. The distal end of the flexible link section 53 is secured to the plug 52. If desired, the entire length of the link section 53 may be covered by a flexible protective sheath 54, such as rubber, elastomer or the like. The distal end of the core 41 could be provided with a distal section, as shown in FIG. 1, if desired. The link section 53 typically has a length from about 1 to about 3 cm and in one presently preferred embodiment, at least some of the links are fabricated from a sheet of radiopaque material, such as molybdenum, rhenium, palladium, platinum, tungsten, and alloys thereof to make the link section more visible under fluoroscopic examination. Alloys of molybdenum and rhenium have been found to be particularly suitable with a nominal composition of 50 percent molybdenum and 50 percent rhenium being preferred. The links may also be made of stainless steel and NITINOL.
An alternative link embodiment is illustrated in FIGS. 7-9. The link preform 60, best shown in FIG. 7, has a pair of opposing discs 61 and a pair of opposing socket sections 62 which are secured to the base 63 which has an aperture 64 therein which is adapted to receive a guiding element (not shown). As depicted in FIGS. 8 and 9, the discs 61 are bent along lines 65 in one axial direction and the socket sections 62 are bent along lines 66 in an axial direction opposite to that of the discs 61. The discs 61 of one link interfit the recess or socket 67 in an axially adjacent link which, as shown in FIG. 9, allows limited movement between the links, yet facilitates the transmission of torque between the links. Preferably, the socket sections 62 and the discs 61 are curved so as to form a generally cylindrical shape.
FIGS. 10-12 illustrate another alternative link design which is suitable for use in the present invention. The link preform 70 is best shown in FIG. 10, whereas the forming and operation of the links are best shown in FIGS. 11 and 12. The preform 70 has a pair of opposing arms 71 which have rounded enlarged ends 72, a pair of opposing socket sections 73 and 74, and a central aperture 75 in the base 76 which is adapted to receive a guiding element (not shown). The arms 71 are bent axially in one direction at fold lines 77 and socket sections 73 and 74 are bent in the same axial direction along fold lines 80 and 81, as shown in FIG. 11. The distal tip of the arms 71 are bent inwardly, as shown in FIG. 11, so as to fit within the socket 82 of an adjacent link and be locked therein by the enlarged end 72 when the socket sections 73 and 74 are bent into their final positions. This construction allows pivotal movement between the links as in the previously described embodiments and provides for the transmission of torque between the links.
Generally, the size and materials of construction for the guidewire or guide element may be conventional, except as noted otherwise. Modifications and improvements can be made to the invention without departing from the scope thereof. | A guidewire or guiding element for vascular catheters, particularly balloon dilatation catheters having an elongated core member with a tapered distal portion with a flexible length of interfitting links on the tapered distal portion. The individual links generally comprise a base with an aperture therein and a plurality of upwardly extending arms with the ends of the arms bent inwardly toward the longitudinal axis of the flexible length to engage the base of an adjacent link. Improved flexibility and torquability are provided by the flexible length of interfitting links. | 0 |
FIELD OF THE INVENTION
[0001] The object of the present invention is a handwheel for hydraulic valve provided with indicator of the level of opening of the same valve.
BACKGROUND OF THE INVENTION
[0002] More particularly the present invention relates to a handwheel for valve provided with an indicator of level of opening which exploits the particular kinematism apt to produce, univocally and ruggedly, the indication of the level of opening of the valve and to allow, at the same time, easy reading of the position of opening of the same.
[0003] As is known, hydraulic valves are typically provided with manoeuvre members defined by a lever or by a handwheel apt to allow the rotation movement of a sphere or translation of a gate or globe to perform the opening/closure of the valve and the choking of the same, so as to regulate the parameters of the flow processed.
[0004] For example, in the case of shut-off valves, the important positions are only two, i.e. the position of opening and of closure of the valve and, therefore, an indication of the intermediate positions is not necessary.
[0005] Contrarily, in the case of valves of calibration or balancing or the like, for the correct use of the valve it is appropriate to be able to allow the user to read, simply and easily, the degree of opening/closure of the valve. In some cases actual industry regulations impose the use of an indicator of the level of opening integrated with the valve (for example BS7350 (British Standard) for globe balancing valves).
[0006] Considering the valves wherein the shutter is actuated by means of a rod or screw, the movement of opening/closure of the valve is of the rotary type and performed by imparting on said rod or screw a certain number of turns, for example by means of a handwheel, in such a way as to allow the passage from a position of maximum opening to one of maximum closure.
[0007] In globe balancing valves, for example, the manoeuvre handwheel has to be provided with an indicator apt to indicate the degree of opening and, consequently, the position of regulation of the same valve with the precision of the tenth of turn. For example the indication 4.2 corresponds to an opening of four whole turns plus two tenths of a turn, i.e. (360° x4)+(36° x2)=1512° of rotation of the manoeuvre member.
[0008] Multiple mechanisms and kinematisms are traditionally used to form the indicators of the degree of opening of a hydraulic valve.
[0009] Generally the degree of opening of the valve is indicated by means of two figures (the figure of the units and the figure of the decimals) displayed in two different windows or in two different positions of the manoeuvre/regulation handwheel.
[0010] In most cases the figure indicating the whole number of turns of opening is displayed inside a window formed on the handwheel, located either in the lateral part or in the upper part of the same handwheel.
[0011] A known handwheel with indicator of the degree of opening is schematised in FIG. 1 and has the figure indicating the whole number of turns written on the base of a cylindrical wheel 10 , hinged on an axis integral with a knob 11 , and actuated by means of a mechanism of the pin-gear wheel ( FIG. 1 ) wherein said driven member or wheel has a series of equally distanced compartments 12 inside whereof a rung 14 engages, integral with a fixed base 16 whereon the decimal figures are indicated. The rung 14 meshes with a compartment 12 only once per turn, making the driven wheel 10 rotate through the angular interval necessary for revealing the next figure.
[0012] According to another known embodiment schematised in FIG. 2 the whole and decimal figures are given on the lateral surface of a cylindrical drum 18 which is defined by two coaxial idle wheels 18 ′ and 18 ″ whereon the figures indicating the whole number of turns and the decimal figures are given respectively. The cylindrical drum 18 is set in rotation by means of a drive wheel 19 provided with a rung 19 ′ apt to engage with a cogged profile of the idle wheel 18 ′ and a cogged ring nut 19 ″ apt to mesh with a conjoined cogged profile of the idle wheel 18 ″.
[0013] According to further known embodiment solutions, such as for example the one schematised in FIG. 3 , the figure indicating the tenths of a turn is printed on a ring 20 integral with a mobile part 21 of the manoeuvre handwheel, while the figure indicating the units is given on a wheel 22 actuated by a mechanism of the pin-gear wheel.
[0014] However these embodiment solutions, exploiting a discontinuous coupling between the driven member and the driving member, require optimal manufacture and high precision in the production of the components apt to enter into a coupling one with the other. This entails a disadvantage linked to the fact that imprecise manufacture may entail the “slipping” of some meshings during the phases of manoeuvre with consequent imprecisions in the indication of the figures relating to the degree of opening of the valve.
[0015] A further disadvantage of the aforesaid known embodiment solutions is represented by the fact that the wheel bearing the figures indicating the whole number of turns or units is always an idle wheel and, consequently, maintains the correct position as a function only of the static friction appropriately designed and produced. Any imprecision whatsoever in manufacture can entail an increase in the clearances between the couplings, reducing said friction with correlated random movements of the driven wheel and consequent imprecisions in the indication of the degree of opening of the valve.
[0016] Another technical solution is schematised in FIG. 4 . The figure indicating the tenths of a turn, given on the mobile part 23 of the manoeuvre handwheel, is displayed through a window 24 formed on a fixed base 25 of the same manoeuvre handwheel, while the figure indicating the whole numbers is printed on a slider 26 coupled to the mobile part 23 via a mechanism of the screw-lead screw type which performs the movement and consequent display of the figures.
[0017] However these traditional solutions, as well as disadvantages linked to the presence of idle wheels, can also have further major disadvantages linked, for example, to the fact that the movement and the display of the figures are actuated by means of a continuous coupling in which the figure of the units is displayed gradually and continuously, reducing the ease of reading.
[0018] Similar disadvantages can also be found in US2013/0133763 in which reference is made to a handwheel for valve provided with an indicator of position and elements of magnetic coupling, with said handwheel comprising a container element provided with a support element, a first shaft with a motor gear, a rotating element of connection between the support element and the first shaft, a train of gears coupled to the motor gear and configured to move a position indicator needle, a first magnet attached to the support element, a second magnet attached to an assembly device for the valve control handwheel and with said first and second magnets configured to maintain the support element in a stationary position with respect to the assembly device for the valve control handwheel.
SUMMARY OF THE INVENTION
[0019] The object of the present invention is that of obviating the disadvantages stated above. More particularly the object of the present invention is that of providing a handwheel for hydraulic valve provided with indicator of the level of opening of the valve apt to allow the display of the degree of opening of the valve by means of a continuous kinematic coupling.
[0020] A further object of the present invention is that of providing a handwheel for hydraulic valve which is precise in the display of the figures indicating the degree of opening of the valve and for which the sensitivity to possible imprecisions of manufacture linked to the process of industrial production of the components constituting the same handwheel is lowered.
[0021] A further object of the present invention is that of providing a handwheel for hydraulic valve apt to allow a simple and easy display of the degree of opening of the same valve.
[0022] A further object of the present invention is that of making available to users a handwheel for hydraulic valve suitable for guaranteeing a high value of resistance and reliability in time and such, moreover, as to be able to be easily and economically manufactured.
[0023] These and other objects are achieved by the invention which has the features as claimed in claim 1 .
[0024] According to the invention a handwheel is provided for hydraulic valve provided with numerical indicator of the valve opening level, comprising a base-body or fixed element apt to be stably restrained with respect to the valve body and supporting a mobile element rotatably coaxial with respect to said base-body, connected with a member for manoeuvre of the valve and provided with a knob apt to be gripped by a user in order to impart a rotation to said manoeuvre member corresponding to the value or degree of opening required for the valve indicated by figures displayed through an opening or window of said knob, said base-body and mobile element rotatably co-operating one with the other by means of a kinematic continuous coupling.
[0025] Advantageous embodiments of the invention are disclosed by the dependent claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] The constructional and functional features of the handwheel for hydraulic valve provided with indicator of the level of opening of the valve will be made clearer by the following detailed description, in which reference is made to the accompanying drawings which represent a preferred and non-limiting embodiment thereof and in which:
[0027] FIGS. 1 to 4 show schematically some known embodiments or solutions for regulation handwheel described previously, shown in an axonometric view;
[0028] FIG. 5 shows schematically a side view of the handwheel for hydraulic valve provided with indicator of the level of opening of the valve of the present invention;
[0029] FIG. 6 shows schematically a sectioned view along an axial plane of the handwheel for hydraulic valve of the invention;
[0030] FIG. 7 shows schematically a view from above of the handwheel for hydraulic valve of the invention;
[0031] FIG. 8 shows schematically a exploded axonometric view of the handwheel for hydraulic valve of the invention.
[0032] Referring to FIGS. 5 to 8 , the handwheel for hydraulic valve provided with indicator of the level of opening of the regulation valve of the present invention, denoted overall by 30 in the aforementioned drawings, comprises a base-body 32 defining a fixed element apt to be stably restrained with respect to the body of the regulation valve (not shown in the drawings) and supporting a mobile element 34 coaxial to said base-body and connected to the member of manoeuvre of the valve (likewise not shown in the drawings) defined by a screw or rod.
DETAILED DESCRIPTION OF THE INVENTION
[0033] The base-body 32 comprises a lower portion 35 , tubular in shape and apt to be fitted on the regulation valve, and an upper portion 36 , developed, starting from an end opposite the one turned in the direction of the valve manoeuvre member, by way of a collar circumferentially developed along a plane perpendicular to the axis of the lower portion 35 .
[0034] On the upper face of the upper portion 36 a rung 40 is developed in a direction perpendicular to said face and away from it, apt to fit a satellite-pinion 42 which has an idle rotation movement with respect to said rung.
[0035] The satellite-pinion 42 comprises a first pinion 43 with a number of teeth z 1 and a second pinion 44 coaxially arranged above the first pinion and provided with a number of teeth z 2 , (z 1 ≧z 2 ). Said first pinion 43 and second pinion 44 are made in a single piece to define an integrated assembly or, according to alternative embodiments, are defined by two separate elements coupled one to the other by gluing, pins or similarly known retaining means.
[0036] The mobile element 34 , rotatably fitted on the base-body 32 , comprises a knob 46 provided above with an opening or window 48 apt to allow the display of figures 50 (whole and decimal) present on the upper face of a crown or annular element 52 arranged inside and coaxially to the knob 46 .
[0037] Elements 38 , developed from the upper face of the portion 36 of the base-body 32 and in a direction parallel to the axis of the same base-body, define two supports to sustain the rotation of the annular element 52 according to what is detailed here below. The knob 46 has a substantially cylindrical shape and is provided with a plurality of pockets 47 formed in a direction parallel to the central axis and along the outer lateral surface with the function of allowing the ergonomic grip by the hand/finger of a user to impart rotation on the valve manoeuvre member.
[0038] The same knob has a central through opening 49 in axial direction, perimetrically circumscribed by a tubular appendage 51 developed integrally with the body of the same knob to form, with the side edges of the knob 46 , an annular chamber 53 inside whereof the crown or annular element 52 is housed. Said central through opening 49 allows restraining of the handwheel to the rod of the valve, blocking them with a nut on the thread of the same rod or in another known and suitable manner and can, optionally, be covered above by a cap (not shown in the drawings).
[0039] Along the inner edge of the tubular appendage 51 turned in the direction of the base-body 32 a knurling 55 is formed with perimetrical development suitable for allowing the attachment of the aforementioned knob with respect to the manoeuvre member (not shown in the drawing) of the valve whereon the regulation handwheel is mounted.
[0040] The knob 46 , at the lower lateral inner edge turned in the direction of the upper portion 36 of the base-body 32 , has a cogged profile 58 perimetrically developed and provided with a number of teeth z 3 . This cogged profile is, preferably, made in a single piece with the same knob.
[0041] The crown or annular element 52 , along the end edge opposite the upper face whereon the figures or numbers 50 are shown indicating the opening of the valve, has a further cogged profile 60 with circumferential development and comprising a number of teeth equal to z 4 . This cogged profile is, preferably, made in a single piece with the crown or annular element.
[0042] The cogged profile 58 of the knob 46 engages with the cogged profile of the first pinion 43 of the satellite-pinion 42 .
[0043] In a substantially similar manner the cogged profile 60 of the annular element 52 is suitable for engaging, in a simultaneous manner, with the second pinion 44 of the satellite-pinion 42 of the base-body 32 .
[0044] The cogged profile 58 of the knob 46 and the further cogged profile 60 of the crown or annular element 52 rotate with respect to a same axis defined by the axis of rotation of the member of manoeuvre of the valve, while the satellite-pinion 42 rotates with respect to the axis of the rung 40 drawn, according to what is detailed here below, by the rotation of the knob.
[0045] The kinematism as defined above allows therefore the display of the figures 50 representing the degree of opening of the valve by means of a double internal parallel gear.
[0046] In a preferred yet non-limiting embodiment the cogged profile 58 of the knob 46 has a number of teeth z 3 =44, the cogged profile 60 of the annular element 52 has a number of teeth z 4 =55 and the first pinion 43 and the second pinion 44 of the satellite-pinion 42 have a number of teeth z 1 =z 2 =13.
[0047] All the profiles of the teeth of the wheels or cogged profiles described above are of the involute to a circle type.
[0048] Moreover all the elements constituting the handwheel are made in thermoplastic polymeric material or in another known plastic material suitable for the purpose.
[0049] The functioning of the handwheel for hydraulic valve of the present invention, described in detail above with reference to its constructional features, is detailed here below.
[0050] With the rotation of the knob 46 , the cogged profile 58 transmits the rotary motion to the first pinion 43 of the satellite-pinion 42 according to a transmission ratio z 1 /z 3 .
[0051] The second pinion 44 , being rigidly restrained to the first pinion 43 , rotates with it, transmitting the rotary motion to the crown or annular element 52 (which bears the figures indicating the variation of opening of the valve) via the meshing with the further cogged profile 60 of the same crown, with a transmission ratio z 2 /z 4 .
[0052] The modulus “m” used for the pair of wheels with number of teeth z 1 and z 3 (first pair) is greater than the modulus used for the pair of wheels with number of teeth z 2 and z 4 (second pair). This means that the further cogged profile 60 of the crown or annular element 52 , while having a number of teeth z 4 higher than the number of teeth z 3 of the cogged profile 58 of the knob 46 , has a smaller primitive diameter and, as a consequence thereof, it is possible to place the second pair of wheels inside the first. The number of teeth used for the cogged profiles described above allows the obtaining of a transmission ratio different from one which performs the rotation of the annular element 52 whereon the numerical figures are given together with the knob 46 but with a slightly smaller angle with respect to that which characterises the rotation of the same knob. This means that a relative movement exists between the knob 46 and the annular element 52 and that the window 48 of the knob 46 progressively reveals different sections of the face with the numerical figures 50 of said annular element allowing the display of the single figure (in the format XX.X, i.e. units and decimals) corresponding to the degree of opening of the valve.
[0053] The total transmission ratio w 1 /w 4 (where w 1 =z 3 /z 1 and w 4 =z 4 /z 2 ), like the angular spacing between the figures 50 on the annular element 52 , are fixed and such that, denoted by N the total number of turns whereon it has been decided to distribute the figures 50 , during this number of turns N, the annular element 52 must accumulate exactly 360° of delay with respect to the knob 46 and, consequently, must travel N−1 turns. Therefore the transmission ratio must be equal to (N−1)/N.
[0054] On the annular element 52 figures 50 are given comprised between 0.0 and (N−0.1) in that on reaching of the Nth turn the window 48 of the knob 46 reveals exactly again the figure 00.0.
[0055] In the case wherein the first pinion 43 and the second pinion 44 of the satellite-pinion 42 were to be characterised by the same number of teeth (z 1 =z 2 ), the handwheel for hydraulic valve of the present invention operates according to what is described above if:
[0000] z 3 /z 4 =( N− 1)/ N
[0056] As can be seen from the above the advantages that the device of the invention achieves are clear.
[0057] The handwheel for hydraulic valve provided with indicator of the level of opening of the valve allows the advantageous display of the degree of opening of the valve by means of a kinematic continuous coupling. In fact the existence of a fully defined transmission ratio different from one allows, as described, rotation of the annular element with the figures through a slightly smaller rotation angle with respect to that of the knob, allowing different sections of the numbered ring to be displayed progressively through the window or opening of the same knob.
[0058] Further advantageous is the fact that the use of cogged wheels with involute to a circle profile allows calculation with high precision of the couplings, minimising the dragging and ensuring the constancy of the transmission ratio, reducing the risk of wear and the consequent deterioration of the geometry of the cogged profiles.
[0059] A further advantage is represented by the fact that the handwheel of the invention allows easy reading of the features of opening of the valve. This in that the window where the figure indicating the degree of opening is read allows the simultaneous display both of the units and of the decimals.
[0060] Although the invention has been described above with particular reference to one of its embodiments given solely by way of a non-limiting example, numerous changes and variations will appear clear to a person skilled in the art in light of the description given above. The present invention intends, therefore, to embrace all the modifications and the variations that fall within the scope of the following claims. | A handwheel ( 30 ) for hydraulic valve provided with numerical indicator of the valve opening level, comprising a base-body ( 32 ) or fixed element apt to be stably restrained with respect to the valve-body and supporting a mobile element ( 34 ) rotatably coaxial with respect to said base-body ( 32 ), connected with a member of manoeuvre of the valve and provided with a knob ( 46 ) apt to be gripped by a user in order to impart a rotation to said manoeuvre member corresponding to the value or degree of opening required for the valve indicated by figures ( 50 ) displayed through an opening or window ( 48 ) of said knob, said base-body ( 32 ) and mobile element ( 34 ) rotatably co-operating one with the other by means of a kinematic continuous coupling with double parallel internal gear. | 5 |
RIGHTS OF THE GOVERNMENT
The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.
BACKGROUND OF THE INVENTION
In a series of three issued U.S. Patents we have heretofore described the environment incurred by military munitions devices during their ballistic termination encounter with a target, particularly a hardened target. We have also discussed in these patents the frequent need to study events attending this terminal encounter from of course a safely remote location. These three issued patents are identified as U.S. Pat. Nos. 6,380,906; 6,453,790 and 6,456,240 all of which became known during the year 2002 and all of which are hereby incorporated by reference herein. It is believed helpful in appreciating these three patents as well as the present invention to recognize that the use of moderate power radio frequency communication apparatus in an environment calling for its shock hardening against large physical stresses represents a combination in the technical arts that has remained largely unexplored until recent years. It is possible to attribute this unexplored status to the fact that moderate power radio frequency communications, the use of class “C” nonlinear amplifier stages in such communications and the shock hardening aspects of such apparatus have each been considered to lie in the black art or empirical design arenas and therefore have either been avoided whenever possible or explored in secrecy. Our inventions are believed to represent part of an emergence of this technology.
The occurrence of deceleration forces measuring in the tens of kilo-G or in excess of ten thousand times the force of gravity during a target encounter event i.e., during a probable time of remote study interest, is of course one of the major components of a target encounter environment to be expected in this technology. Another component of this environment is of present interest and concerns a need to limit the temperature excursion incurred in a power semiconductor device employed in communicating data from the moving munitions device to a safely remote location e.g. to limit temperature in a transistor or integrated circuit device included in a telemetry transmitter apparatus embedded in the munitions device. An additional aspect of this environment is the need to limit the physical size and weight of components associated with the invention in order to make them compatible with the space and weight limitations imposed on a ballistic munitions device and the incurred G forces at impact. A yet additional aspect of this environment is the frequent need for a low impedance electrical connection between one or more terminals of a mounted electrical device and a true ground node of the employed electrical circuit.
The present invention is believed to contribute additional knowledge to the art of accomplishing data communication under these unusual environmental conditions and in fact provides a frequently needed component that can be beneficially used in such systems as the communication apparatus described in the incorporated by reference herein patents. The invention is not however limited to use in such environments and may in fact provide utility in other environments including for example routinely encountered static semiconductor device applications.
The present invention therefore addresses the need to mount for example a semiconductor device in order to assure both its physical integrity and its safety from thermal damage during a brief but nevertheless high stress interval of usage. In a situation typical of the presently described military munitions study environment an involved semiconductor device can be for example of the field effect transistor type as is used in the final amplifier stage of a ultra high radio frequency or very high radio frequency transmitter apparatus that receives energization for one quarter of a second during an actual use event extending from before to during an impact of the munitions device with a target. This semiconductor device may also be of the integrated circuit, power diode or other types of semiconductor devices and the invention may in fact also find utility in the mounting of non-semiconductor devices such as power dissipating resistive components and heat dissipating electromechanical devices.
SUMMARY OF THE INVENTION
The present invention provides a thermally effective G-force tolerant, space and weight conserving and low electrical impedance mounting for a semiconductor device or other energy-dissipating component of an electrical apparatus.
It is therefore an object of the present invention to provide an impact resistant mounting for a thermal energy dissipating electrical device.
It is another object of the present invention to provide an impact resistant mounting for a thermal energy dissipating electrical device usable in the space and weight limited environment of a ballistic munitions device.
It is another object of the invention to provide an impact resistant mounting for a thermal energy dissipating electrical device that also enables achievement of a low electrical impedance between the mounted electrical device and a true ground node of an attending electrical circuit.
It is another object of the invention to provide a physically robust mounting for a plastic encapsulated semiconductor device.
It is another object of the invention to provide a mounting arrangement for a semiconductor device that benefits from both heat absorbing and heat dissipating characteristics.
It is another object of the invention to provide a physically robust mounting for a pulse operated semiconductor device, a mounting having thermal capacity to absorb pulse related energy before significant conduction to a dissipating surface can commence.
It is another object of the invention to provide a physically robust mounting for a pulse operated semiconductor device that can in time conduct thermal energy to surrounding conductors such as an array of printed circuit board traces.
It is another object of the invention to provide a physically robust mounting for a pulse operated semiconductor device that achieves physical shock immunity through use of relatively large mounting elements and surfaces.
It is another object of the invention to provide a mounting arrangement for a relatively small semiconductor device of the SO-8 package size.
It is another object of the invention to provide a small semiconductor device mounting arrangement that may be conveniently expanded, possibly in standard size increments, to accommodate larger semiconductor devices.
It is another object of the invention to provide a heat sinking arrangement for a semiconductor device that also provides desirable electrical conductivity for electrical currents originating in said semiconductor device and in physically adjacent electrical circuits.
It is another object of the invention to improve the state of the electrical art with respect to impact resistant radio frequency energy sources of higher operating frequency and moderate operating power capabilities.
It is another object of the invention to provide a semiconductor device mounting arrangement that is readily fabricated from common materials.
It is another object of the invention to provide a semiconductor device mounting arrangement that uses soldering techniques in achieving a combination of thermal conductivity, electrical conductivity and structural integrity.
It is another object of the invention to provide a semiconductor device mounting arrangement that provides both intra surface and inter surface via electrical conductor functions for a printed circuit board.
It is another object of the invention to provide a semiconductor device mounting arrangement that is comparable to a shirt cuff-link in both physical size and in mounting arrangement.
These and other objects of the invention will become apparent as the description of the representative embodiments proceeds.
These and other objects of the invention are achieved by impact resistant semiconductor device mounting and cooling apparatus comprising the combination of:
a printed circuit board having electrical conductors arrayed on first and second surfaces thereof and having a shaped transverse opening located in a selected portion thereof; an integral metallic heat sink member of first cross section shape conforming with said printed circuit board shaped transverse opening and disposed within in said transverse opening; said integral metallic heat sink member having a second cross sectional shape orthogonal of said first cross sectional shape and inclusive of a wing element portion extending along said printed circuit board first surface; said integral metallic heat sink member having a third cross sectional shape orthogonal of both said first cross sectional shape and said second cross sectional shape and including a recessed saddle portion parallel with said printed circuit board along a first cross sectional extremity and a grooved recess parallel with and adjacent said printed circuit board second surface along a second cross sectional extremity.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings incorporated in and forming a part of the specification, illustrate several aspects of the present invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 shows an enlarged perspective view of a miniature heat sink element for a semiconductor mounting arrangement in accordance with the present invention.
FIG. 2 shows a dimensioned end view of a FIG. 1 heat sink element.
FIG. 3 shows a mounting arrangement for a FIG. 1 and FIG. 2 depicted heat sink element.
FIG. 4 shows a dimensioned elevation view of a FIG. 1 – FIG. 3 heat sink element.
FIG. 5 shows a top view of a FIG. 1 – FIG. 4 heat sink element.
FIG. 6 shows a top view of a FIG. 1 – FIG. 5 heat sink element with a mounted semiconductor device received thereon.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 in the drawings shows an enlarged perspective view of a miniature heat sink element 100 of a semiconductor mounting arrangement in accordance with the present invention. As shown in the FIG. 1 drawing the heat sink 100 may be considered to be of a generally Tee shaped cross sectional configuration (as viewed from its FIG. 1 right or left most ends), and to include the tee stem portion 102 , the tee stem depth portion or saddle—inclusive portion 104 and the pair of integral transverse wings or tee arms shown at 106 and 108 . The FIG. 1 heat sink is preferably composed of gold or copper or some other metal of good thermal and electrical conductivity. Although the metal aluminum is often considered to have such thermal and electrical characteristics, and is indeed a suitable material for some uses of the present invention heat sink, copper or some metal providing desirable soldering characteristics is preferable for incorporating the FIG. 1 heat sink into the circuit assemblies described in the ensuing paragraphs herein and most uses of the invention.
FIG. 2 in the drawings shows an end view of the FIG. 1 heat sink element together with representative or typical dimensions for such a heat sink element as utilized in the pulsed low electrical duty cycle and high impact forces environment described herein. Notably the FIG. 3 heat sink element (herein simply “heat sink”) includes a pair of wing-like elements 201 that are received on top of a tee section heat sink tee stem or body element 202 to form a tee-like structure when viewed from an endmost viewpoint. The FIG. 3 heat sink also includes a slot-like cut 204 usable in holding the FIG. 2 structure securely in a printed circuit board in order to achieve an impact-resistant assembly. The preferred direction of the applied impact forces is indicated at 206 in the FIG. 2 drawing, the most preferred direction of this force being in the downward direction of FIG. 2 ; the FIG. 2 structure is also found to have substantial impact force tolerance in other directions appearing in the FIG. 2 and FIG. 4 drawings.
As indicated by the dimensions appearing in the FIG. 2 drawing the heat sink element of the present invention is typically made to be of a rather small physical size, a size that is actually comparable with for example a naturally occurring individual peanut or cherry pit or shirt cuff-link. This small physical size and the attending relatively small physical mass are of course helpful in limiting the magnitude of the large physical force received by the heat sink during a target impact event, an event such as a smart munitions device encountering a hardened target. In this regard it may be recalled that the force F, generated during a physical deceleration of a moving physical mass M, at a rate A, is predicted by the familiar Newtonian physics mathematical relationship of F=M·A or that the generated force is directly proportional to the amount of mass and its rate of deceleration; the force F in the environment of the present invention is contemplated to be as great as that produced by an acceleration A, of some fourteen thousand (14,000) times the force of gravity.
Equally important with respect to the present invention the small physical size of the FIG. 1 – FIG. 4 heat sink is compatible with the physical size of a family of semiconductor devices that are convenient for use in the electronic circuits embedded in a present day smart munitions device electronic circuits such as a radio frequency energy generating telemetry transmitter or a warhead fuse circuit such as a hard target penetrator fuse. In particular the FIG. 2 and FIG. 3 represented dimensions are compatible with the industry standard eight pin or SO-8 plastic package that is often used to contain a single field effect transistor semiconductor device or a small integrated circuit device. The SO-8 package may for example be conveniently used to contain the 30 watt-rated radio frequency field effect transistors made by Polyfet Devices of Camarillo, Calif. Such transistors have for example proven to be desirable for use in the class “C” final amplifier stage of a 300–500 megahertz telemetry transmitter used in the manner discussed in the above incorporated by reference herein patents in our smart munitions development work. When provided with the heat sink of the present invention this 30 watt transistor is found to be capable of generating a somewhat surprising 42 watt level of radio frequency energy with an overall power in to power out efficiency near seventy percent in the short duty cycle environment characterized by a munitions device telemetry transistor. (A munitions device telemetry transistor can for example be thought of as having an actual in-use operating life measurable in milliseconds of time up to about one quarter of a second; however transmitter tuning and other human interventions often extend the required operating time to at least an integral number of seconds. The heat sink and mounting arrangement of the present invention of course should preferably accommodate the full extent of such duty cycle possibilities.)
Returning now to the description of the present invention heat sink as provided in the FIG. 1 through FIG. 4 drawings, FIG. 3 in these drawings shows how the FIG. 1 and FIG. 2 heat sink 100 may be mounted in a printed circuit board 302 during for example fabrication of the above-described telemetry transmitter. In the FIG. 3 cross sectional view drawing the wing 201 portions of the heat sink 100 are shown to be received on the top most surface of printed circuit board 302 while the body or tee leg portion 202 of the heat sink passes through an aperture 304 of appropriate rectangular configuration that has been pre disposed in the printed circuit board 302 . The relationship of the heat sink tee stem portion 202 with the aperture of the printed circuit board 302 may be, for discussion convenience, likened to the relationship of a cuff link with the shirt cuff it retains. As called-for by this analogy the heat sink tee stem 202 passes through the printed circuit board 302 and is retained in this position by an attached but movable orthogonal member engaged within slot 204 and soldered over all possible surfaces.
The printed circuit board 302 may be made to have a thickness of 0.062 inch or 1/16 of an inch and may be made from the fiberglass—resin composite material identified as FR-4/G10 by its many manufacturers and also by Military Specification. This thickness dimension is compatible with and is actually an extension of a convenience concept by which dimensions for the FIG. 1 through FIG. 4 heat sink are assigned in one sixteenth of an inch-compatible measurement units; units that are a number of increments of printed circuit board thickness. Such units are in fact also compatible with the dimensions to be expected in a segment of transmission line of the fifty ohm characteristic impedance “strip line” type. Other measurement units may of course be used with the present invention, including measurements convenient to the metric system when appropriate. The FR4 printed circuit board material is generally said to be usable up to a frequency of some 500 megahertz and is therefore suited to the 300–500 megahertz band of operation of the herein often referred-to telemetry transmitter. For munitions telemetry usage the printed circuit board 302 may have some unusual lateral shape such as the shape of a crescent in order to for example be conveniently fitted into space available in the trailing end portion of a munitions device. A crescent space of some one inch by one inch cross sectional size and radius between five and 14 inches has, for example, been used to contain a telemetry transmitter printed circuit board of this configuration in some of our experimental work.
Also appearing in the FIG. 3 drawing is an end view or cross sectional view of a locking plate or keeper member or flange member 300 used to retain the heat sink 100 captive in the printed circuit board 302 . The keeper or flange member 300 preferably engages the slot 204 of the body or tee leg 202 in a manually inserted but snug fit that is ultimately fixed into permanence by a flowing solder attachment to the heat sink 100 as is described in detail in paragraphs following herein. Two of the slots 204 are disposed in the heat sink body 202 as may be best appreciated in the FIG. 4 drawing view. These slots 204 may be cut to 0.025 inch top to bottom dimension in FIG. 3 (to mate with 0.250″×0.500″×0.024″ thick copper sheet material keepers) and to a depth of up to 0.030 inch into the heat sink body; desirably such cutting is accomplished by way of a saw cut. Preferably two of the keeper or flange members 300 , one at each end of the heat sink body portion 202 , are used with the slots 204 in order to retain the heat sink 100 captive in the printed circuit board 302 . The slots 204 may of course be extended around the total periphery of the heat sink body 202 and thus engaged by additional keeper or flange members of appropriate length in order to increase the engagement area of the slot or keeper members with the printed circuit board surface and achieve greater impact resistance tolerance when needed.
The keeper or flange members 300 are preferably made of sufficient lateral surface size as to provide the heat sink 100 with a significant capability of resisting impact forces directed upwardly in the FIG. 3 drawing. Soldering of the keepers or flanges 300 as well as the wing-like elements 200 to printed circuit board conductors on each side of the printed circuit board 302 also adds to the impact resistance of the installed heat sink 100 and also to the heat conduction capability of the assembly. The keeper or flange members 300 may be made of the same material such as copper as the heat sink body portion 202 or alternately of some other, preferably solder-capable, material such as brass where greater hardness and resistance to impact force bending is needed.
FIG. 4 in the drawings shows a dimensioned elevation view of the FIG. 1 heat sink element 100 as it is tailored to receive a semiconductor device contained in the above-described eight pin SO-8 size package. From the FIG. 4 view it may also be appreciated that the heat sink of the present invention need not be limited to this SO-8 package and may for example be easily extended to the sixteen pin SO-16 package or to other types and other sizes of package, including packages intended for non semiconductor device usage for example. For use with the SO-16 package for example the 0.2 inch saddle width dimension shown in FIG. 4 may be merely doubled to 0.40 inch and the overall width shown in FIG. 4 increased to 0.525 inch. Again other dimensions are entirely possible when attended by accommodation of the resulting changes in heat sink mass, thermal conductivity and other characteristics.
The wings 201 used to retain the heat sink 100 on the top surface of printed circuit board 302 in the FIG. 3 drawing appear at the upper right and left in the FIG. 3 view. The wing dimensions as shown in FIG. 2 are compatible with the printed circuit board thickness dimension 0.062 inch units of measure already described herein. When made in accordance with these dimensions the heat sink tee leg portion lies ⅓ within the printed circuit board 302 in the FIG. 3 drawing and ⅔ extending below the printed circuit board. For space and mass conservation purposes it may be desirable to limit the extent of this ⅔ extension by either pre assembly or post assembly shortening of the tee leg portion. Similarly shortening may be applied to the wing dimensions shown in FIG. 2 where mass and size limitations are imposed and sufficient surface area contact remains with the printed circuit board to dissipate the encountered impact force. The overall heat sink depth dimension of 0.325 inch shown in the FIG. 4 drawing is also compatible with the 0.062 inch unit of measure arrangement and is selected in accordance with the SO-8 device package size usage of the illustrated heat sink.
The space intermediate the wings 201 in the FIG. 4 drawing, i.e., the space 400 where the semiconductor device package is received, may be referred-to as the heat sink saddle area and is arranged to provide the lowest possible thermal resistance between a mounted semiconductor device and its ultimate thermal energy dissipation media. This lowest possible thermal resistance is achieved by way of the substantial surface area available in the saddle region area 400 for receiving heat from the semiconductor device and the contemplated low thermal resistance connection established in the saddle area with the semiconductor device i.e., the connection established at the surface 406 in FIG. 4 . Although silicone paste based heat conducting media as commonly used in the electronics industry may be used in the saddle area 400 to make an effective thermal connection with a semiconductor device the completely metal connection described below herein is preferred because of its lower thermal resistance. Indeed many of the characteristics of the present invention heat sink are arranged in contemplation of this all-metal connection.
The substantial cross sectional area of the wings 201 and the resulting ability of these elements to conduct heat away from the saddle area 400 may be appreciated in both the FIG. 4 and FIG. 5 drawings. This substantial wing cross sectional area of course also contributes to the thermal mass of the heat sink 100 and is thereby of significant temperature limiting benefit in the short duration or pulse operated environment of the munitions device telemetry function contemplated in the referred-to application of the present invention heat sink. The substantial wing cross sectional area also is effective to communicate saddle area heat to the copper or other conductor material located on the upper surface of the printed circuit board 304 —especially in view of the preferred use of solder between the lower wing surface and the printed circuit board conductor. A top view of the saddle area 400 of a present invention heat sink and the adjoining wings 201 appears in the FIG. 5 drawing. The lines appearing at 408 and 410 in FIG. 4 may at first blush appear to be portions of or extensions of the saddle area 400 and the saddle surface 406 . Actually however these lines 406 and 408 represent the intersection of the lower surface of the wings 201 with the heat sink body portion 202 and thus merely happen to coincide with the elevation of the saddle surface 406 in the illustrated embodiment of the invention.
A top view of a packaged semiconductor device 600 mounted in the saddle area 400 of a present invention heat sink appears in the FIG. 6 drawing. Also appearing in the FIG. 6 drawing are the leads 602 , 604 606 and 608 by which the semiconductor device 600 is later to be electrically interconnected with other elements of a telemetry transmitter or other circuit utilizing the present invention heat sink. In the case of a single transistor being contained in the saddle 400 -mounted semiconductor device, one pair of leads such as leads 604 and 606 on each side of the semiconductor device 600 may be commonly connected both within and external of the semiconductor device 600 . Actually SO-8 transistor packages normally include four leads on each side of the transistor package however in the case of one transistor used with the present invention heat sink, four of the resulting leads are also common to the transistor source electrode and the metal window area of the SO-8 package described in ensuing paragraphs herein and therefore may be removed before transistor mounting. Notably the direct connection of a transistor source element to the metal of the window area 610 as espoused herein, in addition to providing a good thermal path for transistor heat also provides a desirably low electrical inductance path for the transistor's source current to follow. Passing such current through the inductance of bond wires normally disposed within a transistor package can be quite detrimental to the operation of a transistor amplifier functioning in the 300–500 megahertz frequency region.
Before departing from the saddle area 400 and its containment of the mounted semiconductor device 600 it is also desirable to consider that the arm or wing elements 201 as shown in the FIG. 6 drawing provide additional support and stabilization for the semiconductor device 600 in the saddle 400 by way of the physical abutment occurring at 612 and the other similar locations in FIG. 6 . By way of this physical abutment the semiconductor device 600 is restrained from motion in at least one direction even though the shock and shock excited vibration arising from a target impact event may be sufficient to stretch the metal located within the window area 610 or otherwise establish vibrations in the semiconductor device, the printed circuit board and the heat sink structures. This physical abutment restraint is usually solder filled, but may be assisted by adding other suitable filler materials such as an organic sealer or a hardenable substance such as an epoxy between the semiconductor device surface and the adjacent surface of the arm or wing elements 201 .
The heretofore discussed drawings of FIG. 3 , FIG. 4 and FIG. 6 may also be though of as representing three different cross sectional views of the present invention heat sink, three cross sectional views that are each oriented mutually orthogonal with respect to the remaining two views of the heat sink. Cross sectional shading is omitted in all but the FIG. 3 of these potential cross sectional views for convenience and clarity purposes. The arrows at 110 , 112 and 114 in the FIG. 1 drawing show directions of viewing that are appropriate for these three different cross sectional views and are identified with one possible set of cross sectional view identification numbers. Other cross sectional view identification number ordering may of course be assigned as desired. A cross sectional interpretation of the FIG. 3 , FIG. 4 and FIG. 6 drawings is believed helpful in understanding the formal description language relating to the invention included in the attached claims.
The enclosed dotted line window area at 610 in the FIG. 6 drawing of a SO-8 package-contained semiconductor device represents the outline of a lower face exposure metal panel window of the semiconductor device 600 . In some transistor types such as in the Lateral Drain Metal Oxide Silicon (LDMOS) transistor this metal window is in fact physically and electrically connected with one transistor element, such as the transistor source element, of a transistor received in the saddle-mounted device package 600 (i.e., the transistor layers are fabricated on the top surface of the metal window area 610 with for example the transistor source electrode being both formed on and connected with the window metal; package enclosure material is added to the transistor after this fabrication). This transistor fabrication arrangement enables the transistor within the dotted line 610 to be intimately connected electrically and thermally with the transistor package window metal. Notably such intimate connection also continues into the saddle area in the present invention heat sink and moreover allows for the transistor metal to heat sink connection to be accomplished by way of metallic soldering—in order to obtain the lowest possible thermal resistance in the transistor heat dissipation path. A metal to metal connection, even when accomplished by way of tin/lead solder, is of course far superior to an insulated connection (as often accomplished with a mica washer and silicone grease for example) in its low thermal resistance and heat transferring ability.
Fabrication of transistor layers on the top surface of the window area defined by the dotted line 610 and direct connection of this window area to the heat sink 100 also of course provides the desired lowest possible electrical resistance and electrical impedance between a transistor electrode and the true ground node of the electrical circuit utilizing the transistor. The direct soldering connection of a metal transistor fabrication substrate to the heat sink of the present invention of course entails heating of the semiconductor layers of the transistor to solder flow-promoting temperatures for at least the short interval of a soldering event. The resulting semiconductor device temperatures, temperatures in the 500 to 600 degrees Fahrenheit or 260 to 315 degrees Centigrade range when eutectic-proximate tin/lead solder is used, appear to be satisfactorily tolerated by at least silicon semiconductor devices. Semiconductor devices made from gallium arsenide and germanium and other semiconductor materials may be threatened by temperatures of this range and thereby may call for the use of threaded fasteners or thermally conductive adhesives or other lower temperature attachment arrangements at the semiconductor device to heat sink interface in the present invention.
Soldering may be used to electrically connect the wings 201 of the FIG. 1 and FIG. 2 heat sink 102 into the topside printed circuit board electrical circuit and thus enables use of the wings 201 as printed circuit board surface mounted conductors, i.e., as conductors communicating between other topside conductors of the printed circuit board or topside to bottom side communication conductors. This heat sink conductor concept thus enables the tee stem body 202 of the heat sink to communicate electrical currents and thermal energy through the printed circuit board 302 . The electrical conduction of these conductive attributes in fact represents a significant attribute of the present invention, i.e., such conduction may be attributed to the general principle that the present invention heat sink adds significant via conductor capability to a printed circuit board in which it is installed. This via conductor ability may especially be observed, by way of the large cross sectional areas involved, to be significantly more effective than the usual plated through or otherwise arranged circular via holes in connecting front side printed circuit board conductors with backside conductors. Good via conductors are of course of significant assistance in obtaining the desired performance from a circuit operating in the presently considered 300–500 megahertz frequency band. As has been stated in one corollary to the familiar Murphy's law, nothing is so effective in turning an amplifier circuit into an oscillator circuit as a small amount of inductance in a ground path.
Fabrication of the FIG. 1 heat sink element 100 in the present semiconductor device mounting arrangement invention may be accomplished through use of an individual molding or casting sequence that is tailored for the preferred copper or copper inclusive material. Other materials such as brass or possibly aluminum may also be used for the heat sink and fabricated by these processes. Aluminum is however difficult or impossible to solder using at least conventional tin/lead processes and the electrical and thermal conductivity of both brass and aluminum is somewhat lower than that of the preferred copper metal. In addition use of such molding or casting processes can result in metal grain structures characterized by lower thermal and electrical conductivity than is achieved with other fabrication arrangements and can result in exterior heat sink surfaces that are sufficiently rough as to require smoothing for achieving effective thermal and electrical contact with a semiconductor device package. In view of these limitations therefore the preferred arrangement for fabrication of at least small quantities of the FIG. 1 heat sink is through use of machining commenced with conventional rolled soft copper bar stock.
During such individual heat sink element machining it is possible to commence with a billet or blank or having the overall 0.25 by 0.25 by 0.325 inch dimensions shown in the FIG. 2 and FIG. 4 drawings and to then perform milling machine or other machine-tool cutting operations to remove metal from the areas 208 and 210 identified in the FIG. 2 drawing and from the saddle region 400 defined in the FIG. 4 drawing. Alternately it is also possible to commence fabrication of the heat sink 100 with a length of bar stock. Such stock may be first machined and then severed into individual heat sink element lengths or severed first and then machined to achieve the illustrated shapes. Notably a simple straight three-cut or four-cut straight line machining sequence is sufficient to achieve FIG. 1 represented shape using this individual heat sink element machine tool fabrication process. Moreover at least two of these machine cuts can be performed on a multiple heat sink blank wherein the individual heat sink elements are taken from the blank by segregation of adjacent heat sink surfaces 402 and 404 as are shown in the FIG. 4 drawing. A small milling machine such as a computer-controlled machine is convenient in performing these machining steps. In view of the well known chip-reattachment properties and chip pile difficulties encountered in machining metallic copper stock it is well to include a degree of patience or hesitation in the heat sink machining operations.
It is also feasible to machine the FIG. 1 heat sink elements from a multi element blank or billet in which the individual heat sink elements are originally adjacent at the surfaces 212 and 214 in the FIG. 2 drawing—through use of a sawing or other cutting segregation procedure. Machining in this manner enables single cut formation of the slot like cuts 204 and the saddle regions 400 in a plurality of heat sink elements. Additionally it is of course also possible to machine the FIG. 1 heat sink elements from a multi element blank or billet in which the individual heat sink elements are originally adjacent at the surfaces 216 and 218 in the FIG. 2 drawing—by use of another sawing or cutting segregation sequence. As may be observed from this number of fabrication possibilities the optimum method of fabrication is perhaps best defined by available equipment rather than by limitations of the fabricated heat sink.
The relatively small size and mass of the present invention heat sink element also lends to the use of a screw machine or punch press die fabrication process to meet larger quantity heat sink needs. Rearrangement of the described configuration of the heat sink can make use of such equipment easier while maintaining the underlying function of the device.
The significance of a well considered heat sink in critical electrical circuitry, such as in many moderate power radio frequency circuits, may perhaps be better appreciated by recognizing that some of the large semiconductor manufacturers have recently adopted the practice of selling their moderate and large power radio frequency semiconductor devices with a factory installed heat sink already mounted in place. Although this practice limits a user's freedom to employ the semiconductor device in unusual physical arrangements it has doubtless been found helpful in assuring the achievement of adequate cooling and limiting heat-associated semiconductor device problems. The large and fixed shape of such semiconductor device plus heat sink combinations almost universally prohibits their use in our munitions related work; especially when the impact loading forces of our environment are considered. This is perhaps another illustration in support of our belief that the combination of impact loading and moderate radio frequency power in a single electrical circuit is a specialized area that has received little attention in the electronic art.
The present semiconductor device mounting invention is therefore believed to improve the art of impact hardened and moderate radio frequency energy electrical circuits; some of the more significant advantages provided by the invention may be summarized as follows.
Downward movement of the mounted semiconductor device is restricted by wing-bars received on top of the receiving printed circuit board; Upward movement of the mounted semiconductor device is restricted by plates received in semiconductor body slots; Bars and interlocking plates are soldered to an available 2-side plated printed circuit board; Heat transfer is above, through and below the preferably copper printed circuit board Low inductance grounding is above, through and below the preferably copper printed circuit board; Certain transistors such as LDMOS devices have the source element soldered-in a heat sink saddle area by way of a metal window located at the bottom of selected plastic packages. The heat sink retaining bars and plates are disposed at package ends and do not interfere with transistor heat sink center (source) and side-located (gate and drain) leads.
The invention is believed to make a needed contribution to the art of relatively high powered semiconductor devices that must operate in a physically stressful and significant impact inclusive environment.
The foregoing description of the preferred embodiment has been presented for purposes of illustration and description. It is not intended to be exhaustive nor to limit the invention to the precise form disclosed. Obvious modifications or variations are possible in light of the above teachings. The embodiment has been chosen and described to provide the best illustration of the principles of the invention and its practical application in order to thereby enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally and equitably entitled. | A semiconductor mounting arrangement inclusive of a heat sink member enabling desirable resistance to physical impact damage to the semiconductor device, the heat sink and the printed circuit board supporting the semiconductor device and the heat sink. The heat sink is fabricated of thermally and electrically conductive metal such as copper and captured by metallic interconnection such as soldering to conductors of the printed circuit board. Efficient thermal and electrical conductivity between semiconductor device and heat sink are achieved also by metallic interconnection such as soldering intermediate the semiconductor device and the heat sink. Desirable semiconductor device performance under extreme electrical and physical force transient loading conditions are disclosed. | 7 |
BACKGROUND AND SUMMARY OF THE INVENTION
The present invention relates generally to flexible partitions, and more specifically, to a guide for a curtain with an integrated wind-up device.
It is well known to utilize flexible sheet material curtains which roll up and down to divide a partition in a large room, such as in a gymnasium. In most cases, an electric motor drives the shaft on which the curtain is hung. One particular style of roll up includes a shaft in the center of the curtain and the motor mounted within the shaft. This is shown in U.S. Pat. Nos. 5,429,171 and 5,524,693. Such a prior art system is also shown in FIGS. 1-3. The motor in the center of the roll has one or both ends secured by a carriage which rides up and down a tube or guide, the other end drives the center roll to wind the curtain onto and off of the center roll to raise and lower the curtain. After the curtain is rolled up, the wall tube or track still is extending down. In certain installations, this is undesirable. Where a guide is or could not be provided, the torque compensation arm of U.S. Pat. No. 5,524,693 is required.
The flexible partition of the present invention includes a curtain secured to a support structure at its top edge and a shaft secured to the curtain displaced from the top edge and extending across the curtain. A drive is coupled to the shaft to rotate the shaft, thereby rolling the curtain. A carriage connected to one or both ends of the driver is received in a guide to restrict the rotation of the first end of the driver. The guide is pivotally coupled at its upper end to the support structure to move between a raised and lowered position. The guide in the raised position is substantially horizontal. The carriage and guide in the raised position of the guide is adjacent the support structure.
In one embodiment, the guide includes a first portion pivotally coupled to the support structure and the second portion extends at an angle to the first portion. The carriage travels in the first portion between the raised and lowered position of the guides. The second portion of the guide, in the raised position, is substantially horizontal. The length of the second portion and the angle between the first and second portions of the guide are selected such that the second portion of the guide is substantially horizontal in the raised position of the guide.
Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevation of a flexible partition of the prior art fully deployed.
FIG. 2 is an enlarged cross-section taken along lines II--II of FIG. 1.
FIG. 3 is a cross-section taken along lines III--III of FIG. 2.
FIG. 4 is a side elevation of a flexible partition and guide according to a first embodiment of the present invention.
FIG. 5 is a side elevation of a flexible partition and guide according to a second embodiment of the present invention.
FIG. 6 is an enlargement of the carriage of FIGS. 4 and 5.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 1 and 2, there is shown a flexible partition 10 being fully deployed in a Room R. The room R might be a gymnasium or other large room such as in an industrial factory or a convention hall. The room R includes a ceiling 12, a floor 16, and side walls 14. The partition 10 is shown as being hung from a truss girder or support structure 18 extending from one wall 14 to the other lateral side wall 14 and supporting the ceiling 12.
The flexible partition includes a curtain 20 which in this case is made up of an upper portion 22 and a lower portion 24. A shaft 26 is connected to and separates the upper portion 22 from the lower portion 24.
Referring now to FIG. 3, the upper edge of the curtain 20 is suspended from the girder 18 by a track 28. Hangers 32, which fit in grommets provided near the upper edge of the upper portion 22 of the curtain 20, connect the curtain 20 to the track 28.
A valance 36 may be suspended from the ceiling 12 and connected to the upper edge of the upper portion 22 of the curtain 20, a shown in FIG. 1.
A motor 46 is provided within the hollow portion of the shaft 26, at least at one end and includes a rotary drive connection 48 as shown in FIG. 2. The other end of the motor 46 is connected by an extension 46a and flange 56 to a carriage 52 to which is mounted four idler wheels 54 as shown in FIGS. 2 and 3. The idler wheels 54 are adapted to surround a suspended tube 50. When the motor 46 is driven to rotate the shaft 26 by the rotary drive connection 48, the reaction is to resist the torque and thus to prevent the rotation of the motor provided by the carriage 52 on the suspended tube 50. It is contemplated that other torque reaction devices could be used including a fixed vertical guide member, a folding torque arm, fixed guide wires, or a retractable cable.
Although the fixed guide is unobtrusive or not a safety hazard when it is mounted adjacent a side wall 14, there may be installations where the partition is in the middle of the space. Thus, a fixed guide is not and may not be feasible.
In operation, when it is required to wind up the curtain, the motor 46 is activated to rotate the rotary drive connection 48 and thus rotate the shaft 26. Both the upper portion 22 and the lower portion 24 of the curtain 20 will simultaneously be rolled up on the shaft 26 as the cylinder 26 climbs on the upper portion 22.
A weight may also be provided at the lower edge of the lower portion 24 in order to properly hang the curtain 20.
The above description of the prior art devices in FIGS. 1-3 have been with reference to U.S. Pat. No. 5,429,171. The same numbers have been used such that if more detailed explanation is needed, the reference can be made thereto.
The improved guides of FIGS. 4 and 5 are replacement of the tube 50, fixed vertical guide member, folding torque arm, a fixed guide wires or retractable cable described in U.S. Pat. No. 5,429,171. The curtain 20 with the shaft 26 and motor 46 therein is identical to that described for FIGS. 1-3. It should also be noted that it may include any other structure wherein the shaft 26 is mounted displaced from the top edge of the curtain 20 so as to rise and lower as it rolls and unrolls the curtain 20. Though the specific structure of FIGS. 1-3 have been used as an example, the present invention is not to be limited to that particular structure.
The guide 60 of FIGS. 4-6 is pivotally connected at a first end 62 about pivot points 64 to the support structure 18. Wherein the guide 60 in FIG. 4 is a straight continuous element, the guide 60 in FIG. 5 includes a first portion 68 and a second portion 66 at an angle with respect to each other. In both Figures, the curtain 20 is shown in the lowered position in solid and its raised position in phantom. In the raised position of FIG. 4, the guide 60 is substantially horizontal and in FIG. 5, is almost completely horizontal. The length of the first portion 68 and the angle between portion 66 and 68 accommodates the difference between the position of the pivot point 64 and the totally raised position of the rolled curtain 20 so as the second portion 66 is horizontal in the raised position. In FIG. 4 to allow the guide 60 to be as horizontal as possible, the pivot point 64 is connected to the trusts or support structure 18 by a bracket 70 welded to or coupled to the support structure 18.
The distance D1 between the center line of the shaft 26 and the pivotal connection 64 for the guide 60 and the distance D2 between the top of the support structure 18 and the pivot point 64 of FIG. 4 are larger than the distance D3 between the center line of the shaft 26 and the pivot point 64 and the distance D4 between the top of the support structure 18 and the pivot point 64 of FIG. 5. This allows a more compact structure. Both of the structures in FIGS. 4 and 5 raise the guide 60 out of the area where people walk and athletes may play.
The carriage 72 illustrated in FIG. 6 includes a pair of rollers or wheels 74 on opposite sides of the connection of the end of the motor 46a and flange 56 to the carriage 72. The guide 60 is U-shaped having flanges 76 overlapping the carriage 72 and the wheels 74. This provides protection from foreign objects getting caught between the carriage 72 and the guide 60, as well as keeping dirt and other materials out. The prior art also includes a pair of rollers in a channel. The guide 60 may also be a tube or rod which is pivotally connected at its top end and the two rollers 74 or four rollers as in FIG. 3 run on the rod.
Also, the guide 60 and the carriage 72 may be provided at both ends of the shaft 26.
Although the present invention has been described and illustrated in detail, it is to be clearly understood that the same is by way of illustration and example only, and is not to be taken by way of limitation. The spirit and scope of the present invention are to be limited only by the terms of the appended claims. | A flexible partition includes a curtain secured to a support structure at its topped edge and a shaft secured to the curtain displaced from the top edge and extending across the curtain. A driver is coupled to the shaft to rotate the shaft, thereby rolling and unrolling the curtain. A carriage connected to one end of the driver cooperates with a guide to restrict the rotation of the first end of the driver. The guide is pivotally coupled at one end to the support structure to move between raised and lowered positions. | 4 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to an attachment for a skid steer loader, and particularly to a grabbing mechanism for a skid steer loader.
[0002] In fields such as construction, agriculture, and landscaping, it is often necessary to clear an area of rocks, trees, and brush. When clearing an area, it may be possible to use a tractor, front-end loader, or similar large machine to assist with the heavy lifting required to remove trees and rocks. However, tractors and the like are very destructive to the area being cleared, and may leave deep tracks and other disruptions to the ground being cleared. As such, more time and effort must be spent smoothing the area after the use of large machines, which results in increased cost.
[0003] Furthermore, the area in which the work must be done is often so small as to prevent a large tractor from being utilized during clearing. Clearing the area by hand is very labor intensive, and sometimes impossible. For this reason, skid steer loaders are a convenient alternative to large tractors or machines. Skid steer loaders are small enough to maneuver into restricted areas, yet provide the strength required for moving small trees and rocks. Because they are much smaller than a tractor, skid steer loaders often create much less destruction to the soil in the area they are used to clear. Thus, skid steer loaders are a convenient alternative to larger tractors or machines which may have a much greater disruptive impact on the area to cleared.
[0004] Skid steer loaders are often equipped with a bucket attachment. While the bucket attachment is capable of scooping, pushing, and transporting dirt and other material, it is not ideally suited for tree and stump removal, rock removal, or similar tasks. For instance, when using the bucket attachment to remove a tree or tree stump, a significant amount of soil disruption is caused. Specifically, the tree or stump must be removed by digging it out, or by pushing or pulling it out of the ground. When this occurs, a large hole is left behind, often as deep as two feet. As a result, the hole must be filled, which requires extra time, effort, and cost to refill the holes and smooth them over.
[0005] Thus, there is a need in the art for an attachment to a skid steer loader which is capable of grasping trees and removing them with less disruption to the environment.
BRIEF SUMMARY OF THE INVENTION
[0006] The present invention is a grabbing attachment for a skid steer loader. The grabber attachment comprises three prongs which can be powered closed or powered open. The prongs can be closed about logs or small trees, allowing the skid steer loader to lift the logs or remove the trees with minimal disruption to the surrounding soil. A scraper blade is included on the grabber attachment to allow the attachment to clear dead fall and brush. In addition, the blade allows the grabber attachment to push the soil around the roots of live trees to loosen the tree a bit so that it can be removed more easily and with a smaller clump of dirt coming out with the roots as the tree is removed. Side shields are included on the attachment to protect the tractor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] [0007]FIG. 1 is a perspective view of a skid steer loader and the grabber attachment used to remove a log.
[0008] [0008]FIG. 2 is a perspective view of the grabber attachment.
[0009] [0009]FIG. 3 is a side view of the grabber attachment.
[0010] [0010]FIG. 4A is a top plan view of the grappber attachment in an open position.
[0011] [0011]FIG. 4B is a top plan view of the grabber attachment in a closed position.
[0012] [0012]FIG. 5 is a perspective view of the rear of the grabber attachment.
DETAILED DESCRIPTION
[0013] [0013]FIG. 1 is a perspective view of a skid steer loader 10 having a grabber attachment 12 . The skid steer load 10 comprises a frame 14 located on four wheels 16 . The frame 14 comprises an operator cab 18 inside which are located a series of operator controls which allow an operator to steer and maneuver the skid steer loader 10 . Arms 20 are also connected to the frame 14 . The grabber attachment 12 is located on a front side of the arms 20 . The arms can be raised or lowered using vehicle controls in the cab 18 , and the grabber attachment 12 can likewise be maneuvered using a variety of operator controls located in the cab 18 .
[0014] The grabber attachment 12 is particularly suited for clearing both live trees as well as dead fallen trees. The grabber attachment 12 can close about a tree so that the tree can be removed from the ground and moved to either a pile or container for disposal. Similarly, the grabber attachment 12 can be closed about a dead tree or log, and thus allow the operator to move the log so that it can be stacked neatly for transport or burning. The grabber attachment 12 is designed to be attached to the skid steer loader so that while the tree or log is grasped by the grabber attachment 12 , the grabber attachment 12 can be positioned so that the operator's view from the cab 18 remains relatively unobstructed. In this manner, the operator can more effectively maneuver the skid steer loader 10 as well as position the tree or log 22 carried by the grabber attachment 12 .
[0015] [0015]FIG. 2 is a perspective view of the grabber attachment 12 of the present invention. Visible in FIG. 2 is aback plate 30 , side guards 32 , and bottom blade 34 . Near the top of the back plate 30 are two reinforcing bars 36 which meet near the middle of the grabber 12 at center pin 38 . Also connected to the back plate 30 are two hydraulic cylinders 40 , 42 . Connected to the center pin 38 are a tine 44 and a double tine 46 . The tine 44 contains a single prong, while the double tine 46 contains two prongs. The tines 44 , 46 are arranged vertically.
[0016] The first hydraulic cylinder 40 is connected to tine 44 and the second hydraulic cylinder 42 is connected to double tine 46 . The second hydraulic cylinder 42 connects to a bracket 48 on a vertical bar 50 located between the double tines 46 . Similarly, the hydraulic cylinder 40 connects to the single tine 44 at a bracket 48 located on the tine 44 . The other end of the hydraulic cylinders 40 , 42 connect to the back plate 30 at another bracket 48 .
[0017] Each hydraulic cylinder has two hydraulic connections 52 . Hydraulic hoses 54 are routed from the hydraulic cylinders 40 , 42 across the top reinforcing bars 36 of the grabber 12 . The hydraulic hoses 54 are secured at various parts on the grabber 12 and arms 20 , and eventually connect to the hydraulic system on the skid steer loader 10 . The hydraulic connections are made in a manner well known in the art.
[0018] In operation, the grabber 12 is opened or closed using hydraulic pressure supplied to the hydraulic cylinders 40 , 42 by the hoses 54 . By applying hydraulic pressure at the cylinder 40 , 42 , the tines 44 , 46 can be powered closed, or powered open. Thus, the tines 44 , 46 can be used to close about a log or tree, or the tines 44 , 46 can further be used to push things to the side or move otherwise heavy objects. The ability to power the tines 44 , 46 both open and closed increases the flexibility of the grabber attachment 12 .
[0019] In addition, the bottom blade 34 allows the grabber attachment 12 to push a small amount of material. The side guards 32 protect the rest of the loader 10 and in particular the tires 16 from debris as the grabber 12 is used to clear an area.
[0020] [0020]FIG. 3 is a side view of the grabber attachment 12 . In FIG. 3, the blade 34 is more clearly visible. The blade 34 is slightly angled to increase the ability of the blade 34 to push material located close to the ground. In addition, a bottom brace 60 is shown supporting the center pin 38 . The bottom brace 60 is attached to the back plate 30 and provides strength support for the tines 44 , 46 as they close about debris and other material.
[0021] [0021]FIGS. 4A and 4B are top views illustrating the operation of the tines 44 , 46 of the grabber attachment 12 . Shown in FIGS. 4A and 4B are the back plate 30 , the bottom blade 34 , the reinforcing bars 36 , and the center pin 38 . In addition, the right tine 44 and double tine 46 are visible, as well as the hydraulic cylinders 40 , 42 . For simplicity, the hydraulic connections 52 and hoses 54 are not shown in FIGS. 4A and 4B.
[0022] As can be seen by comparing FIGS. 4A and 4B, the tines 44 , 46 can be moved so that they pivot about a vertical axis at center pin 38 . When fully opened, the tines 44 , 46 may have a distance from the tip 62 of the single tine 44 to the tip 62 of the double tine 36 of about 18 inches to as large as about 22 inches. As shown in FIG. 4B, when closed, the tips 62 of the tines 44 , 46 overlap slightly.
[0023] The center pin 38 is preferably made out of a solid shaft of steel. In addition, the tines 44 , 46 are preferably formed of a solid metal, approximately two inches by two inches square. The tips 62 are preferably tapered or otherwise shaped in such a manner to allow the tines 44 , 46 to more easily pick up a round material such as a tree log. By allowing the tines 44 , 46 to overlap, it is possible to close the grabber 12 around a variety of trees having diameters as small as three to four inches to as large as 18 inches. The back plate 30 , as well as the bottom blade 34 and side guards 32 are preferably formed of 8 inch steel. The bottom blade 34 may further comprise a five inch cutting edge made of harden steel.
[0024] [0024]FIG. 5 is a rear view of the grabber attachment 12 illustrating the side which attaches to the skid steer loader. Located on the rear of the grabber 12 is an upper attachment flange 70 and two lower attachment brackets 72 . On each attachment bracket 72 are located two attachment holes 76 . The grabber attachment 12 can thus be quickly and easily attached to the skid steer loader by positioning the front portion of the skid steer loader 10 underneath the upper flange 70 and positioning a wedge through the holes 76 . This method of quickly attaching to the skid steer loader is well known in the art. In addition, other methods of attaching to a skid steer loader to allow for maximum flexibility and allow the grabber 12 to fit on the majority of different brands of skid steer loaders is likewise possible.
[0025] Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. | An attachment for use with a skid steer loader having a single tine and a double tine connected at a center pin. The tines are configured to be powered open or closed about a vertical axis created by the center pin. The tines can be actuated by hydraulic cylinders. A scraper blade is included on the grabber attachment to allow the attachment to clear dead fall and brush. Side shields are included on the attachment to protect the tractor. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority to Japanese Patent Application No. 2011-213137, filed on Sep. 28, 2011, the disclosure of which is hereby incorporated by reference herein in its entirety.
BACKGROUND
This disclosure relates to a sewing machine and a computer-readable medium. The sewing machine is configured such that en embroidery frame is detachably attachable to the sewing machine. The computer-readable medium stores a program for the sewing machine.
A sewing machine is widely known that is configured to sew am embroidery pattern using an embroidery frame. The embroidery frame is a circular form. The embroidery frame is configured to be rotatable to an intended angle. For example, the embroidery frame that comprises a pair of embroidery frames and an outer frame is configured to be attachable to the sewing machine. The pair of embroidery frames comprises a small embroidery frame and a big embroidery frame. The small embroidery frame is a circular form and the big embroidery frame is also a circular form. An inner diameter of the big embroidery frame is longer than an outer diameter of the small embroidery frame. A work cloth can be held between the small embroidery frame and the big embroidery frame. The outer frame can hold the pair of embroidery frames such that the pair of embroidery frames is rotatable. A fixation screw is provided on a side face of the outer embroidery frame. A triangular mark is provided on an upper face of the big embroidery frame and a plurality of scale marks indicative of angles are provided on the outer embroidery frame. The pair of embroidery frames can be rotated to the intended angle with respect to the outer embroidery frame by a user of the sewing machine, as the user looks at the triangular mark and the plurality of scale marks. After rotating, the fixation screw can be tightened by the user. In this manner, the pair of embroidery frames can be fixed to the outer embroidery frame.
SUMMARY
When the embroidery frame as described above is used by the user, the user has to adjust the pair of embroidery frames with respect to the outer embroidery frame, as the user looks at the triangular mark and the plurality of scale marks. In that case, the triangular mark or the scale mark may be covered by the work cloth. As a result, it may be difficult for the user to see the triangular mark or the scale mark. Alternatively, it may be difficult to increase accuracy of adjusting the angle, because the user has to adjust the pair of embroidery frames with respect to the outer embroidery frame by visually checking the triangular mark and the scale mark.
Various exemplary embodiments of the general principles herein provide a sewing machine and a non-transitory computer-readable medium which allows a user to adjust the angle of an embroidery frame easily.
Exemplary embodiments herein provide a sewing machine that comprises a mounting portion, an image capturing device, a processor, and a memory. The mounting portion may be configured to be mounted with an embroidery frame. The embroidery frame may comprise a frame configured to hold a work cloth and an outer frame configured to be detachably attached to an outside of the frame and configured to rotatably hold the frame. The image capturing device may be configured to capture an image including the embroidery frame mounted on the mounting portion. The processor may be configured to execute instructions. The memory may be configured to store computer-readable instructions therein, wherein the computer-readable instructions instruct the sewing machine to execute steps comprising identifying a mark from the image captured by the image capturing device, wherein the mark is provided on the embroidery frame or on the work cloth held by the embroidery frame, determining a rotation angle of the frame with respect to the outer frame based on the identified mark, and notifying rotation information based on the determined rotation angle. The rotation information may be information for adjusting the rotation angle to a specified rotation angle.
Exemplary embodiments also provide a non-transitory computer-readable medium storing computer-readable instructions that, when executed, instruct a sewing machine. The sewing machine may comprise a mounting portion and an image capturing device. The mounting portion may be configured to be mounted with an embroidery frame. The embroidery frame may comprise a frame configured to hold a work cloth and an outer frame configured to be detachably attached to an outside of the frame and configured to rotatably hold the frame. The image capturing device may be configured to capture an image including the embroidery frame mounted on the mounting portion. The computer-readable instructions may instruct the sewing machine to execute steps comprising identifying a mark from the image captured by the image capturing device, wherein the mark is provided on the embroidery frame or on the work cloth held by the embroidery frame, determining a rotation angle of the frame with respect to the outer frame based on the identified mark, and notifying rotation information based on the determined rotation angle. The rotation information may be information for adjusting the rotation angle to a specified rotation angle.
BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments of the present disclosure will be described below in detail with reference to the accompanying drawing in which:
FIG. 1 is en oblique view of a sewing machine 1 on which an embroidery frame 9 is mounted;
FIG. 2 is a figure that shows a needle bar 6 to which a sewing needle 7 is attached, and an area around the needle bar 6 , as seen from the left side of the sewing machine 1 ;
FIG. 3 is a figure that shows the needle bar 6 to which a cutwork needle 8 is attached, and the area around the needle bar 6 , as seen from the left side of the sewing machine 1 ;
FIG. 4 is an oblique view of the embroidery frame 9 ;
FIG. 5 is an oblique view that shows an internal structure of the embroidery frame 9 that is shown in FIG. 4 ;
FIG. 6 is an exploded oblique view of the embroidery frame 9 ;
FIG. 7 is a plan view of the embroidery frame 9 ;
FIG. 8 is a block diagram that shows an electrical configuration of the sewing machine 1 ;
FIG. 9 is a diagram of a data configuration of a outwork data table 59 ;
FIG. 10 is a flowchart of cutwork processing;
FIG. 11 is a flowchart of frame rotation processing;
FIG. 12 is a figure that shows an example of an image that is displayed on a liquid crystal display 15 ;
FIG. 13 is a figure that shows another example of an image that is displayed on the liquid crystal display 15 ; and
FIG. 14 is a figure that shows yet another example of an image that is displayed on the liquid crystal display 15 .
DETAILED DESCRIPTION
Hereinafter, an embodiment of the present disclosure will be explained with reference to the drawings. A configuration of a sewing machine 1 will be explained with reference to FIGS. 1 and 2 . In FIG. 1 , the side where a user of the sewing machine 1 is positioned is defined as the front side of the sewing machine 1 , and the opposite side is defined as the rear side. The left-right direction as seen by the user is defined as the left-right direction of sewing machine 1 . That is the face of the sewing machine 1 on which a switch cluster 25 that will be described later is provided is the front face of the sewing machine 1 . The longitudinal direction of a bed 11 and an arm 13 are the left-right direction of the sewing machine 1 , and a side on which a pillar 12 is positioned is the right side of the sewing machine 1 . A direction in which the pillar 12 extends is the up-down direction of the sewing machine 1 .
As shown in FIG. 1 , the sewing machine 1 includes a bed 11 , a pillar 12 , an arm 13 , and a head 14 . The bed 11 is a base portion of the sewing machine 1 and extends in the left-right direction. The pillar 12 extends upward from the right end of the bed 11 . The arm 13 extends to the left from the upper end of the pillar 12 . The head 14 is provided on the left end of the arm 13 . A needle plate (not shown in the drawings) is provided in the top face of the bed 11 . A feed dog (not shown in the drawings), a cloth feed mechanism (not shown in the drawings), a feed adjustment pulse motor 78 (refer to FIG. 8 ), and a shuttle mechanism (not shown in the drawings) are provided within the bed 11 , underneath the needle plate. The feed dog may feed, by a specified feed amount, a work cloth on which sewing is performed. The cloth feed mechanism may drive the feed dog. The feed adjustment pulse motor 78 may adjust the feed amount.
In a case where embroidery sewing is performed with the sewing machine 1 , an embroidery frame 9 , which holds a work cloth 100 , may be disposed on the top side of the bed 11 . An area inside the embroidery frame 9 is an embroidery area in which stitches of an embroidery pattern can be formed. A moving unit 19 that is configured to move the embroidery frame 9 may be removably mounted on the bed 11 . A carriage cover 35 , which extends in the front-rear direction, is provided on the upper part of the moving unit 19 . A Y axis moving mechanism (not shown in the drawings) is provided inside the carriage cover 35 . The Y axis moving mechanism is configured to move a carriage (not shown in the drawings) in a Y axis direction (the front-rear direction of the sewing machine 1 ). The embroidery frame 9 may be removably mounted on the carriage. A mounting portion 351 , on which the embroidery frame 9 can be mounted, is provided on the right side of the carriage. The mounting portion 351 projects to the right from the right side face of the carriage cover 35 . An attachment portion 942 (refer to FIG. 4 ) that is provided on the embroidery frame 9 may be mounted on the mounting portion 351 . The carriage, the Y axis moving mechanism, and the carriage cover 35 may be moved in an X axis direction (the left-right direction of the sewing machine 1 ) by an X axis moving mechanism (not shown in the drawings). The X axis moving mechanism is provided inside the body of the moving unit 19 .
The X axis moving mechanism and the Y axis moving mechanism may be respectively driven by an X axis motor 83 (refer to FIG. 8 ) and a Y axis motor 84 (refer to FIG. 8 ). A needle bar 6 (refer to FIG. 2 ) and the shuttle mechanism (not shown in the drawings) may be driven as the embroidery frame 9 is moved in the X axis direction and the Y axis direction. In this manner, an embroidery sewing operation that sews a specified embroidery pattern or the like in the work cloth 100 that is held by the embroidery frame 9 and a cutwork operation that forms cuts in the work cloth 100 in a specified shape may be performed. In a case where an ordinary pattern, which is not an embroidery pattern, is sewn, the moving unit 19 may be removed from the bed 11 . Then ordinary sewing may be performed as the work cloth 100 is moved by the feed dog.
A vertically rectangular liquid crystal display 15 is provided on the front face of the pillar 12 . Images of various types of items, such as a plurality of types of patterns, names of commands that cause various types of functions to be performed, various types of messages, images that have been captured by an image sensor 48 (refer to FIG. 2 ), and the like, may be displayed on the liquid crystal display 15 . A transparent touch panel 26 is provided on the front face of the liquid crystal display 15 . Using a finger or a special touch pen, the user may perform a pressing operation on the touch panel 26 . Hereinafter, this operation is referred to as a panel operation. The touch panel 26 may detect a position that is pressed by a finger or a special touch pen etc., and the sewing machine 1 may determine the item that corresponds to the detected position. Thus, the sewing machine 1 may recognize the selected item. By performing the panel operation, the user can select a pattern to be sewn or a command to be executed.
The structure of the arm 13 will be explained. An cover 16 is provided in the top part of the arm 13 . The cover 16 is axially supported such that the cover 16 can be opened and dosed by being rotated about an axis that extends in the left-right direction at the upper rear edge of the arm 13 . Underneath the cover 16 , that is, in the interior of the arm 13 , a thread container portion (not shown in the drawings) is provided that may contain a thread spool (not shown in the drawings) that supplies an upper thread. The upper thread may be supplied from the thread spool to a sewing needle 7 (refer to FIG. 2 ) through a thread hook portion that includes a tensioner, a thread take-up spring, and a thread take-up lever, which are not shown in the drawings. The tensioner is provided in the head 14 and configured to adjust the thread tension. The thread take-up lever may be driven reciprocally up and down and pull the upper thread upward. The sewing needle 7 may be attached to the needle bar 6 (refer to FIG. 2 ). The needle bar 6 may be moved up and down by a needle bar up-and-down moving mechanism (not shown in the drawings), which is provided inside the head 14 . The needle bar up-and-down moving mechanism may be driven by a drive shaft (not shown in the drawings) that is rotationally driven by a sewing machine motor 79 (refer to FIG. 8 ). In other words, the needle bar 6 may be driven by the sewing machine motor 79 .
A switch cluster 25 is provided in the lower part of the front face of the arm 13 . The switch cluster 25 includes a sewing start/stop switch 21 . The sewing start/stop switch 21 may be used to start or stop the operation of the sewing machine 1 . That is, the sewing start/stop switch 21 may be used by the user to issue commands to start or stop the sewing.
As shown in FIG. 2 , the needle bar 6 is provided in the lower portion of the head 14 . One of the sewing needle 7 (refer to FIG. 2 ) and a outwork needle 8 (refer to FIG. 3 ) can be attached to the lower end of the needle bar 6 . A presser bar 45 is provided to the rear of the needle bar 6 . A presser holder 46 may be attached to the lower end of the presser bar 45 . A presser foot 47 , which may press down on the work cloth 100 , may be fixed to the presser holder 46 . The image sensor 48 is provided inside the head 14 . The image sensor 48 is configured to capture an image of an area that includes the embroidery frame 9 that is mounted on the mounting portion 351 .
The outwork needle 8 will be explained. As shown in FIG. 3 , a cutting portion 89 is formed at the tip of the outwork needle 8 . The cutting portion 89 has a sharp-pointed shape (not shown in the drawings) in a front view and has a specified width in the front-rear direction (the left-right direction in FIG. 3 ) in a side view. The front edge of the cutting portion 89 extends slightly lower than does the rear edge. The portion of the cutting portion 89 from the front edge to the rear edge is curved slightly upward. When the outwork operation is performed with the outwork needle 8 , a out that extends in the front-rear direction is formed in the work cloth 100 . The length of the cut is the same as the width of the cutting portion 89 of the outwork needle 8 . The outwork operation can be performed when the outwork needle 8 is attached to the lower end of the needle bar 6 . The embroidery sewing operation can be performed when the sewing needle 7 is attached to the lower end of the needle bar 6 , as shown in FIG. 2 .
The embroidery frame 9 will be explained with reference to FIGS. 4 to 7 . In the explanation that follows, the up-down direction in FIGS. 4 and 5 is defined as the up-down direction of the embroidery frame 9 . As shown in FIGS. 4 to 6 , the embroidery frame 9 is formed by combining an inner frame 91 , a middle frame 92 , and an outer frame 94 , each of which has a circular frame shape. As shown in FIG. 4 , in the embroidery frame 9 , the middle frame 92 is disposed to the outside of the inner frame 91 in the radial direction. The outer frame 94 is disposed to the outside of the middle frame 92 in the radial direction. The embroidery frame 9 is configured to clamp the work cloth 100 between the inner frame 91 and the middle frame 92 and has a structure in which the inner frame 91 and the middle frame 92 can rotate in relation to the outer frame 94 . The inner frame 91 and the middle frame 92 can be rotated about a rotational axis R shown in FIG. 6 , in relation to the outer frame 94 . Note that, in the embroidery frame 9 according to the present embodiment, the rotational axis R passes thorough the center of each circle that is formed by each of the inner frame 91 , the middle frame 92 , and the outer frame 94 (specifically, frame portions 911 , 921 , and 941 , which are described below). Hereinafter, the direction of the rotational axis R is simply referred to as an “axial direction”.
As shown in FIGS. 4 to 6 , the inner frame 91 includes a circular frame portion 911 . The frame portion 911 has thicknesses in the axial direction and the radial direction. The inner frame 91 includes an adjustment portion 915 that can adjust the diameter of the inner frame 91 . The diameter of inner frame 91 may be adjusted according to the thickness of the work cloth 100 that is clamped between the inner frame 91 and the middle frame 92 . The adjustment portion 915 includes a parting portion 916 , a pair of screw mounting portions 917 , and an adjusting screw 918 . The parting portion 916 is a location where a portion in the circumferential direction of the frame portion 911 of the inner frame 91 is discontinuous through the axial direction. The pair of the screw mounting portions 917 are provided in upper portions of the frame portion 911 on both sides of the parting portion 916 . The pair of the screw mounting portions 917 project to the outside in the radial direction and are positioned opposite one another. The pair of the screw mounting portions 917 are provided with holes 9171 , 9172 that are through-holes in a direction that is orthogonal to the faces of the screw mounting portions 917 that are opposite one another (refer to FIG. 6 ). Of the two holes 9171 , 9172 , the hole 9172 (the hole on the lower right in FIG. 6 ) is provided with an embedded nut (not shown in the drawings) in which a threaded hole is formed.
The adjusting screw 918 is a threaded member that includes a large-diameter head portion 9181 , which the user may rotate by gripping with his fingers, and a small-diameter shall portion 9183 that extends as a single piece from the head portion 9181 . A male threaded portion 9182 is formed from roughly the center of the axial direction of the shaft portion 9183 to the tip. A narrow groove 9184 is formed in the shaft portion 9183 in a location that is close to the head portion 9181 . A retaining ring 9185 may be fitted into the narrow groove 9184 . The adjusting screw 918 may be mounted by passing the shaft portion 9183 through the hole 9171 and screwing the male threaded portion 9182 into the threaded hole in the embedded nut in the hole 9172 . In this state, with the retaining ring 9185 fitted into the narrow groove 9184 of the shaft portion 9183 , the adjusting screw 918 can be held such that it can rotate in the screw mounting portion 917 on the side where the hole 9171 is located and cannot move in the axial direction. At this time, if the user grips the head portion 9181 of the adjusting screw 918 with his fingers and performs a rotation operation, the screw mounting portion 917 on the side where the hole 9172 is located moves through the embedded nut in the axial direction of the shaft portion 9183 . The direction of that movement is determined by the direction of rotation of the adjusting screw 918 . In this way the adjusting screw 918 may be coupled with the pair of the screw mounting portions 917 and adjust the gap between the pair of the screw mounting portions 917 such as to make the gap wider or narrower. The adjusting of the gap between the pair of the screw mounting portions 917 adjusts the diameter of the inner frame 91 in accordance with the thickness of the work cloth 100 . For example, to the extent that the gap between the pair of the screw mounting portions 917 becomes narrower, the diameter of the inner frame 91 becomes smaller. Therefore, the embroidery frame 9 is able to clamp the work cloth 100 that has a greater thickness between the middle frame 92 and the inner frame 91 . Note that, for ease of explanation, the retaining ring 9185 is omitted from all of the drawings except FIG. 6 .
A marker 110 is provided on an edge face on the top side of the inner frame 91 . As shown in FIG. 7 , the marker 110 is provided by the drawing of a first circle 101 , a second circle 102 , a first center point 111 , and a second center point 112 on the edge face on the to side of the inner frame 91 . The second circle 102 and the first circle 101 are contiguous with one another in the circumferential direction of the inner frame 91 . The diameter of the second circle 102 is smaller than the diameter of the first circle 101 . The first center point 111 is in the center of the first circle 101 . The second center point 112 is in the center of the second circle 102 .
As shown in FIGS. 4 to 6 , the middle frame 92 includes a circular frame portion 921 . The frame portion 921 has an inside diameter that is larger than the outside diameter of the frame portion 911 of the inner frame 91 . The middle frame 92 may be removably mounted on the inner frame 91 by removably mounting the frame portion 921 of the middle frame 92 on the outer side of the frame portion 911 of the inner frame 91 in the radial direction. As shown in FIGS. 5 to 7 , a plurality of first engaging portions 930 are provided on the outer circumferential side face of the lower edge portion of the frame portion 921 of the middle frame 92 . The first engaging portions 930 are made up of a plurality of recessed portions 931 , each of which is formed approximately in the shape of a V. The plurality of the recessed portions 931 are formed at intervals of a specified angle, for example, every four degrees, around the entire outer circumferential side face of the tower edge portion of the frame portion 921 of the middle frame 92 . In their entirety, the plurality of the first engaging portions 930 are formed in the shape of a gear. Hereinafter, the portion of the middle frame 92 where the plurality of the first engaging portions 930 form the gear shape is called a gear portion 934 . The middle frame 92 can be locked to the outer frame 94 at one of a plurality of predetermined rotation angles (for example, one rotation angle every four degrees) by engaging a second engaging portion 947 , which will be described later, with one of the plurality of the recessed portions 931 .
A flange portion 929 is provided in a central portion in the axial direction of the outer circumferential side face of the frame portion 921 , on the upper side of the gear portion 934 . The flange portion 929 projects to the outside in the radial direction around the entire circumference of the frame portion 921 . A support portion 936 is provided on an inner circumferential side face of the lower edge of the frame portion 921 . The support portion 936 projects to the inside in the radial direction around the entire circumference of the frame portion 921 . The support portion 936 is a portion that supports a lower edge face of the inner frame 91 .
As shown in FIGS. 4 to 6 , the outer frame 94 includes a circular frame portion 941 . A support portion 946 that projects to the inside in the radial direction around the entire circumference of the frame portion 941 is provided on an inner circumferential side face of the lower edge of the frame portion 941 . The support portion 946 is a portion that supports a lower edge face of the middle frame 92 . The attachment portion 942 is provided on the outer side of the frame portion 941 in the radial direction. The embroidery frame 9 may be affixed to the sewing machine 1 (refer to FIG. 1 ) by mounting the attachment portion 942 on the mounting portion 351 of the card age (refer to FIG. 1 ).
A box-shaped coupling portion 943 is provided between the frame portion 941 and the attachment portion 942 . The coupling portion 943 couples the frame portion 941 and the attachment portion 942 . As shown in FIGS. 5 and 7 , the interior of the coupling portion 943 is hollow. The second engaging portion 947 is provided in the coupling portion 943 near the edge on the side of the frame portion 941 (the side that faces toward the middle frame 92 ). In the present embodiment, the second engaging portion 947 is a flat spring 948 .
As shown in FIG. 5 , a threaded attachment portion 956 that projects upward from a bottom face of the coupling portion 943 is provided inside the coupling portion 943 . A threaded hole (not shown in the drawings) is formed in the threaded attachment portion 956 . A base end portion 957 of the flat spring 948 is disposed on the top side of the threaded attachment portion 956 . A hole (not shown in the drawings) is provided in the center of the base end portion 957 . The base end portion 957 of the flat spring 948 is affixed to the threaded attachment portion 956 by attaching a screw 958 , which passes through the hole, to the threaded attachment portion 956 .
A free end portion 955 extends from the base end portion 957 of the flat spring 948 . As shown in FIG. 7 , the free end portion 955 is bent downward (refer to FIG. 5 ) at the right edge (the right side in FIG. 7 ) of the base end portion 957 and extends toward the front (toward the bottom of FIG. 7 ). A protruding portion 952 is provided at the front end of the free end portion 955 . The protruding portion 952 is formed approximately in the shape of a V, such that it protrudes toward the middle frame 92 . The tip of the protruding portion 952 is able to engage with one of the plurality of the recessed portions 931 . At that time, the elastic force of the flat spring 948 energizes the protruding portion 952 in such a direction that the tip of the protruding portion 952 presses against the recessed portion 931 .
The engaging of the tip of the protruding portion 952 with one of the plurality of the recessed portions 931 and its pressing against the recessed portion 931 by the elastic force of the flat spring 948 can lock the middle frame 92 such that it cannot be rotated in relation to the outer frame 94 . In a case where the user rotates the middle frame 92 in relation to the outer frame 94 , one of the oblique faces of the recessed portion 931 (one of the oblique faces of the V shape) pushes the protruding portion 952 in a direction in which the protruding portion 952 is separated from the middle frame 92 , in opposition to the elastic force of the flat spring 948 . At this time, the free end portion 955 of the flat spring 948 bends such that the engagement of the protruding portion 952 and the recessed portion 931 is released. Then the protruding portion 952 engages with the recessed portion 931 that is adjacent to the recessed portion 931 with which the protruding portion 952 has been engaged previously.
If the rotating of the middle frame 92 is continued further, the engaging and the releasing of the engagement of the protruding portion 952 with one of the recessed portions 931 are repeated. The plurality of the recessed portions 931 are provided at four-degree intervals, so the user is able to set the angle of rotation of the middle frame 92 in relation to the outer frame 94 at four-degree intervals.
The mode in which the inner frame 91 , the middle frame 92 , and the outer frame 94 are combined will be explained. First, the user may place the middle frame 92 on a desktop or the like such that the gear portion 934 that includes the first engaging portion 930 is on the bottom side. Then the user may insert the inner frame 91 into the inner side of the middle frame 92 from the top side of the middle frame 92 , thus clamping the work cloth 100 between the inner frame 91 and the middle frame 92 . At this time, the user, by adjusting the adjustment portion 915 , may adjust the diameter of the inner frame 91 in accordance with the thickness of the work cloth 100 . In the explanation that follows, the frame that is formed by the combining of the inner frame 91 and the middle frame 92 is called an assembled unit 95 .
Next, the user may place the assembled unit 95 into the outer frame 94 from the top side of the outer frame 94 . At this time, the user may place the assembled unit 95 into the frame portion 941 such that the protruding portion 952 engages with one of the plurality of the recessed portions 931 . When the assembled unit 95 is placed into the outer frame 94 , a state is created in which the protruding portion 952 is engaged with one of the recessed portions 931 . Thus the second engaging portion 947 and the first engaging portion 930 may be engaged, and the rotation of the middle frame 92 (the assembled unit 95 ) may be locked in relation to the outer frame 94 . The inner frame 91 , the middle frame 92 , and the outer frame 94 can be combined as described above, to obtain the completed form of the embroidery frame 9 . Then the user may attach the completed form of the embroidery frame 9 to the carriage of the moving unit 19 that is mounted on the sewing machine 1 (refer to FIG. 1 ). The user is able to rotate and lock the middle frame 92 (the assembled unit 95 ) in relation to the outer frame 94 .
An electrical configuration of the sewing machine 1 will be explained with reference to FIG. 8 . As shown in FIG. 8 , a control portion 60 of the sewing machine 1 includes a CPU 61 , a ROM 62 , a RAM 63 , an EEPROM 64 , and an input/output interface 65 , all of which are connected to one another by a bus 67 . Programs for the performing of processing by the CPU 61 , as well as data and the like, are stored in the ROM 62 . The EEPROM 64 includes at least a outwork data storage area 641 . A plurality of outwork data tables, an example of which is a outwork data table 59 (refer to FIG. 9 ), are stored in the cutwork data storage area 641 . A plurality of embroidery data sets for the performing of embroidery sewing by the sewing machine 1 are also stored in the EEPROM 64 .
The sewing start/stop switch 21 , the touch panel 26 , and drive circuits 71 , 72 , 75 , 85 , 86 , and 87 are electrically connected to the input/output interface 65 . The drive circuit 71 may drive the feed adjustment pulse motor 78 . The drive circuit 72 may drive the sewing machine motor 79 . The drive circuit 75 may drive the liquid crystal display 15 . The drive circuits 85 and 86 may respectively drive the X axis motor 83 and the axis motor 84 that move the embroidery frame 9 . The drive circuit 87 may drive the image sensor 48 . By controlling the image sensor 98 , the CPU 61 (refer to FIG. 8 ) can capture an image of the area that includes the embroidery frame 9 that is mounted on the mounting portion 351 .
The outwork data table 59 will be explained with reference to FIG. 9 . The cutwork data table 59 that is shown in FIG. 9 contains data for cutting out a plurality of areas 107 on inner sides of a plurality of flower petal patterns 106 in a flower pattern 105 (refer to FIG. 12 ) that has been embroidered in the work cloth 100 . The cutwork data table 59 may be stored in the outwork data storage area 641 (refer to FIG. 8 ).
As shown in FIG. 9 , columns are provided in the outwork data table 59 for a variable N, frame rotation data, an X coordinate, and a Y coordinate, and data may be stored in association with each of the items. The variable N is a variable that indicates an order in which a cut is formed in the work cloth 100 . The frame rotation data are data that indicate predetermined rotation angles of the middle frame 92 in relation to the outer frame 94 . The X coordinate and the Y coordinate are coordinates for predetermined needle drop points. Note that in the present embodiment, the coordinates at the center of the embroidery frame 9 in an image 151 that will be described later (refer to FIG. 12 ) are defined as the coordinates of the origin point (X coordinate 0, Y coordinate 0), with the coordinate in the left-right direction defined as the X coordinate and the coordinate in the up-down direction defined as the Y coordinate (refer to FIG. 12 ). In a case where the areas 107 on the inner sides of the flower petal patterns 106 are cut out, the middle frame 92 is rotated, in relation to the outer frame 94 , to each of the rotation angles based on the frame rotation data, in the order of the variables N 1 to 221. A cut is formed in the work cloth 100 by using the outwork needle 8 at each needle drop point that is defined by the X coordinate and the Y coordinate for the corresponding variable N.
Cutwork processing that is performed by the CPU 61 of the sewing machine 1 will be explained with reference to FIGS. 10 to 14 . In the explanation that follows, a case in which a outwork of the flower pattern 105 is created by cutting out the areas 107 on the inner sides of the four flower petal patterns 106 that are shown in FIG. 12 will be explained as a specific example.
In the specific example, when the areas 107 on the inner sides of the four flower petal patterns 106 are to be cut out, the user attaches the cutwork needle 8 to the needle bar 6 (refer to FIG. 3 ). The orientation of the cutting portion 89 of the outwork needle 8 is fixed such that the cutting portion 89 extends in the front-rear direction, as shown in FIG. 3 . Therefore, in order to cut all four of the areas 107 out of the work cloth 100 , it is necessary to form cuts along the outlines of the inner sides of the flower petal patterns 106 as the rotation angle of the middle frame 92 (the assembled unit 95 ) is changed in relation to the outer frame 94 . Accordingly, the user performs a panel operation to cause the sewing machine 1 to perform the outwork processing, which causes the sewing machine 1 to cut out the areas 107 while changing the rotation angle of the middle frame 92 (the assembled unit 95 ) in relation to the outer frame 94 . In the outwork processing, various types of information are reported to the user so that the user can adjust the rotation angle of the middle frame 92 in relation to the outer frame 94 to a specified rotation angle. In the explanation that follows, the information for adjusting the rotation angle of the middle frame 92 in relation to the outer frame 94 to the specified rotation angle is called rotation information.
When a command to perform the cutwork processing is input by the panel operation. The CPU 61 of the sewing machine 1 reads out a program for the cutwork processing that is stored in the ROM 62 . The CPU 61 performs the cutwork processing in accordance with instructions included in the program that is read out from the ROM 62 . As shown in FIG. 10 , in the cutwork processing after the embroidery frame 9 has been moved to an initial position where the center of the embroidery frame 9 is the needle drop point, the image sensor 48 is controlled such that the image 151 , which includes the area that includes the embroidery frame 9 that is mounted on the mounting portion 351 , is captured (Step S 11 ). The image 151 that is captured at Step S 11 is displayed on the liquid crystal display 15 (Step S 12 ). An example of the displayed image 151 is shown in FIG. 12 . Note that for the purpose of the explanation, only a portion of the work cloth 100 that resides on the inner side of the inner frame 91 is shown in FIG. 12 (the same is true for FIGS. 13 and 14 ).
The marker 110 that is provided on the embroidery frame 9 is identified based on the image 151 , the rotation angle of the middle frame 92 in relation to the outer frame 94 is detected based on the identified marker 110 , and the detected rotation angle is set to zero degrees (0°) (Step S 13 ). For example, in a case where the image 151 that is shown in FIG. 12 is captured, the marker 110 that is provided on the embroidery frame 9 is identified. Any known method may be used for identifying the marker 110 . For example, the method may be used that is described in Japanese Laid-Open Patent Publication No. 2009-172123, the relevant portion of which is hereby incorporated by reference. The detected rotation angle is then set as zero degrees, by storing in the RAM 63 , as a zero-degree line, a virtual line that links the origin point (the center position of the embroidery frame 9 ) to the coordinate position of the first center point 111 of the first circle 101 (Step S 13 ). In the explanation that follows, the rotation angle of the middle frame 92 in relation to the outer frame 94 that is detected at one of Steps S 13 and S 34 (described later) is called the detected angle. At Step S 13 , the detected angle is zero degrees. In the explanation that follows, the clockwise direction from the detected angle of zero degrees in FIG. 12 is expressed as positive (+), and the counterclockwise direction from the detected angle of zero degrees is expressed as negative (−).
A determination is made as to whether or not one of the outwork data tables that are stored in the EEPROM 64 is selected by the user (Step S 14 ). At Step S 14 , a plurality of outwork patterns are displayed on the liquid crystal display 15 . The user selects one of the outwork patterns by performing the panel operation. When one of the outwork patterns is selected by the user, a determination is made that the corresponding one of the outwork data tables is selected (YES at Step S 14 ). In a case where none of the outwork data tables is selected (NO at Step S 14 ), the processing returns to Step S 14 . In the specific example, the cutwork data table 59 (refer to FIG. 9 ) for cutting out the areas 107 on the inner sides of the flower petal patterns 106 is selected.
In a case where the cutwork data table 59 is selected (YES at Step S 14 ), the variable N is set to 1 and is stored in the RAM 63 (Step S 15 ). The detected angle that was detected at Step S 13 is compared to the rotation angle (hereinafter called the target rotation angle) that is based on the frame rotation data that correspond to the variable N in the outwork data table 59 (Step S 16 ). A determination is made as to whether or not the result of the comparison is that the detected angle matches the target rotation angle (Step S 17 ). In a case where the detected angle matches the target rotation angle (YES at Step S 17 ), the processing advances to Step S 22 (described later).
In the specific example, a determination is made that the detected angle of zero degrees does not match the target rotation angle of +44 degrees that corresponds to the variable N 1 (refer to FIG. 9 ) (NO at Step S 17 ). In a ease where the detected angle does not match the target rotation angle (NO at Step S 17 ), information that indicates that the detected angle does not match the target rotation angle is reported as rotation information (Step S 18 ). At Step S 18 , a message that says, for example, “Please rotate the embroidery frame” is displayed on the liquid crystal display 15 (refer to FIG. 12 ). The user is thus able to know that it is necessary to rotate the embroidery frame 9 . In other words, the user is able to know that the detected angle does not match the target rotation angle.
The rotation angle (the target rotation angle) that is based on the frame rotation data is reported as rotation information (Step S 19 ). At Step S 19 , a message that says, for example, “Target rotation angle: +44°” is displayed on the liquid crystal display 15 (refer to FIG. 12 ). The user is thus able to recognize that the embroidery frame 9 needs to be rotated to +44 degrees. Next, frame rotation processing is performed (Step S 20 ).
The frame rotation processing will be explained with reference to FIG. 11 . The frame rotation processing is processing for assisting the user in adjusting the rotation angle of the middle frame 92 in relation to the outer frame 94 to the target rotation angle by rotating the middle frame 92 (the assembled unit 95 ). As shown in FIG. 11 , in the frame rotation processing, the image sensor 48 is controlled in the same manner as at Step S 11 (refer to FIG. 10 ), such that the image 151 , which includes the area that includes the embroidery frame 9 that is mounted on the mounting portion 351 , is captured (Step S 31 ). The captured image 151 is displayed on the liquid crystal display 15 (Step S 32 ). The marker 110 that is provided on the embroidery frame 9 is identified based on the captured image 151 , and the rotation angle of the middle frame 92 in relation to the outer frame 94 is detected based on the identified marker 110 (Step S 33 ).
The detected angle is reported as rotation information (Step S 34 ). At Step S 34 , the detected angle is displayed on the liquid crystal display 15 , for example. The user is thus able to accurately recognize the current rotation angle. In the specific example, the initial detected angle is zero degrees, so a message that says, for example, “Current rotation angle: 0°” is displayed on the liquid crystal display 15 (refer to FIG. 12 ).
In the same manner as at Step S 16 (refer to FIG. 10 ), the detected angle is compared to the target rotation angle (Step S 35 ). In the same manner as at Step S 17 (refer to FIG. 10 ), a determination is made as to whether or not the result of the comparison is that the detected angle matches the target rotation angle (Step S 36 ). In a case where the detected angle does not match the target rotation angle (NO at Step S 36 ), the processing returns to Step S 31 . That is, the processing at Steps S 31 to S 36 is repeated until the user rotates the middle frame 92 in relation to the outer frame 94 such that the detected angle matches the target rotation angle. The repeating of Steps S 31 to S 36 causes the image 151 of the embroidery frame 9 to be captured and displayed on the liquid crystal display 15 in real time (Steps S 31 and S 32 ) during the time that the user is adjusting the rotation angle of the middle frame 92 . The current rotation angle (the detected angle) of the middle frame 92 in relation to the outer frame 94 is also displayed on the liquid crystal display 15 in real time (Step S 34 ).
For example, in a case where the user has rotated the middle frame 92 clockwise to the position of +20 degrees, an image 152 , in which the middle frame 92 has been rotated to +20 degrees, and the message “Current rotation angle: +20°” are displayed on the liquid crystal display 15 , as shown in FIG. 13 . Because the current rotation angle (the detected angle) is displayed in this manner, the user is able to easily adjust the rotation angle of the middle frame 92 in relation to the outer frame 94 to the target rotation angle while checking the current rotation angle of the middle frame 92 in relation to the outer frame 94 . When the middle frame 92 is rotated to the position of +44 degrees, as shown in an image 153 in FIG. 14 , the determination is made that the detected angle matches the target rotation angle (YES at Step S 36 ), the frame rotation processing is terminated, and the processing advances to Step S 21 (refer to FIG. 10 ).
As shown in FIG. 10 , at Step S 21 , information that indicates that the detected angle and the target rotation angle match is reported as rotation information (Step S 21 ). At Step S 21 , the message “Rotation angle matches target rotation angle,” for example, is displayed on the liquid crystal display 15 . Thus the user can easily know that the rotation angle of the middle frame 92 in relation to the outer frame 94 matches the rotation angle (the target rotation angle) that is based on the frame rotation data.
Based on the data that corresponds to the value of the variable N, a cut is formed (Step S 22 ). For example, in a case where the variable N in the outwork data table 59 is 1, the X coordinate is 27, and the Y coordinate is 9. Therefore, the X axis motor 83 and the Y axis motor 84 are driven, and the embroidery frame 9 is moved, such that the position specified by the X coordinate 27 and the Y coordinate 9 is the needle drop point. Then the needle bar 6 is driven, and a cut is formed by the outwork needle 8 at the position in the work cloth 100 that is specified by the X coordinate 27 and the Y coordinate 9 (refer to FIG. 14 ). In FIG. 14 , white circles represent needle drop points 108 for the outwork needle 8 for forming cuts in the work cloth 100 when the rotation angle that is based on the frame rotation data is +44 degrees (when the variable N is from 1 to 38). In the present embodiment, the work cloth 100 is cut in the front-rear direction of the sewing machine 1 (the orientation of the cutting portion 89 of cutwork needle 8 ), such that the white circles are joined.
The variable N is incremented (Step S 23 ). A determination is made as to whether or not the cutwork has been completed (Step S 24 ). At Step S 24 , the determination as to whether or not the cutwork has been completed is made by determining whether or not data such as the frame rotation data and the like that correspond to the current value of the variable N exist in the outwork data table 59 . For example, if the current variable N is 222, the data do no exist in the outwork data table 59 , so the determination is made that the cutwork has been completed.
In a case where the outwork has not been completed (NO at Step S 24 ), a determination is made as to whether or not it is necessary to change the rotation angle of the middle frame 92 in relation to the outer frame 94 (Step S 25 ), the determination being made by determining whether or not the rotation angle that is based on the frame rotation data in the outwork data table 59 has changed. For example, as shown in the cutwork data table 59 (refer to FIG. 9 ), during the time that the variable N is from 1 to 38, the rotation angle that is based on the frame rotation data is +44 degrees and does not change. Thus, the determination is made that it is not necessary to change the rotation angle of the middle frame 92 in relation to the outer frame 94 (NO at Step S 25 ), the processing returns to Step S 22 . The forming of the cuts is continued.
In the case where the variable N changes from 38 to 39, for example, the rotation angle that is based on the frame rotation data changes from +44 degrees to zero degrees (refer to FIG. 9 ). It is therefore determined that it is necessary to change the rotation angle of the middle frame 92 in relation to the outer frame 94 (YES at Step S 25 ), and the processing returns to Step S 18 . Information that indicates that the detected angle does not match the target rotation angle (zero degrees) is reported as rotation information (Step S 18 ), and the target rotation angle is reported (Step S 19 ). Then, in the same manner as in the previously described case where the middle frame 92 was rotated from zero degrees to +44 degrees, the user rotates the middle frame 92 in relation to the outer frame 94 while referring to the image 151 of the embroidery frame 9 that is displayed at Step S 32 and to the detected angle that is displayed at Step S 34 . The user adjusts the rotation angle of the middle frame 92 in relation to the outer frame 94 to the target rotation angle of zero degrees. Then, when the detected angle matches the target rotation angle of zero degrees (YES at Step S 36 ), a cut is formed at the target rotation angle of zero degrees (Steps S 22 to S 23 ).
Thereafter, the forming of the cuts is continued by repeating the rotation of the middle frame 92 and forming of a cut in the work cloth 100 . Then, when it is determined that the cutwork has been completed (YES at Step S 24 ), the outwork processing is terminated. Thus the completed form of the flower pattern 105 is produced, in which all of the areas 107 have been cut out on the inner sides of the four flower petal patterns 106 .
The cutwork processing in the present embodiment is performed as described above. In the present embodiment, rotation information is reported that is information for adjusting the rotation angle of the middle frame 92 to a specified angle based on the detected angle (Steps S 18 , S 19 , S 21 in FIG. 10 ; Step S 34 in FIG. 11 ). Therefore, the user is able to adjust the rotation angle of the middle frame 92 in relation to the outer frame 94 by referring to the reported rotation information. It is thus possible for the user to easily adjust the rotation angle of the middle frame 92 in relation to the outer frame 94 without being required to look at a graduated scale or markings, as with the known embroidery frame.
More specifically, the sewing machine 1 reports the rotation information based on the detected angle and the frame rotation data (Steps S 18 , S 19 in FIG. 10 ). It is thus possible for the user to easily adjust the rotation angle of the middle frame 92 in relation to the outer frame 94 by referring to the rotation information that is reported. Accordingly, the user is able to adjust the rotation angle of the middle frame 92 in relation to the outer frame 94 even more easily.
The sewing machine 1 is able to report the rotation information in a case where the detected angle matches the rotation angle (the target rotation angle) that is based on the frame rotation data (Step S 21 ). It is thus possible for the user to easily know that the rotation angle of the middle frame 92 in relation to the outer frame 94 matches the rotation angle that is based on the frame rotation data. Accordingly, the user is able to easily adjust the rotation angle of the middle frame 92 in relation to the outer frame 94 .
The sewing machine 1 is able to report the rotation information in a case where the detected angle does not match the rotation angle (the target rotation angle) that is based on the frame rotation data (Step S 18 ). It is thus possible for the user to easily adjust the rotation angle of the middle frame 92 in relation to the outer frame 94 such that the rotation angle matches the rotation angle that is based on the frame rotation data.
The sewing machine 1 is able to report the rotation angle that is based on the frame rotation data as the rotation information (Step S 19 ). The user is therefore able to easily know the rotation angle (the target rotation angle) that is based on the frame rotation data. Thus the angle that is the target can be made clear, and the rotation angle of the middle frame 92 in relation to the outer frame 94 can be matched to it efficiently.
The sewing machine 1 is able to report the detected angle that is detected at Step S 33 as the rotation information (Step S 34 ). It is thus possible for the user to easily know the current rotation angle of the middle frame 92 in relation to the outer frame 94 . Accordingly, the user is able to adjust the rotation angle of the middle frame 92 in relation to the outer frame 94 while referring to the detected angle that has been reported.
The sewing machine 1 is able to display the detected angle (Step S 34 ) while also displaying the target rotation angle (Step S 19 ). It is therefore possible for the user to easily know that the current rotation angle of the middle frame 92 in relation to the outer frame 94 does not match the target rotation angle. It is also possible for the user to adjust the rotation angle of the middle frame 92 in relation to the outer frame 94 even more easily by referring to the current rotation angle of the middle frame 92 in relation to the outer frame 94 and to the target rotation angle at the same time.
In a case where the detected angle matches the rotation angle (the target rotation angle) that is based on the frame rotation data (YES at Step S 17 or YES at Step S 36 ), the needle bar 6 is driven, and the cutting is performed (Step S 22 ). In a case where the detected angle does not match the rotation angle (the target rotation angle) that is based on the frame rotation data (NO at Step S 17 or NO at Step S 36 ), the processing at Step S 22 is not performed, and the cutting of the work cloth 100 is not performed. Therefore, it is possible to prevent the work cloth 100 from being out by mistake in a case where the detected angle does not match the rotation angle that is based on the frame rotation data.
Because the rotation information is displayed on the liquid crystal display 15 (Steps S 18 , S 19 , S 21 in FIG. 10 ; Step S 34 in FIG. 11 ), the user can easily know the rotation information by checking the liquid crystal display 15 . The convenience for the user can be thus improved.
Note that the present disclosure is not limited to the embodiment that has been described above, and various types of modifications can be made. For example, the rotation information is reported to the user by being displayed on the liquid crystal display 15 (Steps S 18 , S 19 , S 21 in FIG. 10 ; Step S 34 in FIG. 11 ), but the present disclosure is not limited to this example. For example, one of a light emitting diode (LED) and a lamp may be provided, and in a case where the detected angle matches the target rotation angle, in a case where the detected angle does not match the target rotation angle, and the like, information may be reported to the user by causing the one of the LED and the lamp to one of turn on and flash. Information may be reported to the user by changing the color of the one of the LED and the lamp. In this case as well, the user is able to easily match the rotation angle of the middle frame 92 in relation to the outer frame 94 to the rotation angle that is based on the frame rotation data by adjusting the rotation angle while checking the one of the LED and the lamp. The sewing machine 1 may also be provided with one of a speaker and a buzzer, and information may be reported to the user in the form of sound.
In the embodiment the marker 110 is provided on the inner frame 91 of the embroidery frame 9 in the form of drawing, but the present disclosure is not limited to this example. For example, the marker 110 may be drawn on one face of a sheet of a specified size, and an adhesive is applied to the other face of the sheet. The sheet may then be affixed to the work cloth 100 that is clamped between the inner frame 91 and the middle frame 92 . In this case, the rotation angle of the middle frame 92 in relation to the outer frame 94 can be detected (Steps S 13 and S 33 ) based on the marker 110 that has been affixed to the work cloth 100 .
The embroidery frame 9 is not limited to the case of the present embodiment, and an embroidery frame that has a different structure may also be used, as long as it is a rotatable embroidery frame. For example, it is possible to use an embroidery frame that includes a frame member that is configured to hold the work cloth 100 and an outer frame that is configured such that it can be removably mounted on the outer side of the frame member and that is configured to rotatably hold the frame member.
It is not necessary for all of the rotation information that is described in the embodiment to be reported, and only a portion of the rotation information may be reported. The frame rotation data are used in the reporting of the rotation information in the embodiment, but the present disclosure is not limited to this example. For example, it is acceptable to report only the current rotation angle of the middle frame 92 , based only on the detected angle, without using the frame rotation data.
A specific example has been explained of an embodiment in which the middle frame 92 is rotated in relation to the outer frame 94 when the outwork is performed, but the present disclosure is not limited to this example. For example, the reporting of the rotation information and other procedures that are described above may also be performed in a case where the middle frame 92 is rotated in relation to the outer frame 94 while embroidery sewing is being performed with the sewing needle 7 (refer to FIG. 2 ).
The apparatus and methods described above with reference to the various embodiments are merely examples. It goes without saying that they are not confined to the depicted embodiments. While various features have been described in conjunction with the examples outlined above, various alternatives, modifications, variations, and/or improvements of those features and/or examples may be possible. Accordingly, the examples, as set forth above, are intended to be illustrative. Various changes may be made without departing from the broad spirit and scope of the underlying principles. | A sewing machine may comprise a mounting portion configured to be mounted with an embroidery frame comprising a frame and an outer frame. The sewing machine may also comprise an image capturing device configured to capture an image including the embroidery frame mounted on the mounting portion. The sewing machine may further comprise a processor configured to execute instructions, and a memory. The memory may be configured to store computer-readable instructions that instruct the sewing machine to execute steps comprising identifying a mark from the captured image, wherein the mark is provided on the embroidery frame or on a work cloth held by the embroidery frame, determining a rotation angle of the frame with respect to the outer frame based on the identified mark, and notifying rotation information based on the determined rotation angle. The rotation information may be information for adjusting the rotation angle to a specified rotation angle. | 3 |
BACKGROUND
[0001] 1. Field of the Invention
[0002] The present invention relates generally to data storage, and more in particularly, to data storage media.
[0003] 2. Background Information
[0004] With the expansion of information technology, increasing amount of data is recorded on data storage media for safekeeping and redundancy. Certain technologies such as high definition video technology generate large volumes of data. Conventionally, magnetic tape is used for mass data storage. However, magnetic tape is expensive, occupies large volume of space, and has limited durability (5-50 years). The limited durability requires tape archives to be re-read and re-copied regularly (every decade or so). As such, storing very large quantities of data inexpensively (both at low cost per byte and at low weight/volume per byte) for long periods of time (400 to 1000 years) remains challenging.
BRIEF SUMMARY
[0005] A method and apparatus for storing data is provided. One implementation involves providing a fiber medium for storing data, the fiber medium having a characteristic configured to irreversibly change when exposed to write irradiation having first attributes. The fiber is logically partitioned into cells along the length of the fiber medium. Data stored in a cell of the fiber medium by exposing the cell to write irradiation to irreversibly change characteristic of the bulk of the cell.
[0006] The fiber medium may have an irradiation absorption characteristic configured to irreversibly increase when exposed to write irradiation. Storing data in a cell of the fiber medium may then include storing data in a cell of the fiber medium by exposing the cell to write irradiation to irreversibly increase absorption characteristic of the bulk of the cell. The fiber medium may comprise a fiber of amorphous solids. The fiber may be processed by doping with a photosensitive substance to irreversibly increase when exposed to write irradiation. The fiber medium may comprise a glass fiber processed to irreversibly increase its irradiation absorption when exposed to irradiation. The irradiation may comprise an ultraviolet beam and the fiber medium may be about 1 μm to 10 μm in thickness.
[0007] Reading data from a cell of the fiber medium may comprise detecting irradiation absorption of the cell. Reading data from the cell may further include exposing the cell to read irradiation having second attributes, and detecting irradiation absorption of the cell, such that if the detected irradiation absorption of the cell is above an absorption threshold then the cell stores data. Different absorption levels may represent different data. Reading data from a cell may be performed at a lower intensity irradiation than writing. Reading data from a cell may be performed at a longer wavelength irradiation than writing. Writing and reading data is performed while the fiber moves past a read/write head.
[0008] Other aspects and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0009] For a fuller understanding of the nature and advantages of the invention, as well as a preferred mode of use, reference should be made to the following detailed description read in conjunction with the accompanying drawings, in which:
[0010] FIG. 1 illustrates an example process for utilizing a fiber medium for data storage, according to an embodiment of the invention;
[0011] FIG. 2 illustrates an example process for recording data on a fiber medium, according to an embodiment of the invention;
[0012] FIG. 3 illustrates an example process for reading data from a fiber medium, according to an embodiment of the invention.
DETAILED DESCRIPTION
[0013] The following description is made for the purpose of illustrating the general principles of the invention and is not meant to limit the inventive concepts claimed herein. Further, particular features described herein can be used in combination with other described features in each of the various possible combinations and permutations. Unless otherwise specifically defined herein, all terms are to be given their broadest possible interpretation including meanings implied from the specification as well as meanings understood by those skilled in the art and/or as defined in dictionaries, treatises, etc.
[0014] The description may disclose several preferred embodiments for storing information on processed fibers of glass or quartz, which are examples of microcrystalline and amorphous solids, as well as operation and/or component parts thereof. While the following description will be described in terms of glass fibers for clarity and to place the invention in context, it should be kept in mind that the teachings herein may have broad application to other types of materials (e.g., quartz), systems, devices and applications.
[0015] In tape information storage technology, a very thin magnetic layer is glued on a relatively thick plastic tape that provides mechanical support for the magnetic material. The magnetic material is for storing data only. The plastic tape only functions as mechanical support for the magnetic material. As such, much of the storage volume in terms of cubic meters is used for storing the plastic tape that supports the thin magnetic layer.
[0016] According to an embodiment of the invention, thin fibers of glass or quartz, which are examples of microcrystalline and amorphous solids are processed and used as data storage media. Storing data involves changing a physical characteristic (such as irradiation absorption, transparency) of the fiber. The fibers may be very thin, and can retain high data density. Because the storage process involves only such fibers and inorganic chemistry, the fiber is inexpensive and stored data is very persistent for long periods of time (e.g., 400 to 1000 years).
[0017] Referring to FIG. 1 , in one embodiment, such a thin fiber 10 is used as a bulk data storage medium. To write data, optical absorption of the fiber is changed by a process of exposing the fiber to write irradiation of certain attributes such as a strong and focused ultraviolet (UV) beam 11 of a laser 12 . To read data, the fiber is exposed to read irradation of certain attributes (such as visible light) to detect the changed property of the fiber. If the changed property (e.g., absorption level) of the property is above a threshold, then the fiber is considered to be storing data.
[0018] The fiber diameter is selected to maximize the physical storage density, while taking into account 10 (input/output or read/write) speed and longevity of the data. Substantially, the entire bulk of the fiber media is used for data storage (versus tape wherein only the thin magnetic layer is used for storing data).
[0019] This allows reliable storage of large amounts of data for a long period (e.g., over 400 years). The information in such a fiber using bulk of the fiber, wherein the fiber (or strand) provides both the mechanical support and the storage medium (i.e., the data storage material provides mechanical support for itself).
[0020] The fiber is processed by doping with a compound which causes any portion of the fiber that is exposed to radiation to permanently turn dark. The process of irradiation changes one of the bulk properties of an exposed portion of the fiber in an irreversible fashion (e.g., darkening it), wherein the changed portion represents a recorded unit of information unit relative to unchanged portions. The amount of change in the property can have multiple levels to represent multiple types of information stored.
[0021] In one implementation, a thin (e.g., on the order of 1 μm to 10 μm) glass fiber is doped with a material that changes the light absorption of the glass when irradiated, for example with UV light. The fiber is doped with a photosensitive material, such as AgCl. The processed fiber has photosensitive properties, wherein the fiber turns irreversibly dark when exposed to UV radiation. Photosensitive means that the material changes properties irreversibly when exposed to certain radiation.
[0022] The fiber is read and written perpendicularly, conceptually by dividing the glass volume into optical “cells” 14 as shown by the example write and read operations in FIGS. 2 and 3 , respectively. To write the data, the fiber is irradiated, for example with a modulated UV laser. To read the fiber, the fiber is illuminated either at a low power level (which does not cause further darkening) or at lower energies (e.g., visible light, Infra Red (IR)). Referring to the write process in FIG. 2 , recording data is performed as the fiber moves under a read/write head (e.g., irradiation source 12 in FIG. 1 ) which illuminates the fiber 10 using a high-powered UV light source, for example a laser, modulated to encode the write data. For example, using a typical UV laser illuminator at a wavelength of 337 nm (Nitrogen laser) or 248 nm (KrF excimer laser), a 200 nm (0.2 μm) region of the fiber can be illuminated, thereby darkening an individual cell 14 that occupies a spatial volume of 0.2 μm×(1 μm) 2 =2×10 −19 m 3 . Each cell 14 can store at least 1 bit (unit) of information (multi-level storage provides more storage capacity).
[0023] The recorded information bits can be read back from the fiber 10 by measuring properties of the fiber (a changed property of a portion of the fiber represents a cell that stores information relative to a portion of the fiber with unchanged property). Reading may be performed at a much longer wavelength than writing. For example, optical or near-UV irradiation beam may be used (using focusing or electronics to handle “crosstalk” between neighboring bits). Further, as shown in FIG. 3 , a UV beam at much lower power densities can be used for reading, to prevent the fiber characteristics from being changed again when reading. As the fiber moves under a read/write head such as detector 15 , the beam passes through the fiber and the beam intensity exiting the fiber is detected by the detector 15 . When the detector 15 detects reduced beam intensity due to the beam passing through a cell 14 , then a bit of recorded information is detected.
[0024] The read/write process naturally partitions the fiber into unit cells. The cells are separated by the relative motion between the media and the read/write station (i.e., light source, detector, optics, etc.). The cells are arranged along the direction of the media motion. Generally the fiber 10 possesses physical characteristics, such that the storage process changes the bulk of the fiber, not a thin layer as in magnetic tape. The storage cells are addressed only in the direction of motion of the media, not perpendicular to it The fiber allows cell size to be reduced, with one track using all the material without an inert carrier, essentially maximizing volumetric storage density. For increased storage density, the cells may be made smaller or more bits may be stored into each cell (multi-level storage).
[0025] The fiber may be stored on spools/reels 13 ( FIG. 1 ) which may be housed inside cartridges (not shown). Assuming a macro packing efficiency of only 50%, then half the space is used for spool cores that the fiber is wound on, and the gaps between round spools. This leads to a density of 2.5 Pb/l, equivalent to about 1 Pb/kg (glass has a density of about 2.6 g/cm 3 ). Assuming that a volume of 2×10̂-19 m̂3 is written at a spooling speed of 25 m/s (the speed at which glass fiber is manufactured), IO speed per fiber is 125 Mb/s. Multi-level recording or higher transport speeds provide higher IO speed. An example fiber has the following characteristics:
Fiber diameter: 1 μm to 10 μm; Bit cell length: 200 nm-400 nm; Bits per cell: 1-5 bits; 1 bit volume=2×10 −19 m 3 ; Packing efficiency: 50%; Density: 2.5 Pbit/l, 1 Pbit/kg; Pbit/l: 1 Pbit/kg; Spooling speed: 25 m/s; 1 bit length: 200 nm; Read/Write speed: 125 Mbit/s.
Making photosensitive glass is an old and well-known technique. The most common chemical that is added to glass (i.e., doping) to make it photosensitive is silver chloride (AgCl). The process for adding doping materials to glass before extruding it into fibers is also well known. Common photosensitive glass (such as used for crafts) fibers are useful with the present invention.
[0035] In the description above, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. For example, well-known equivalent components and elements may be substituted in place of those described herein, and similarly, well-known equivalent techniques may be substituted in place of the particular techniques disclosed. In other instances, well-known structures and techniques have not been shown in detail to avoid obscuring the understanding of this description.
[0036] While certain exemplary embodiments have been described and shown in the accompanying drawings, it is to be understood that such embodiments are merely illustrative of and not restrictive on the broad invention, and that this invention not be limited to the specific constructions and arrangements shown and described, since various other modifications may occur to those ordinarily skilled in the art. | A method and apparatus for storing data is provided. One implementation involves providing a fiber medium for storing data, wherein the fiber medium has a characteristic configured to irreversibly change when exposed to write irradiation. The fiber medium is logically partitioned into cells along the length of the fiber medium. Data is stored in a cell of the fiber medium by exposing the cell to write irradiation to irreversibly change characteristic of the bulk of the cell. | 6 |
BACKGROUND
[0001] 1. Field of the Invention
[0002] The present invention relates to a method for implementing a serialization construct within an environment of parallel data flow graphs.
[0003] 2. Description of the Related Art
[0004] Data flow graphs are used to implement operations taking place in order to verify the correct functional behavior of a logic design for an electronic circuit. An example is a main memory read operation in a computer system, wherein a data flow graph implementation consists of a node and an address. Said node controls signals of the logic design. The address is applied to the main memory while a following node receives and checks the data provided by the main memory.
[0005] A test generator which is used in the logic design verification can continuously generate data flow graphs with different operations. The data flow graphs can be chained together, so that a data flow graph chain represents a sequence of randomly selected operations. An environment of parallel data flow graphs allows the parallel execution of the data flow graphs. Thus, multiple data flow graph chains are usually running in parallel.
[0006] The patent application US 2006/0195732 A1, incorporated herein by reference, describes an integrated verification framework for concurrent execution of random and deterministic test cases. This is a data flow architecture, wherein random and deterministic test sequences are modeled into data flow graphs and executed in parallel. The verification framework does not contain a way to serialize the execution into a single test sequence. All active data flow graphs are executed independent of each other.
[0007] Such a serialization is required for some applications. For example, for the verification of an address translation unit in a processor design where such a framework is used, a serial construct is required. In the known IBM System z mainframe computing system, such serial construct is needed because changes to an address mapping table used for the dynamic address translation from virtual to real addresses must be done by one processor only. In this case all other processors using the same translation space must be stopped until an address mapping table update is completed.
[0008] In the environment described above, the only way to achieve this behavior is to signal a quiesce request to all test case generators in the environment in order to prevent a generation of new test sequences until the quiesce operation is finished. The drawback of this approach is that its implementation is specific for this application. But the number and type of test case generators depend on the device under verification. Its implementation breaks the data flow concept of the underlying framework.
[0009] It is therefore an object of the present invention to provide an improved method for implementing a serialization construct within an environment of parallel data flow graphs.
BRIEF SUMMARY
[0010] The above object is achieved by a method as laid out in the independent claims. Further advantageous embodiments of the present invention are described in the dependent claims and are taught in the description below.
[0011] The advantages of the invention are achieved by providing a set of special administrative nodes. Unlike regular nodes within the framework of the data flow graph, said administrative nodes do not interact with a device under test or another device connected to the framework. The administrative nodes are multiple quiesce nodes, a serialize node and a serialize end node. The multiple quiesce nodes, the serialize node and the serialize end node are provided to temporarily cache the tokens from the data flow graph to the next data flow graph.
[0012] The administrative nodes may be controlled by at least one quiesce manager. If a serial operation or a serial sequence of operations is required, then the quiesce nodes are appended to every active data flow graph by the quiesce manager. The serial operation or the sequence of serial operations is started by a serialize node and terminated by a serialize end node. In this context, the term “serial data flow graph” is referring to a data flow graph which is executed while all other data flow graphs are inactive. The invention describes a mechanism to restrict the parallel execution of data flow graphs to a single data flow graph. After execution of the single or serial data flow graph, parallel execution is resumed. The parallelism inside the serial data flow graph is not restricted, but it may have any structure possible. In other words, the parallelism is allowed within the serial data flow graph.
[0013] The quiesce nodes have a callback function implemented in order to call the serialize node. The serialize node is required in the beginning of the serial operation or the sequence in order to run without any other test activity.
[0014] Whenever an active data flow graph ends, then the quiesce node is activated. The callback to the quiesce manager flags the termination of the corresponding data flow graph. When all active data flow graphs are finished, then the quiesce manager activates the serialize node, which fires and triggers the first operating node of the serial sequence.
[0015] During the execution of the serial sequence all quiesce nodes are still active. After the serial operation or the serial sequence of operations has been finished, the regular parallel execution can be resumed. This allows the test case generators to be continuously active. The test case generators can append new test sequences to the existing data flow graphs.
[0016] However, these new sequences are not activated before the serial sequence has been finished. Thus, there is no interaction with the test case generators required. The inventive method works completely within the framework of the data flow graph. Due to the automatic insertion of quiesce nodes, the overhead to implement a serial sequence is negligible.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0017] The above features and advantages of the present invention, as well as the additional objectives, will be apparent in the following detailed written description.
[0018] The novel and inventive features believed characteristic of the invention are set forth in the appended claims. The invention itself, their preferred embodiments and advantages thereof will be best understood by reference to the following detailed description of the preferred embodiments in conjunction with the accompanied drawings, wherein:
[0019] FIG. 1 shows a diagram of an environment with parallel data flow graphs and a serial data flow graph according to the present invention,
[0020] FIG. 2 shows a schematic flow chart diagram illustrating the behavior of a quiesce node according to the present invention,
[0021] FIG. 3 shows a schematic flow chart diagram illustrating the behavior of a serialize node according to the present invention,
[0022] FIG. 4 shows a schematic flow chart diagram illustrating the behavior of a serialize end node according to the present invention, and
[0023] FIG. 5 shows a schematic flow chart diagram illustrating the behavior of a quiesce manager according to the present invention.
DETAILED DESCRIPTION
[0024] The preferred embodiment is an extension of the test environment described in US 2006/0195732 A1. In this data flow graph framework, the data flow graphs are implemented as objects, which are instances of C++ classes. The nodes of a data flow graph are also implemented as objects, namely instances of a further specific C++ class. The nodes are arranged in a chained list as part of the data flow graph object. Also the data flow graph objects are arranged in form of a chained list. In another embodiment, a different object oriented programming language such as Java can be used instead in order to implement the objects.
[0025] FIG. 1 shows a schematic diagram of an environment with parallel data flow graph objects and a serial data flow graph object. In FIG. 1 a first data flow graph object 10 , a further data flow graph object 12 and a serial data flow graph object 14 are shown. In general, the first data flow graph object 10 and the further data flow graph 12 object may be comprised of a number of data flow graph objects, for which their interconnection is implemented by means of a chained list of data flow graph objects. An arbitrary number of data flow graph objects 10 and 12 may be active in parallel within the environment. The data flow graph objects 10 and 12 may be generated at the simulation startup time by a test case generator.
[0026] Each of the data flow graph objects 10 , 12 and 14 comprises a plurality of regular node objects 16 . The regular node objects 16 represent instructions or operations for a device under verification. The arcs between the regular nodes 16 of the data flow graphs 10 and 12 describe the structure of the test case. An arc in a data flow graph object is implemented as a pointer from one node object to the next node object in the chained list of node objects. The inputs of the device under verification are stimulated by the test case generators within a verification environment. The information stored in the active regular node objects 16 of the data flow graph objects 10 , 12 and 14 is used.
[0027] When the test case generator creates a serial sequence, its first node object is a special serialize node object 18 . Said serialize node object 18 is registered within a quiesce manager 20 , which is an instance of a C++ class. The quiesce manager 20 appends then a quiesce node object 22 to the chained list of node objects of each of the data flow graph objects 10 and 12 , which is currently active. Whenever the processing of one of the data flow graph objects 10 and 12 is finished and the quiesce node 22 is activated, a callback function of the data flow graph object calls the quiesce manager 20 in order to set a flag which indicates that the processing of the corresponding data flow graph objects 10 or 12 has been completed. When the processing of all active data flow graph objects 10 and 12 is finished, then the serialize node object 18 is activated by the quiesce manager 20 .
[0028] The quiesce manager 20 activates a serial sequence by calling a certain entry function of the corresponding data flow graph object. During processing of said serial sequence, all quiesce node objects 22 stay active, so that they prevent the activation of the data flow graph objects 10 and 12 appended to them. In this way, the test case generators may stay active and create test operations at will. These test case operations will be activated only then, if the serial sequence has been finished and a serialize end node object 24 has been activated. The serialize end node object 24 sends to the quiesce manager 20 a message that the serial sequence has been finished. Then the quiesce manager 20 in turn sends said message to every quiesce node object 22 , which is currently active. On reception of said message, the quiesce node object 22 terminates and activates the corresponding data flow graph objects 10 or 12 , which are connected to it.
[0029] The concept of the present invention enhances the existing data flow graph framework while keeping a backward compatibility. There are no modifications necessary to existing test cases or codes. Due to the automatic handling of the quiesce node objects 22 by the quiesce manager 20 , the overhead to use the invention is minimal.
[0030] FIG. 2 shows a schematic flow chart diagram, which illustrates the behavior of the quiesce node object 22 . Whenever a serialization operation is required, the quiesce node object 22 is appended to the data flow graph objects 10 and 12 , which are currently active.
[0031] In a step 30 the quiesce node object 22 begins its processing. In a loop 32 it is determined if a token from the data flow graph object 10 and/or 12 is passed to the quiesce node object 22 . The token is sent by the quiesce node object 22 to the quiesce manager 20 in a further step 34 , wherein the quiesce node object 22 passes the information about the termination of the previous data flow graph object to the quiesce manager 20 .
[0032] In a next step 36 , it is determined if a token from the quiesce manager 20 has been received. Then the quiesce node object 22 waits until it is signaled by the quiesce manager 20 that the execution may be proceed. Then the quiesce manager 20 sends a token in order to activate the following data flow graph object in a further step 38 . In a last step 40 the quiesce node object 22 ends its processing.
[0033] FIG. 3 shows a schematic flow chart diagram, which illustrates the behavior of the serialize node object 18 . The serialize node object 18 marks the beginning of the serial data flow graph object 14 . The serialize node object 18 receives an activation token from the quiesce manager 20 and passes it onto the serial data flow graph object 14 , wherein said serial data flow graph object 14 will be activated.
[0034] In step 44 , the serialize node object 18 begins its processing. In loop 46 , it is determined if a token from the quiesce manager 20 is received. In a next step 48 , the token is sent to serial data flow graph object 14 . In a last step 50 , the serialize node object 18 ends its processing.
[0035] FIG. 4 shows a schematic flow chart diagram, which illustrates the behavior of the serialize end node object 24 . The serialize end node object 24 marks the end of the serial data flow graph object 14 . The serialize node object 18 receives its activation token from the serial data flow graph object 14 . Then the serialize end node object 24 sends a token back to the quiesce manager 20 . Said token indicates the completion of the processing of the serial data flow graph object 14 .
[0036] In step 54 , the serialize end node object 24 begins its processing. In loop 56 , it is determined if a token from the serial data flow graph 14 is received. In a next step 58 , the token is sent to the quiesce manager 20 . In a last step 60 , the serialize end node object 24 ends its processing.
[0037] FIG. 5 shows a schematic flow chart diagram, which illustrates the behavior of the quiesce manager 20 . The quiesce manager 20 keeps track of all the data flow graph objects 10 and 12 , which are currently active.
[0038] In step 64 , the quiesce manager 20 begins its processing. In loop 66 , it checks if a serial execution has been requested. If a serialization is required, the quiesce manager 20 appends a quiesce node object 22 to each active data flow graph object 10 and 12 in a next step 68 . The quiesce manager 20 also precedes the serial data flow graph object 14 with a serialize node object 18 and appends a serialize end node object 24 to the end of the serial data flow graph object 14 .
[0039] In a further step 70 , it is determined if a token from the quiesce node object 22 has been received. In step 72 , it is further determined if all data flow graph objects 10 and 12 have been quiesced. Then the quiesce manager 20 waits for the quiesce nodes 22 of the data flow graph objects 10 and 12 . Said quiesce nodes 22 indicate that the previous data flow graph objects 10 and 12 have completed their processing and the data flow graph objects 10 and 12 are quiesced. After all quiesce node objects 22 have sent their token to the quiesce manager 20 , the system is quiesced and the serial data flow graph object 14 can be started. Therefore the quiesce manager 20 sends a corresponding token to the serialize node object 18 in a step 74 .
[0040] In a next step 76 , it is determined if a token from the serialize end node object 24 has been received. The quiesce manager 20 receives a token from the serialize end node object 24 after the serial data flow graph object 14 has finished its execution. In a last step 78 , the quiesce manager 20 sends tokens to all quiesce node objects 22 in the system. Step 78 indicates that the serialization has been ended and a parallel execution may resume.
[0041] The present invention can also be embedded in a computer program product which comprises all the features enabling the implementation of the methods described herein. Further, when loaded in computer system, said computer program product is able to carry out these methods.
[0042] Although illustrative embodiments of the present invention have been described herein with reference to the accompanying drawings, it is to be understood that the present invention is not limited to those precise embodiments, and that various other changes and modifications may be affected therein by one skilled in the art without departing from the scope or spirit of the invention. All such changes and modifications are intended to be included within the scope of the invention as defined by the appended claims. | A serialization construct is implemented within an environment of a number of parallel data flow graphs. A quiesce node is appended to every active data flow graph. The quiesce node prevents a token from passing to a next data flow graph within a chain before an execution of the active data flow graph has been finished. A serial data flow graph is implemented to provided for a serial execution while no other data flow graph is active. A serialize node is appended to a starting point of a serial data flow graph. A serialize end node is appended to an endpoint of the serial data flow graph. The serialize node is activated to start a serial operation. The serialize end node is activated after the serial operation has been terminated. | 6 |
This is a continuation of Ser. No. 449.715, filed Dec. 14, 1982, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to a twin-wheel caster comprising a pair of coaxial wheels.
So-called twin-wheel casters comprise a pair of wheels mounted rotatably on an axle. The axle is carried on a support which includes an upright wall extending between the wheels and has a well formed therein for accommodating a pivot pin provided for assembling the caster to a chair or other item of furniture associated therewith.
The top edge of the upright wall follows the curvature of the wheels, and a shroud or shell is connected thereto which encloses the wheel peripheries.
The well for the articulation pin has a tubular portion which protrudes upwardly from the shroud.
Some problems are encountered with twin-wheel casters especially as regards their attachment to the furniture item. In fact, it has been found that the tubular portion of the well generally falls short of the requisite strength and is also deficient from the aesthetic point of view. This is particularly disadvantageous on account of casters being available in a wide range of sizes, so that any approach to strengthen the region of the tubular portion is bound to involve a number of modifications to the manufacturing equipment.
SUMMARY OF THE INVENTION
Thus, the task of this invention is to provide a twin-wheel caster wherein the aforesaid drawbacks are all substantially reduced.
According to one aspect of the present invention the above task is achieved by a twin-wheel caster comprising a pair of coaxial wheels carried on an axle mounted in a support which includes a vertical wall extending between the wheels and wherein a well is formed which receives a pivot pin for articulating the caster to an item of furniture, said wall having a shroud member enclosing the tops of said wheels, said well being extended above said shroud with a tubular portion thereof, characterized in that a collar member is provided and arranged to overlap said tubular portion and equipped with means of attachment to said shroud.
BRIEF DESCRIPTION OF THE DRAWINGS
Further features and advantages of this invention will be more clearly understood from the following description of some embodiments thereof, as illustrated in the accompanying drawings, where:
FIG. 1 is a sectional view through one portion of the caster concerning its swivel mount to the item of furniture;
FIG. 2 is a bottom view of the collar;
FIG. 3 is a side view of a caster provided with the collar of FIGS. 1 and 2, but having increased dimensions;
FIG. 4 is a front view of the caster shown in Fig. 3;
FIG. 5 is a sectional view through a caster, illustrating yet another way of anchoring the collar; and
FIG. 6 is a sectional view of another embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Making reference to FIGS. 1, 2, and the numeral 1 designates generally a twin-wheel caster of conventional design, and, accordingly, no further described in detail. A caster of this type is illustrated, for example, in the U.S. Pat. No. 4,077,088.
Said caster comprises two wheels 2, wherebetween a wall 3 is arranged which defines at its center a hub 4 for the wheel carrier axle.
The wall 3 has, located offcentered with respect to the wheel axle, a boss 5 wherein a vertical well 6 is formed which is open at the top.
The wall 3 is substantially configured as a semicircle and, along its upper peripheral edge, carries a shroud made rigid therewith which encloses the wheels 2. The well 6 is extended above the shroud 7 into a tubular portion 8 which is prolonged upwards to a higher level than the shroud horizontal tangency plane.
In a conventional manner, the well 6 accommodates a pivot pin 9 which bears on the well bottom through a ball 10 and is prevented from sliding out by an annular rib 11 which engages in a mating groove 12 on the pin.
The pin 9 is provided, above the tubular portion 8, with an annular boss 13 which acts as a shoulder for insertion into a specially provided seat in the item of furniture wherewith this caster is associated. In the example shown, it has been assumed that the pin has been inserted into a seat in a leg or foot of a chair, generally indicated at 14.
According to this invention, to strengthen the tubular portion 8, a reinforcing collar structure indicated generally with reference numeral 15 is provided which encircles an opening 16 having the same diameter as the portion 8. The reinforcing collar structure 15 defines, at the bottom, a surface 17 having a pattern which is complementary to that of the shroud 7 thereby, by superimposing the collar 15 onto the tubular portion 8, a perfect joint is achieved between the shroud and reinforcing collar structure. The collar 15 comprises a sector formation 18 which extends along the shroud 7 and downwards, and is provided at its lower end with a dog 19 adapted to engage under the shroud front edge. As visible in the drawing the collar structure 15 has a ring-like body portion 15a snugly surrounding the tubular portion 8.
The above-described collar is completed with a ring or sleeve formation 20 which surrounds a seat 20a for accommodating the boss 13 and conceal it from view. As visible in the drawing the sleeve formation as an inner diameter greater than the outer diameter of said ring-like body portion 15a and downwardly extends into said sector formation 18.
Between sleeve formation 20 and the ring-like body portion 15a, a cylindrical interspace 20b is formed.
It will be apparent that the invention just described fully achieves its objects. In particular, it should be noted that the reinforcing collar structure 15, additionally to strengthen the tubular portion 8, affords the possibility of accomplishing an aesthetically more attractive connection of the caster to the chair foot. In fact, as may be seen in FIG. 1, the collar structure 15 constitutes an extension of sort of the foot 14.
From the manufacturing standpoint, the collar structure involves no alterations of the caster, it being available as an accessory with outside dimensions which can be selected as desired. Thus, the caster is a constant feature and the collar structure is assigned the function of caster adaptation.
FIGS. 3, 4 show in fact a collar structure with a correspondingly larger diameter to fit a larger size foot. In this case, since the collar width exceeds the shroud width, the external body portion formed of said sleeve formation 20 and sector formation 18 of the collar structure is formed at the lower edge thereof, with side flanges 21 which overlap the edges of the shroud, and with the lower dog 19, define the fitting seat therefor.
Of course, the manner how the collar is associated with and secured to the shroud may be manifold. In FIG. 5, a solution which provides for the use of a bushing 22 inserted into the well 6, between the inner wall of the latter and pin 9, is shown. The bushing 22 is provided at the bottom with annular inner and outer projections 23 which engage in corresponding grooves on the pin and well. A flange 24 at the top of the bushing prevents the collar from sliding out by restraining it axially.
The same result may be achieved in a simpler construction by providing, on the inside of the ring-like body portion of the collar structure, an annular rib 25 which engages in a corresponding annular seat on the tubular portion 8, as shown in FIG. 6.
Where the materials selected allow for it, the connection of the collar to the shroud may be accomplished by force fitting the collar onto the tubular portion, or by adhesive application.
It is a not negligible feature of this invention that this caster may be adapted to suit the item of furniture also under the profile of color matching. In fact, the collar 15 may be either chrome-plated, or gold-plated, or subjected to other surface finish treatments, separately from the shroud. Of course, such treatments would also include any processing directed to provide special embossed patterns and shapes, such as knurling, notching, and the like.
In practicing the invention, the shape of the collar may be any desired one, such as prismatic, conical, or crowned for radiusing to the shroud.
Expediently, the collar would be molded from a plastic material. | The caster comprises a pair of coaxial wheels mounted in a support wherein a well is formed receiving a pivot pin for articulating the caster to an item of furniture and being extended by a tubular portion above a support shroud, a stiffening collar member being further provided in overlapping relationship with respect to the tubular portion for tightly engaging the shroud and facilitating the coupling of the caster to the furniture item. | 8 |
The present invention pertains generally to a blanket assembly and apparatus selectively adjustable to provide cooled or heated air to the blanket assembly, as desired.
BACKGROUND OF THE INVENTION
The subject of conditioning air for increasing the comfort of human beings has been the subject of intense study for many years from which it has been learned that for optimal results attention must be paid to a number of factors other than merely heating or cooling the air.
For example, in The Handbook of Engineering Fundamentals, John Wiley & Sons, Third Edition 1975, air conditioning is defined broadly as the simultaneous control of temperature, humidity, motion, and purity of air to meet the requirements of human comfort. Some of the principal factors affecting human comfort and welfare as influenced by air environment are the (1) air dry-bulb temperature, (2) humidity, (3) motion, (4) distribution, (5) dust control, (6) bacteria content, and (7) odors. Other factors which may influence comfort, but the effects of which are not so well established at the present time, are (8) light, (9) ozone content, (10) ionic content, and (11) pressure. Human occupancy of a confined space produces a number of important alterations in the properties of the air: (1) oxygen content is decreased slightly; (2) carbon dioxide content is increased slightly; (3) products of decomposition, usually accompanied by odors, are given off; (4) air temperature is raised; (5) humidity is increased by evaporation of moisture from the skin and the lungs; and (6) the number of positive and negative ions in a unit volume of the air is decreased. Also, it has been found that in an occupied space, at least 10 cubic feet of fresh air per minute per person should be provided to adequately remove body heat, body odors, and products of respiration.
Still further, the American Society of Heating and Ventilation Engineers provides that the relative humidity shall not be less than 30 percent, nor more than 60 percent, and that the effective temperature shall range between 64° and 69° Fahrenheit when cooling or dehumidification is required.
OBJECTS AND SUMMARY OF THE DISCLOSURE
It is a primary aim and object of the present invention to provide a blanket assembly interconnected with apparatus that is selectively adjustable to provide a supply of either cooled or heated air, as desired.
Another object is the provision of blanket assembly for directing a large number of low velocity and pressure micro-streams of temperature modified air onto an individual covered by the blanket.
Yet another object of the invention is the provision of interconnection means for distributing a portion of the temperature modified air to pillows to be used in conjunction with the blanket assembly.
A still further object is the provision of a blanket assembly and air modifying apparatus as in the above objects in which the humidity of the modified air is controlled and a pleasant scent is added to the air.
In accordance with the disclosure herein, a first version of blanket assembly is provided having an outer layer constructed of a relatively close weave fabric preventing air flow therethrough and which is of suitable geometry and dimensions for use in covering a bed top, for example. Underneath the top layer is a second layer of material edge connected to the top layer and which is constructed of a material permeable to air, such as relatively thin taffeta, for example. A cavity or pocket is formed between the two layers which, in a way to be described, receives pressurized cooled or heated air that passes through the air permeable layer to cool or heat, as the case may be, the individual using the blanket assembly. One end portion of the blanket assembly has an inlet nozzle which can be formed directly from the materials composing a blanket assembly layer, for example, or may include a fitting suitably secured within an opening to the blanket assembly cavity or chamber.
A modified blanket assembly construction includes rigid edge wall members holding the outer and inner layers separated at a predetermined spacing which reduces the possibility of "pinch-off" between the layers restricting air flow within parts of the cavity or chamber.
The apparatus for conditioning air to either a cooled or heated state includes a first heat exchanger consisting of a finned heat exchanging element enclosed within a manifold, which manifold has entrance and exit openings. A second heat exchanger of substantially the same construction as the first is arranged closely adjacent the first heat exchanger. A surface of each exchanger is brought into contact with a plurality of semiconductor plates or elements which upon selective energization warm or cool one of the exchanger surfaces while effecting the opposite to the other exchanger surface. More particularly, electric power interconnected with the thermoelectric plates passes D.C. current through the plates in either of two different directions, one direction effecting cooling and the other producing heating. First and second air impellers are mounted in the heat exchanger manifolds to provide a continuous flow of air therethrough. A flexible hose has one end interconnected with the second heat exchanger and the other with the air inlet to the blanket assembly. A removable condensate collection pan or trap is provided adjacent each exit opening of the second heat exchanger.
In operation, the air impellers are actuated, and electric power is applied to the thermoelectric modules which in accordance with a principle known as the Peltier effect serves to pump heat from one junction for absorption at another junction. Assuming that the ambient temperature is cooler than desired and, therefore, heat is desired in the blanket, the first heat exchanger will be the reference junction for the thermoelectric modules and with electric current passed through the semiconductor plates in the proper direction, heat absorbed at this junction is pumped to the second heat exchanger at a rate proportional to the electric current. The air passing through the second heat exchanger is heated and then pumped to the blanket assembly. The heated air added to the blanket assembly cavity can only make its way out through the relatively thin and air permeable inner layer where it is played upon the body of an individual wrapped in the blanket in low pressure, slow moving micro-streams as well as by direct conduction through the second layer.
Alternatively, when the ambient temperature is warmer than desired, and, therefore, cooling is called for, the electrical supply is switched and now heat absorbed at the second heat exchanger at a rate proportional to the electric current passing through the modules thereby effecting cooling of the air passing through the second heat exchanger. As before, pressurized cool air is passed to the blanket assembly cavity.
Optionally, the apparatus can include a filter to remove dirt and dust, a humidifier (e.g., ultrasonic humidifier), and equipment for ionizing and adding a pleasant scent to the modified air.
DESCRIPTION OF THE DRAWING
FIG. 1 is a perspective view of a temperature conditioned blanket and conditioning apparatus of the present invention shown stored in a luggage case.
FIG. 2 shows the temperature conditioned blanket in place on a bed and interconnected with the conditioning apparatus adjacent thereto.
FIG. 3 is a perspective, partially fragmentary view of one form of temperature conditioned blanket.
FIG. 4 is a sectional view taken along the line 4--4 of FIG. 2.
FIG. 5 is a side elevational, sectional view taken through the blanket 90-degrees to that of FIG. 4 along line 5--5 of FIG. 2.
FIG. 6 is a sectional view along line 6--6 of FIG. 5.
FIG. 7 is a further sectional view taken along the line 7--7 of FIG. 5.
FIG. 8 is a perspective, partially fragmentary view of an alternate form of temperature conditioned blanket.
FIG. 9 is a sectional view through the blanket of FIG. 8 taken along line 9--9.
FIG. 10 is a still further embodiment of the invention showing the blanket with a temperature conditioned pillow.
FIG. 11 is a still further embodiment of temperature conditioned blanket.
FIG. 12 is a sectional view taken along line 12--12 of FIG. 11.
FIG. 13 is a sectional view taken along line 12--12 of FIG. 12.
FIG. 14 is a side elevational, sectional view of a further embodiment.
FIG. 15 is a side elevational, sectional view of a still further blanket embodiment.
FIG. 16 is a side elevational, sectional view through the air temperature conditioning apparatus taken along line 16--16 of FIG. 2.
FIG. 17 is a further sectional view taken along line 17--17 of FIG. 16.
FIG. 18 is yet another sectional view taken along the line 18--18 of FIG. 16.
FIG. 19 is a perspective view of the temperature conditioning apparatus.
FIG. 20 is an exploded view of the various parts of the apparatus of FIG. 19.
FIGS. 21A, B and C depict, in schematic form, different ways of passing air through the temperature conditioning apparatus.
FIG. 22 is a function block schematic of the electrical control and power supply for the air temperature conditioning apparatus.
FIG. 23 is a detailed circuit schematic of the electrical control and power supply apparatus of FIG. 21.
FIGS. 24A and B show two additional forms of cascading Peltier effect elements.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference now to both FIGS. 1 and 2, a blanket of selectively modifiable temperature is enumerated generally as 30 and, in a way that will be described, is interconnected to air temperature control apparatus 31 which can selectively cool or heat air supplied to the blanket, as desired. That is, a fundamental aspect of the present invention is the provision of a blanket for conventional use on a bed 32, for example, and which in cold weather can be supplied with heated air, or during warm weather with cooled air. When not in use, the apparatus 31 and the blanket 30 may be stored in a luggage case 32' for ready transportation from one location to another during traveling, for example.
With reference now to FIGS. 3 and 4, the blanket 30 is seen to include an outer fabric layer 33 made of a soft pliable fabric material which is closely woven so as to prevent substantially all transfer of air therethrough, or, preferably, the layer may be made of latex. The outer layer can also have any of the usual surface adornment features found in conventional blankets or bed covering coverlets, for example, and is of such dimensions as to extend over the main top surface of the bed 32 and, if desired, downwardly at the sides and end of the bed.
Underneath the part of layer 33 that is intended to extend across the bed top surface, there is a second layer or sheet 35 made of an air permeable material. This second layer 35 is edge stitched or sealed to the layer 33 forming an air chamber or cavity 36 between the layers 33 and 35. As noted, the layer 35 is made of a material that readily allows air to move therethrough such as, for example, taffeta, such that the user of the blanket will be warmed or cooled, as the case may be, by pressurized temperature modified air applied to the chamber 36.
As can be seen best in FIG. 3, the layers 33 and 35 are edge stitched or sealed in a suitable manner around substantially the entire periphery except for a short portion at the front or leading edge of the blanket as it lies on the bed. At the front edge a portion of the air impervious layer 33 is bent onto itself forming a hollow tube or nozzle 37 with an open end 38 that is in direct communication with the chamber 36.
In use of the blanket as described to this point, the blanket 30 is located on the bed or wrapped about the individual. A flexible tube or hose 39 has one end interconnected with the air temperature controlling apparatus 31 and its other end received within nozzle opening 38. Since the edges of the blanket are sealed, pressurized conditioned air entered into the cavity 36 moves outwardly through the air permeable layer 35 to be directed onto the individual over a relatively large surface and through a very large number of small pores in the layer 35.
The inlet nozzle 37 for the blanket 30 may be relatively short so as to really only extend partway down the end of the bed and be covered by the bedspread, or it may be longer extending to the floor, as shown in FIG. 5, for example.
FIGS. 8 and 9 depict a further form of blanket 39 for use with the apparatus 31. As in the first described blanket it includes an outer air impervious layer 40 and an inner air-permeable layer 41 which are edge stitched or sealed to form an intervening chamber or cavity 42. Additionally, a length of flexible tubing 43 formed from a porous material is located within the cavity 42 and has one end affixed to an air inlet nozzle 44 and its other end sealed off. The tubing 43 is arranged into a sinuous path so as to extend over substantially the full horizontal region of the blanket. Pressurized conditioned air moves into the flexible tubing 43, outwardly through the tubing pores and then through layer 41 to warm or cool the user, as the case may be.
FIG. 10 depicts yet another embodiment in which another conditioned air hose 45 interconnects with the primary air hose from the apparatus 31 to provide conditioned air to a bed pillow 46. In this way, conditioned air is made available to the neck and shoulders of an individual resting or sleeping in the bed as well as being directed onto the trunk and extremities as already described.
A still further version of blanket for use with the apparatus 31 is shown in FIGS. 11 through 13 and enumerated as 47. In this embodiment the upper air impervious layer 48 not only covers the entire upper surface of the bed but has a further portion extending down the front of the bed substantially to floor level (FIG. 12). The underlying air permeable layer 49 is edge stitched or otherwise sealed to layer 48 and has a geometry and dimensions sufficient to cover only substantially the upper surface of the bed. An air impervious section 50 is sealed or stitched to layer 49 along the upper front edge of the bed and extends downwardly to the floor level. In addition, a plurality of longitudinal stitch or sealing lines 51, 51'--are provided between the layers 48 and 49, and between the layer 48 and section 50 as is shown in FIG. 13. These sealing lines serve to form a plurality of longitudinally extending chambers 52, 52'--from just short of the floor level in the front of the bed all the way to the opposite extremity of the blanket. As before, an inlet nozzle 53 receives an end of the flexible tubing interconnected with the air conditioning apparatus. In use, the pressurized conditioned air moves from the inlet nozzle into plurality of the blanket chambers 52, 52'--of which establishes a superior and highly uniform distribution of conditioned air.
FIG. 15 shows a still further form of blanket or cover 53 which offers increased uniformity of modified air transfer in that pinch-off of the air chamber between the blanket layers is prevented or substantially reduced. Comparing with the FIG. 4 embodiment, it is to be noted that a pair of wall members 54 and 55 are formed at each side of the air chamber 56 by incorporating extra blanket material into those regions. The permeable inner layer 58 is secured to the outer layer at points below the lower edge of the wall members 54 and 55. In use, even though a user's body will cause the inner layer to bulge upwardly toward the blanket outer layer, the wall members maintain a substantial space for the chamber 56 avoiding pinch-off.
For the ensuing description of the air temperature modification or conditioning apparatus 31, reference is now made to FIG. 20 where its various parts are shown in exploded relation. The essential temperature modification means consists of a plurality (e.g., three) of heating/cooling semiconductor plate elements 59 which, in a way that will be described, have their temperature increased or decreased, as desired, depending upon the manner of electrical energization. More particularly, such elements consist of a quantity of bismuth telluride heavily doped to produce either an N or P type semiconductor. These semiconductor elements are located in contact with two air transfer means, one in contact with ambient air outside the blanket and another of which contacts air to be modified and pumped into the blanket chamber/s. It can be shown that, heat absorbed at a "cold" junction of the semiconductor elements is pumped to the "hot" junction at a rate proportional to the electric current passing through the elements, with the direction of heat flow being determined by the polarity of energizing current. Such elements are commercially available under the trade designation 950-71 from Thermoelectric Cooling of America, Chicago, Ill.
A first heat exchanger 60 is preferably a metal (e.g., copper) extrusion, stamping or forging, having a plurality of upstanding, spaced apart plates or fins 61 on one surface and the opposite surface 62 being relatively flat for contacting engagement with conductor elements 59 during assembly. The first heat exchanger 60 finned side is enclosed within a manifold housing 63 with two end caps 64 and 65 enclosing the housing ends. A fan 66 is fixedly secured in the upper wall of the housing such that it will take air from the surrounding or ambient environment and pump it into the manifold across the fins or plates of the exchanger where heat is exchanged in accordance with known physical laws and then pumped out through end cap openings 67 and 68 back in the environment.
A second heat exchanger 69, which is larger than the first described heat exchanger, has its flat surface 70 brought into abutting contact with the opposite major surfaces of semiconductor plates or elements 59. A manifold housing 71 is received over the exchanger fins 71' or plates and the ends are enclosed by end caps 72 and 73 having nozzle-like openings which can receive the end of a flexible hose for a purpose to be described. The outer housing wall has an opening within which is received a further fan or air impeller 74 which in one mode of use draws air from the outside inwardly to the manifold and across the heat exchanging surfaces of the fins and outwardly through a flexible tube received in an end cap opening to the blanket assembly. The remaining end cap opening is closed off to increase air flow.
Exchanger 69, E2, has a smaller Δt (i.e.) temperature differential) than E1 because it is larger and has more air passing through it. For optimum Peltier performance, the total Δt between the "cold" side and the "hot" side of an element should be held to a minimum. Since E1 is on the working side, it is desirable to have as much of the Δt as possible occur on this side. In explanation, there is only a given amount of t available for a given power setting of the apparatus, and by the described construction the t for E2 (the non-working side) is kept as low as possible.
The lower walls of end caps 72 and 73 are open, and spaced apart guide rails 75 and 76 extending transversely of the caps and defining the lower opening of each. An open-top condensate pan or trap 77 has outwardly extending flanges of such dimensions as to enable sliding receipt on the guide rails. The pans receive condensate during use and are readily removable to dispose of the collected condensate as needed. These pans are only needed on the heat exchange delivering modified air, since the reference heat exchanger air experiences a much smaller temperature variation and will, accordingly, produce much less moisture.
FIGS. 16 and 19 show the air temperature modification apparatus parts of FIG. 20 in assembled unitary relation. Also, FIGS. 16, 17 and 18 show the unitary air conditioning apparatus of FIG. 19 mounted within a housing along with other control and electrical energizing apparatus, to be described. It is this entire arrangement that is depicted as the apparatus 31 in FIGS. 1 and 2, for example.
FIGS. 17 and 18 show the detailed surface configuration of the heat exchanger fins or plates 61 as having a plurality of longitudinally extending surface grooves 78. In this manner, the heat exchanging surface of the plates 61 is substantially increased which enhances overall apparatus operational efficiency.
For the ensuing discussion of various ways to pass air through the apparatus for achieving cooled or heated air, reference is made to FIGS. 21A, 21B, and 21C. FIG. 21A shows the manner of passing air through the first and second heat exchangers as it has been described to this stage, namely, the air is forced into both manifolds by the fans centrally located in the respective manifold housings and air exits through one or both of the openings in the end caps.
FIG. 21B shows an alternate form of air passage through the heat exchangers in which one of the heat exchangers, E2, is operated in the same way as in 21A. However, in the second exchanger the fan instead of pumping air into the manifold pumps it out drawing air into each of the end cap openings.
FIG. 21C is a still further embodiment in which an air impeller may be located in either end cap opening of the exchanger E1 and there is no central manifold housing opening. Accordingly, air either forced or drawn into the manifold passes across the exchanger fins and out the other end cap. The heat exchanger E2 is the same as in FIGS. 21A and 21B.
A function block circuit schematic of the electrical control and energization for the semiconductor elements 59 to either heat or cool air is depicted in FIG. 22. The block identified as E2 is the heat exchanger through which ambient air is passed and serves as a reference temperature for the apparatus. A thermistor T1, which is a well-known device having electrical resistance functionally related to its temperature, is located within the E2 manifold and has leads interconnected within the block identified as On-Off and Duty Cycle Control providing an electric reference signal representative of the ambient air temperature. E1 is the heat exchanger for modifying or conditioning the air and includes a further thermistor T2, the output thermistor, for measuring the temperature of the air after it has been conditioned. A Switch Mode Power Supply is under the control of the On-Off and Duty Cycle Control which determines when and how long the power is to be applied to the semiconductor elements, and, more particularly, the direction of the current flow through the elements in order to either cool or heat the air passing through heat exchanger E1.
An optional control identified generally as Infra-Red Remote Control is actuated by pushbuttons to increase or decrease the heating or cooling of the apparatus and accomplishes by sending out an infrared signal which is picked up by a detector located at the apparatus 31 and, which, in turn, through appropriate circuit logic interconnects and energizes the Switch Mode Power Supply to operate the apparatus as commanded.
A detailed circuit schematic of a preferred form of power and energization control for the apparatus 31 is shown in FIG. 23. A manually operated On-Off switch 79 when switched to On applies line power to the motor drive for the fans 66, 74. This switch as well as all other manual switches of the momentary contact type.
One side of the domestic A.C. power is now available through switch 79 (now closed) to one input terminal of a silicon controlled rectifier (SCR) 80. The other side of the A.C. power is applied to the SCR through normally-open relay point 81 which is closed when power switch 82 is closed energizing relay coil 83'. This relay as well as the others are all latching relays. The SCR on being energized provides a D.C. voltage of appropriate voltage to drive the semiconductor plates 59 for cooling/heating as already described. A full-wave SCR bridge suitable for present purpose is manufactured by Dart Controls of Zionsville, Ind. and sold under the trade designation 250B.
Assuming mode switch 83 is open, a first D.C. line 84 interconnects one output terminal of the SCR through a N/C relay point 85 to one side of semiconductor plates 59, while a second D.C. line 86 passes through a further N/C relay point 87 to energize the other side of semiconductor plates. The semiconductors are now operating in one mode, say, heating.
It is to be noted that when the SCR is connected to provide D.C. power to the semiconductor plates N/C relay point 88 is open preventing energization of mode relay coil 89. The purpose of this is to protect the SCR which could be damaged if its output side were switched (e.g., mode changed) while delivering power. Accordingly, if it is desired to effect a mode switch, first the power switch 82 must be opened taking power off the SCR and closing relay point 88. Now, on closing mode switch 83 coil 89 can be picked up which transfers relay points 85 and 87 to reverse D.C. polarity connection with the SCR. Power switch 82 may now be closed causing the SCR to once again apply power to the semiconductor plates 59, although now in a polarity to effect cooling. N/O relay points 90 are closed when mode relay coil 89 is energized and keep the relay coil energized when power is on the SCR (i.e. when 88 opens).
Light emitting diodes 91-93 (LED) are interconnected with a low D.C. voltage source 94 (e.g., 5 VDC) which is energized when fan switch 79 is closed. At this time D.C. power is applied to the LED's in such polarity as provide a certain color light (e.g., red) which identifies, say, that the apparatus is in "heating" mode.
Simultaneously with mode switch 83 closing, relay coil 95 is energized transferring points 96 and 97 which reverses polarity of the D.C. voltage applied to LED's 91-93. Polarity reversal produces a different color of illumination by the LED's (e.g., green) signifying that the apparatus is now in the "cooling" mode.
The silicon controlled rectifier 80 is heat sensitive and, therefore, should be located within the apparatus 31 in a manner not exposing it to excessive heat from the semiconductor plates 59. As shown in FIG. 19 the SCR 80 is mounted directly onto the top surface of the manifold 63 and in good contact therewith such that heat generated by the SCR is at least partly conducted away in the air stream.
In the first described embodiment, the Peltier plates 59 are arranged in a single plane with all of the plates contacting surface 62 of exchanger 60 as a temperature reference and contacting surface 70 of exchanger 69 to modify its temperature. FIGS. 24A and B depict a cascading arrangement of Peltier semiconductor plates that is believed to posses certain advantages in operation over the single plane arrangement. As shown in FIG. 24A a first set of Peltier devices 98 are mounted onto an interface plate 99 and all have a surface contacting heat exchanger surface 62. A second set of Peltier devices 100, which in number exceed the devices 98, are mounted to contact the opposite side of the interface plate as well as exchanger surface 70.
FIG. 24B includes a first module 101 consisting of a base plate 102 with a number of Peltier devices 103 mounted thereon, and a second module 104 consisting of a base plate 105 with a larger number of Peltier devices mounted thereon. The two modules are assembled together by abutting the base plates together and with a thermal grease 106 increasing the thermal contact, or, optionally, providing a solder layer interface. The two so assembled modules are then brought into contact with the heat exchanger surfaces 62 and 70.
By the use of either cascading system of FIGS. 24A or 24B, the total Δt is increased allowing for a smaller exchange E1 for achieving the same cooling or heating power output allowing savings in size, weight and manufacturing cost.
It is contemplated that the described air modifying apparatus can be enhanced by adding known equipment to ionize the conditioned air or to add a pleasant scent to the air. Moreover, under certain circumstances it may be desirable to humidify the conditioned air and could most effectively be accomplished by coupling an ultrasonic humidifier with the conditioned air outlet. | A blanket assembly has an outer layer constructed of a relatively close weave fabric preventing air flow therethrough. Underneath the top layer is a second layer of material edge connected to the top layer and which is constructed of a material permeable to air, such as relatively thin taffeta, for example. A cavity exists between the two layers which receives pressurized cooled or heated air that passes through the air permeable layer to cool or heat the individual using the blanket assembly. A modified blanket assembly construction includes rigid edge wall members holding the outer and inner layers separated at a predetermined spacing reducing "pinch-off" between the layers restricting air flow within parts of the cavity or chamber. Peltier effect elements are selectively energizable to heat or cool air provided to the blanket assembly cavity. | 8 |
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates to cartons, and more particularly to a carton for holding an active material and controllably releasing it to the air.
2. Description of the Prior Art
There are a variety of active materials for use in household and commercial applications which it is desirable to contact with and release into the ambient air. Among these are insecticides and air fresheners which can be packaged in solid form in containers having air passages which permit release. Frequently, products of this type are packaged in containers having a plurality of openings which are closed at the time of purchase but which are opened at the time of use to allow room air to circulate over the surface of the solid active material.
In one type of carton, the openings are covered with a panel of release paper. When the consumer is ready to use the product, such as an air freshener, the release paper is peeled from the face of the container to allow room air to begin circulating through the openings. In another type of carton, the consumer activates the air freshener material by squeezing to release an encapsulated active ingredient. In yet another type of carton, holes in an outer wall are opened or closed by a slidable inner sheet which acts as a valve.
Molded plastic containers, usually consisting of a molded shell and a separate molded cover, have been employed to hold air freshener material. However, while molded plastic containers have an aesthetically pleasing appearance, the cost of making them is higher than might be desired. The shell and cover must be moled in separate operations and stored in unassembled form until the air freshener insert is loaded. The cover then must be glued or otherwise secured to the shell to provide a closed container. The extra time required for the separate manufacturing and assembly operations results in added manufacturing costs for the package and ultimately for the product sold therein. The fact that the molded shells and covers must be shipped and stored in their molded form will also cause increased transportation and storage costs.
In a prior patent application, U.S. Ser. No. 25,012 filed Mar. 29, 1979 now U.S. Pat. No. 4,219,145 entitled "CARTON WITH ADJUSTABLE AIR PASSAGES", assigned to the same assignee as the present invention, an improved package for controllably releasing active materials to the air is disclosed which has inner and outer slidable members constructed of a sheet material wherein the inner and outer members can be slidably moved between open and closed positions. The carton has a plurality of adjustable air passages and comprises: (a) a first tapered sleeve forming an outer carton unit, said first sleeve being closed at at least one end and having a plurality of spaced openings therein; and (b) a second tapered sleeve forming an inner carton unit, said second sleeve being nested within said first sleeve and being slidable between a first position and a second position, said second sleeve being closed at at least the end opposite said end closed in said first sleeve and having a plurality of spaced openings therein arranged complementarily to said spaced openings in said outer carton unit to align with the openings therein when said inner carton unit is in said first position, and to align with the spaces between said openings in said outer carton unit when said inner carton unit is in said second position.
SUMMARY OF THE INVENTION
The present invention relates to an improved package of the type having an inner and outer tapered carton unit provided with complementary openings, which when aligned permit the release or diffusion of material housed within the inner unit to the air. The tapered sleeves normally bind when moved relative to each other when the openings are out of alignment, to maintain the closure, when the diffuser is inoperative. However, movement in the opposite direction causes the openings in the inner and outer sleeves to be readily and easily aligned.
The package of the present invention employs a stop on the outwardly tapering end of the outer carton sleeve to restrict movement of the inner carton sleeve when the air diffuser openings are aligned. Additionally, a shiftable, removably mounted blocking tab formed integral with the opposed edge of the outer sleeve is disposed inside the outer sleeve in blocking relationship to the inner sleeve to prevent relative movement between the sleeves until the package is ready for initial use. A scored, adhesive tear dot in the blocking tab secures the blocking tab to an interior side wall of the outer sleeve; the end of the blocking tab is grasped and pulled by a user to withdraw such tab from the outer sleeve, thereby freeing the inner sleeve for sliding movement within the outer sleeve.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and its advantages will be more apparent from the following detailed description, especially when read in light of the attached drawings wherein:
FIGS. 1 and 2 are plan views of the blanks for forming the outer and inner carton sleeves, respectively, of the carton of the present invention;
FIGS. 3 and 4 are perspective views illustrating the initial stages of folding of the blanks shown in FIGS. 1 and 2, respectively;
FIG. 5 is a perspective view illustrating the final assembly of the composite carton of the present invention;
FIG. 6 is a perspective view of the assembled carton of the present invention showing the air passages in their operative, open position;
FIG. 7 is a cross-sectional view taken along line 7--7 in FIG. 6;
FIG. 8 shows the carton shown in FIG. 6 with the openings in their inoperative, closed position;
FIG. 9 is a cross-sectional view taken along line 9--9 in FIG. 8; and
FIG. 10 is a perspective view of the assembled carton of the present invention mounted on a support hook and illustrating its optical manner of use when so supported.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention provides a two component carton having adjustable air passages and a blank for forming it. The carton is especially adapted for use in storing a solid active material such as an insecticide or a room air freshener during transportation and display, and then functioning as a dispenser for the active material by controllably releasing the active material to ambient air through adjustable air passages during use. The carton is formed of slidable inner and outer tapered sleeves having complementary, spaced openings. The openings are positioned to permit room air to circulate into contact with the active material and back to the room in their open position and to also permit their partial or complete closure as the sleeves are moved to a second, closed position.
The carton 10 in FIGS. 6-10, inclusive, is a presently preferred embodiment according to this invention. The carton 10 can be supported by means such as a tab 300 having a opening 302, hung from a hook 304 mounted on a vertical support wall W. Alternatively, the carton 10 can be free standing, as illustrated in FIGS. 6 and 8, supported on a rectangular base, in which case the tab is torn away from the carton and discarded.
The carton 10 has a substantially rectangular cross-section at any point perpendicular to the vertical axis. While this embodiment is preferred, it is to be understood that the carton can have other cross-sectional shapes perpendicular to the axis along which it slides. For example, it is possible to have virtually any cross-section such as triangular, square, pentagonal, hexagonal, octangonal, and the like. The objects of the present invention are equally well attained despite the particular cross-section, and can be attained even with circular and oval cross-sections.
With this general explanation, the following detail will be directed toward a preferred embodiment of the invention which is particularly well suited for use in dispensing air fresheners which are held in solid form within the carton 10.
Referring now to FIGS. 6, 8 and 10, carton 10 is shown in FIGS. 8 and 10 (in phantom lines) in the closed position and is shown in FIGS. 6 and 10 (face line position) in the fully open position. It will be understood that the openings 12 can be adjusted to any degree between the first position wherein they are completely open and the second position wherein they are completely closed. Adjustment between the open and the closed positions is obtained by moving outer carton unit 14 relative to inner carton unit 16 to obtain the desired degree of alignment and therefore opening of the apertures in the inner carton 16 and outer carton unit 14. The openings 12 are shown on the front and back panels, but this is preferred only. The openings can be positioned as desired.
The detail of the construction of the preferred embodiment will be better understood by viewing FIGS. 1 through 5 which show the various stages of construction of the carton 10. FIG. 1 shows an outer blank 100 for forming the outer carton unit 14 and FIG. 2 shows an inner blank 200 for forming the inner carton unit 16.
FIG. 1 shows outer blank 100 for forming the outer carton unit 14. This blank 100 is being viewed from what will be its outside surface. As will be seen in FIG. 3, the blank 100 can rest on back panel 102 for assembly by folding the other panels upwardly from the horizontal to the final form. The blank comprises rectangular front panel 104, rectangular rear panel 102, and trapezoidal side wall panels 106 and 108. These parts are of essentially the same dimensions as those of the like parts of the inner carton blank 200. If desired, to obtain a better sliding engagement, the outer and inner carton units 14 and 16 can differ in overall dimension by about 1 to 2 times the thickness of the sheet material for forming the cartons. The sheet materials used in forming the carton can be any of those typically employed for making disposable cartons. Preferably, a paperboard material or a laminate of a paperboard with a plastic material will be employed.
Referring again to FIG. 3, the outer carton blank 100 also has a glue flap 110 as well as flaps 114, 116 and 118 for closing one end of the outer carton unit 14. Flaps 116 and 118 are hingedly connected to the bottom edge of front panel 104 and back panel 102, respectively, while flap 114 is hingedly connected to bottom edge 134 of trapezoidal side panel 106. The tab 300 is hingedly connected to bottom edge 136 of trapezoidal side panel 108 and includes scored tear out dot or circle 306 which may form opening 302. The inner face of tear out dot 306 has an adhesive 307 preapplied thereto for purposes which will become later apparent. Tab 300 is bendable 180 degrees inwardly along a score line 136 into overlapping face-to-face contact with side wall panel 108. Score line 308 divides the tab 300 into an intermediate stretch or section 311 and a free outer extremity or section 309. Apertures or openings 112 are provided in spaced relation on both the front and the back panels. The openings are arranged such that in the final construction they will be complementary to similar spaced openings 212 in the inner carton unit 16 to align with the openings 212 therein when said inner carton unit 16 is in the first or open position (as shown in FIG. 6), and to align with the spaces between the openings 112 in the outer carton unit 14 when the inner carton unit 16 is in the second or closed position (as shown in FIG. 8).
It is preferred that the openings 112 be of essentially the same shape and size as the openings 212 in the inner carton blank 200. Because it is desired in the preferred embodiment of the invention to enable the complete closing of the openings, the space between the openings 112 on the outer carton blank 100, as measured along any line parallel to the vertical axis of the final carton 10, must be of greater vertical extent than the openings 112 themselves. The openings 212 in the inner carton blank 200 must be similarly positioned and spaced so that alignment with openings 112 in the constructed carton 10 will be facilitated.
In assembling the outer carton unit 14 from the blank 100, panels 102, 104, 106, 108 and glue flap 110 are folded about fold lines 126, 128, 130 and 132 as shown in FIG. 3. The blank 100 is then glued in folded position by securing flue flap 110 of the interior of side panel 106. The flaps 116 and 118 are then folded 90 degrees relative to the bottom edges of panels 104 and 102, respectively, and adhesively secured to the lower surface of flap 114 to form a stop to limit movement of the inner carton unit 16 by abutment with the closed lower end of inner carton unit 16. If used in its free standing mode (FIGS. 6 and 8), tab 300 may be torn along bottom edge 136 and removed entirely; bottom edge 136 may be scored if desired to facilitate such tearing.
The inner blank 200 is shown in FIG. 2 and comprises a rectangular back panel 202, a rectangular front panel 204 and two trapezoidal side panels 206 and 208. As will be seen in FIG. 4, the blank 200 can rest on back panel 202 with the other carton panels being folded up from the horizontal to the final form. A glue tab 210 is provided for sealing the inner blank 200 into a sleeve by connecting to the interior of side panel 206. The inner blank 200 has a substantially rectangular cross-section after folding as shown in FIG. 4. Both the front panel 204 and the rear panel 202 have spaced openings 212 therein.
After insertion of the product, the inner carton unit 16 is closed at both ends. The top end has flaps 214, 216, 218 and 220 which are folded over and adhesively connected to form a closed end. Flap 216 is bendable from back panel 202 about a fold line 222. Similarly, flap 220 can be bent from front panel 204 about fold line 224, while flaps 214 and 218 are bendable about fold lines 234 and 236, respectively. The bottom end has flaps 246, 248, 250 and 252 which are similarly folded over about fold lines 254, 260, 256 and 258, respectively and adhesively connected to form a second closed end.
Referring to FIG. 4, the sequence of construction of the inner carton unit 16 can be seen more clearly where the panels 202, 206, 204, 208 and glue flap 210 are folded about intermittent score lines 226, 228, 230 and 232. Then, glue flap 210 is adhered to wall 206. Tabs 214 and 218 are folded about fold lines 234 and 236 and then overlayed by upper tabs 216 and 220 which are folded about fold lines 222 and 224, respectively. Tabs 216 and 220 are preferably adhesively secured in known manner. Similarly, tabs 248 and 252 are folded about fold lines 260 and 258 and then overlayed by tabs 246 and 250, folded about lines 254 and 256 and adhesively joined.
Referring now to FIGS. 5 and 7, there is shown the next stage in construction of the carton wherein the inner carton unit 16 in fully constructed form is slidably passed into partially assembled outer carton unit 14. After insertion of inner carton unit 16 into outer carton unit 14, flaps 114, 116 and 118 are folded about fold lines 134, 122 and 124 to provide a stop on the bottom end of the outer carton unit 14 to preclude excessive movement of the inner carton relative to the outer carton towards the outwardly tapered or flared end of carton 10. Then, tab 300 is folded inwardly 180 degrees along score line 136 into face-to-face engagement with the inside face of side wall panel 108 and is adhered to the latter by virtue of adhesive 307 on tear out dot 306. Simultaneous with the folding of tab 300 about score line 136, the outer free extremity of tab 300 engages the bottom flap 250 of innercarton 16 and is forced to fold 90 degrees into flush contact with bottom flap 250 and is disposed essentially perpendicular to the side wall panel 108. The outer free extremity of tab 300 is thus disposed in blocking engagement with the inner carton unit 16 and maintains the latter in its closed position until the package is ready for use. Tab 300 is held in blocking relationship to the inner carton unit by the adhesive 307 which holds the intermediate stretch of tab 300 essentially parallel to side wall panel 108.
The tapered side panels promote tight frictional engagement of the inner and outer carton units in intermediate relative positions, to selectively adjust the width of the complementary openings. The tapered side panels preclude complete disassociation of the inner and outer carton units in one direction of movement by wedging engagement. The tight friction fit produced by the tapered side walls serves to prevent or at least substantially reduce air flow between the interior of the package and the atmosphere when the package is closed, thereby preventing sublimation of the product during periods of non-use. The primary and most important purpose of tab 300 is to initially hold the inner carton unit in its raised, closed position (FIG. 8) in order to prevent inadvertant opening and activation of the package prior to use thereof by a consumer, as might occur during shipping for example. When the package is about to be used, the consumer merely grasps the free outer extremity 309 of the tab 300 and pulls the tab 300 outwardly from the interior of the outer carton unit 14. Upon pulling of the tab 300, the intermediate stretch 311 tears around the perforated score lines defining tear out dot 306, leaving tear out dot adhered to the side wall panel 108 and forming the opening 302 in tab 300. At this point, the inner carton unit 16 may slide downwardly within outer carton unit 16 to open and thereby activate the package. The tab 300 may then be removed by tearing the same along bottom edge 136, or, if desired the tab 300 can remain on the package and be employed to hang the same from the hook 304, as discussed previously. In any event the stop panels on the outer carton unit 16 preclude disassociation of inner and outer carton units once the tab 300 is pulled from its blocking position. | Disclosed is a carton having adjustable air passages and a blank for forming it. The carton is formed of slidable inner and outer tapered sleeves having complementary spaced openings. The openings are positioned to provide open air passages when the inner sleeve is slid to a first position, and to close the passages as the inner sleeve is moved toward a second position. A stop is provided in the outer sleeve to limit movement of the inner sleeve when slid to the first position, while the taper between the sleeves precludes undue movement of the sleeves past the second position. A shiftable tab is also provided on the outer sleeve to block sliding movement of the sleeves relative to each other until the carton is ready for initial use. | 1 |
REFERENCE TO RELATED APPLICATIONS
[0001] Reference is made to U.S. Provisional Patent Application Ser. No. 61/070,377, filed Mar. 20, 2008 and entitled: Social and Contextual-Based Facial Recognition, the disclosure of which is hereby incorporated by reference and priority of which is hereby claimed under 37 CFR 1.78(a)(4) and (5)(i).
FIELD OF THE INVENTION
[0002] The present invention relates to systems and methods for mapping interpersonal relationships.
BACKGROUND OF THE INVENTION
[0003] The following publications are believed to represent the current state of the art:
[0004] U.S. Pat. Nos. 5,164,992; 5,963,670; 6,292,575; 6,819,783; 6,944,319; 6,990,217; 7,274,822 and 7,295,687; and
[0005] U.S. Published Patent Application Nos.: 2006/0253491 and 2007/0237355.
SUMMARY OF THE INVENTION
[0006] The present invention seeks to provide an improved system for mapping interpersonal relationships. There is thus provided in accordance with a preferred embodiment of the present invention a method for mapping interpersonal relationships including processing a multiplicity of images and contextual information relating thereto including creating and prioritizing a list of a plurality of candidate persons having at least a predetermined relationship with at least one person connected to at least one image, using multi-dimensional information including visually sensible information in the multiplicity of images and contextual information relating thereto and searching the list of a plurality of candidate persons based at least in part on the prioritizing to select at least one of the candidate persons as having at least a predetermined relationship with the at least one person.
[0007] There is additionally provided in accordance with a preferred embodiment of the present invention a system for mapping interpersonal relationships including processing functionality operative to process a multiplicity of images and contextual information relating thereto including creating and prioritizing a list of a plurality of candidate persons having at least a predetermined relationship with at least one person connected to at least one image, using multi-dimensional information including visually sensible information in the multiplicity of images and contextual information relating thereto and searching functionality operative to search the list of a plurality of candidate persons based at least in part on the prioritizing to select at least one of the candidate persons as having at least a predetermined relationship with the at least one person.
[0008] Preferably, the searching also employs the multi-dimensional information.
[0009] In accordance with a preferred embodiment of the present invention, the multi-dimensional information includes at least one of visual information appearing in an image, geographical information appearing in the image, visual background information appearing in the image, images of other persons appearing in the image and person identifiers appearing in the image and at least one of information relating to an image collection of which the image forms a part, a time stamp associated with the image, information not appearing in the image but associated therewith, geographical information not appearing in the image, visual background information appearing in another image and person identifiers not appearing in the image but otherwise associated therewith.
[0010] More preferably, the multi-dimensional information includes at least one of visual information appearing in an image, geographical information appearing in the image, visual background information appearing in the image, images of other persons appearing in the image and person identifiers appearing in the image and at least two of information relating to an image collection of which the image forms a part, a time stamp associated with the image, information not appearing in the image but associated therewith, geographical information not appearing in the image, visual background information appearing in another image and person identifiers not appearing in the image but otherwise associated therewith.
[0011] Even more preferably, the multi-dimensional information includes at least one of visual information appearing in an image, geographical information appearing in the image, visual background information appearing in the image, images of other persons appearing in the image and person identifiers appearing in the image and at least three of information relating to an image collection of which the image forms a part, a time stamp associated with the image, information not appearing in the image but associated therewith, geographical information not appearing in the image, visual background information appearing in another image and person identifiers not appearing in the image but otherwise associated therewith.
[0012] Most preferably, the multi-dimensional information includes all of the following: visual information appearing in an image, geographical information appearing in the image, visual background information appearing in the image, images of other persons appearing in the image; person identifiers appearing in the image, information relating to an image collection of which the image forms a part, a time stamp associated with the image, information not appearing in the image but associated therewith, geographical information not appearing in the image, visual background information appearing in another image and person identifiers not appearing in the image but otherwise associated therewith.
[0013] In accordance with a preferred embodiment of the present invention, the at least one image is a composite image, which includes images of multiple persons, at least one of whom is unknown. Alternatively, the at least one image is a composite image, which includes images of multiple persons, none of whom are known.
[0014] Preferably, the at least one person connected with the at least one image appears in the image.
[0015] In accordance with a preferred embodiment of the present invention, the method also includes tagging the at least one person connected with the at least one image with a person identifier. Additionally or alternatively, the processing includes iterative generation of relationship maps based on at least visually sensible information and also on additional, non-visually sensible information related to persons who either appear in the at least one image or are otherwise associated therewith.
[0016] Preferably, the non-visually sensible information is meta-data associated with image data. Additionally, the meta-data includes data derived from a social network. Alternatively or additionally, the meta-data includes data attached to the image data of the composite image.
[0017] In accordance with a preferred embodiment of the present invention, the iterative generation of relationship maps starts from a precursor relationship map, containing information on relationships of at least one known person in the at least one image.
[0018] Preferably, the relationship map is also based on inter-personal relationship data received from at least one of a social network and earlier instances of relationship mapping based on analysis of other images. Additionally or alternatively, the relationship map includes an indication of at least strength of the relationship between two persons. Alternatively or additionally, the relationship map includes a face representation which identifies each of the persons in the map.
[0019] In accordance with a preferred embodiment of the present invention, the relationship map includes an indication of whether each person in the map is a male or female. Additionally, the indication of whether each person in the map is a male or female is provided by at least one of a social network and operation of image attribute recognition.
[0020] Preferably, the prioritizing employs an indication of whether a person is a male or female. Additionally or alternatively, the prioritizing employs an indication of whether a person appears in the same album in a social network as another person appears.
[0021] In accordance with a preferred embodiment of the present invention, the processing includes seeking candidate persons having at least a predetermined relationship with a known person in at least one image. Additionally, the seeking candidate persons is carried out by starting with the generation of a list of candidate persons who have a temporal association with the known person based on visually-sensible information contained in the at least one image as well as non-visually sensible information. Additionally, the non-visually sensible information includes at least one of the time and geographical location where the composite image was taken and an identification of an album on a social network with which it is associated. Additionally or alternatively, the non-visually sensible information is obtained at least by interfacing with social network APIs to find persons who appeared in other pictures in the same album, or persons that appeared in other albums taken in the same geographical location at the same time.
[0022] Preferably, the list of candidate persons is extended and further prioritized by analyzing relationships of the persons appearing in a relationship map. In accordance with a preferred embodiment of the present invention, the prioritizing employs image attribute filtering.
[0023] In accordance with a preferred embodiment of the present invention, the processing includes facial representation generation performed on an unknown person in at least one image. Additionally, the method also includes comparing the facial representation with previously generated facial representations of the candidate persons in accordance with and in an order established by the prioritizing. Preferably, the comparing is terminated and a candidate person is selected when a combined priority/similarity threshold is reached for a given candidate person, the priority/similarity threshold taking into account the similarity of a facial representation of a candidate person to the facial representation of an unknown person, the priority of that candidate person established by the above-referenced prioritizing and the quality of the facial representation of the candidate person.
[0024] Preferably, user feedback confirming that the person whose image is believed to be a given person is or is not that person is employed in generation of a further iterative relationship map. Alternatively, user feedback confirming that the person whose image is believed to be a given person is or is not that person is employed in improving the face representation.
[0025] In accordance with a preferred embodiment of the present invention, the searching includes comparison of face representations of persons in the list of candidate persons with face representations of persons in the relationship map.
[0026] In accordance with a preferred embodiment of the present invention, the method also includes searching at least one of the relationship maps. Additionally, the searching of the at least one of the relationship maps employs search terms including at least one of uniquely identified persons, an additional image of a person, relationships between various persons, gender and face representations. Alternatively or additionally, the searching of the at least one of the relationship maps employs a user interface. Additionally or alternatively, the searching of the at least one of the relationship maps is carried out via at least one social network having access to the at least one of the relationship maps.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The present invention will be more fully understood and appreciated from the following detailed description, taken in conjunction with the drawings in which:
[0028] FIGS. 1A and 1B are together a simplified generalized illustration of relationship mapping functionality, employing multi-dimensional context, including facial recognition, operative in accordance with a preferred embodiment of the present invention; and
[0029] FIG. 2 is a simplified functional block diagram of a system for relationship mapping employing multi-dimensional context including facial recognition in accordance with a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0030] Reference is now made to FIG. 1A , which is a simplified generalized illustration of relationship mapping functionality employing multi-dimensional context, including facial recognition, operative in accordance with a preferred embodiment of the present invention. Facial recognition preferably includes facial representation generation and subsequent comparison of multiple facial representations.
[0031] The functionality may be understood and visualized by starting with a composite image, represented by a line drawing 100 , which includes images of multiple people, at least one of whom is known. In the present example, exemplified by line drawing 100 , one person, here labeled John, is known and a second person, here labeled Unknown, is not known. In this example, the person who took the picture represented by line drawing 100 is also known.
[0032] In accordance with a preferred embodiment of the invention in order to identify an unknown person, an iterative relationship map is generated based inter alia on visually sensible information contained in the composite image represented by line drawing 100 and also on additional, non-visually sensible information related to the above-mentioned persons who either appear in the composite image or are otherwise associated therewith. In a preferred embodiment, the non-visually sensible information may be meta-data attached to or associated with image data. The image data typically includes images in JPEG or PNG format. The meta-data may be data in XML or other suitable formats derived from a social network, such as FACEBOOK®, MYSPACE® AND FLICKR® as well as data conventionally attached to image data, such as XML, EXIF tag or other standard image contextual data. Typically, in the present example, John and Peter are uniquely known on a social network. The person who took the picture containing the composite image represented by line drawing 100 is identified as Greg, preferably by XML data attached to the image data of the composite image represented by line drawing 100 .
[0033] Generation of the relationship map preferably starts from a pre-existing iterative relationship map, here termed a precursor relationship map, represented by a diagram 102 , containing information on relationships of a known person or known persons in the composite image, in this case John. The precursor relationship map is also based on the inter-personal relationship data received from one or more social networks as well as inter-personal relationship data derived from earlier instances of operation of the relationship mapping functionality of the present invention based on analysis of other composite images.
[0034] Diagram 102 indicates that John, a male, is known to have a social relationship with Sharon, a female, who in turn has a social relationship with Mike, a male. John also has a social relationship with Peter, a male. The symbology employed in the relationship map indicates various parameters, including strength of the relationship between two persons. In the present example, a number inserted in a relationship indicating arrow indicates the strength of the relationship in the direction indicated by the arrow. The higher the number, the stronger the relationship in the illustrated example.
[0035] In the example of diagram 102 , the relationship between John and Mike is expected to be relatively strong, by virtue of the relationship between John and Sharon ( 85 ) and the relationship between Sharon and Mike ( 100 ), notwithstanding that it is an indirect relationship, through Sharon. This strength may be evidenced by multiple composite images in which Sharon appears with Mike and separately with John. The relationship between John and Peter is indicated, by the number 10, to be relatively weak, notwithstanding that it is a direct relationship. For example John and Peter may both appear together only in one composite image and that image may include many other people.
[0036] The precursor relationship map also includes a face representation produced by conventional facial representation generation techniques, such as techniques described in either or both of U.S. Pat. No. 5,164,992, entitled “Face recognition system” and U.S. Pat. No. 6,292,575, entitled “Real-time facial recognition and verification system”. The face representation is typically in the form of a vector, which identifies each of the persons in the map.
[0037] The precursor relationship map also includes an indication of whether each person in the map is a male or female, indicated by the letters M and F. This indication may be provided by various sources, such as a social network or by operation of image attribute recognition, which may be entirely conventional, such as described in U.S. Pat. No. 6,990,217 entitled: “Gender classification with support vector machines”. Additional attributes may be generated by image attribute recognition and can be included within the precursor relationship map. These may include complexion, eye color and hair color. Conventional image attribute recognition is known to have accuracy of above 90% in determining gender.
[0038] The precursor relationship map and subsequent relationship maps preferably also include information from visual background analysis.
[0039] Generation of the relationship map employs information from the composite image represented by line drawing 100 , such as that John appears in the composite image together with an unknown individual. Image attribute analysis is preferably applied to the composite image represented by line drawing 100 , in order to determine whether the unknown individual is a male or a female.
[0040] In accordance with a preferred embodiment of the present invention, candidate persons having at least a predetermined relationship with the known person, John, in the composite image are sought. This is preferably done by starting with the generation of a list of candidate persons who have a temporal association with the known person based on visually-sensible information contained in the composite image as well as the non-visually sensible information typically available as meta-data.
[0041] Such non-visually sensible information may include the time and geographical location where a picture was taken and the album on a social network with which it is associated. For example, by interfacing with social network APIs, queries can be made to find persons who appeared in other pictures in the same album, or persons that appeared in other albums taken in the same geographical location at the same time. These persons would typically be on an initial list of candidate persons.
[0042] In accordance with a preferred embodiment of the present invention, the list of candidate persons is extended and further prioritized by analyzing relationships of the persons appearing in the precursor relationship map. In practice, the precursor relationship map may include millions of people. It is a particular feature of the present invention that prioritization of the persons appearing in the precursor relationship map is carried out. This prioritization preferably includes image attribute filtering, which eliminates persons who are of a gender other than the gender of the unknown person in the composite image. For example, referring to diagram 102 , the persons appearing are Mike and Sharon. Image attribute filtering is used to eliminate Sharon, since, image attribute recognition indicates that the unknown person in the composite image represented by line drawing 100 is a male.
[0043] The prioritization preferably relies heavily on the strengths of relationships between the known person and various other persons in the precursor relationship map and gives much higher priority to persons having the strongest relationship with the known person. Thus in the present example, Mike is prioritized over Peter. The prioritization is given expression in operation of the functionality of the present invention preferably by initially performing facial recognition on the images of persons having highest priority. Thus, when the pool of candidates includes millions of people, the prioritization which is a particular feature of the present invention, is of great importance.
[0044] Facial representation generation, which may be entirely conventional, is performed on the unknown person in the composite image represented by line drawing 100 . The resulting facial representation is compared with previously generated facial representations of the candidate persons in accordance with and in the order established by the above-described prioritization. The result of the comparison is a metric depicting the similarity between the two different facial representations. The comparison is cut off and a candidate is selected when a combined priority/similarity threshold is reached for a given candidate person.
[0045] The priority/similarity threshold takes into account the similarity of a facial representation of a candidate person to the facial representation of the unknown person, the priority of that candidate person established by the above-referenced prioritization and a metric which indicates the quality of the facial representation of the candidate person. This metric is a function of various parameters, such as the number of images of that person that have been analyzed by the system and previous user feedback. A preferred quality metric, Qi, is given by the following expression:
[0000]
Qi
=
[
[
1
-
(
1
n
)
2
]
×
q
]
×
[
tp
fp
×
(
1
fn
)
2
]
[0046] where n is the count of images including the face representation, fp is the percent of false positives indicated so far by user feedback, tp is the percent of true positives indicated so far by user feedback, fn is the percent of false negatives indicated so far by user feedback and q is a weighting of variance of the vectors representing the images that compose the face representation.
[0047] The match between the unknown person and the selected candidate person is then employed to provide an initial revised relationship map, indicated by a diagram 104 . In the illustrated example, the unknown person is tentatively identified as Mike and the relationship between Mike and John is initially indicated as being a relatively weak relationship. It is noted that Greg also appears in diagram 104 as having a weak one-directional relationship with John, based on Greg having taken the photograph containing the composite image represented by line drawing 100 .
[0048] If any positive user feedback is received via a social network confirming that the person whose image is believed to be Mike is indeed Mike, this feedback is used to strengthen the relationship between Mike and John as expressed in a subsequent revised relationship map, not shown, and to strengthen the metric which indicates the quality of the facial representation of Mike. Conversely, receipt of negative feedback indicating that the person whose image is believed to be Mike is not Mike weakens the relationship between Mike and John as expressed in a subsequent revised relationship map, not shown, and weakens the metric which indicates the quality of the facial representation of Mike. Additionally it serves as a negative example for future facial representation comparison.
[0049] Reference is now made to FIG. 1B , which is another simplified generalized illustration of relationship mapping functionality employing multi-dimensional context, including facial recognition, operative in accordance with a preferred embodiment of the present invention.
[0050] The functionality may be understood and visualized by starting with a composite image, represented by a line drawing 200 , which includes images of multiple people. In the present example, exemplified by line drawing 200 , three persons here labeled Unknown 1 , Unknown 2 and Unknown 3 , appear. All are not known. In this example, the person who uploaded the picture to the social network site represented by line drawing 200 is known to be the abovementioned John. Identification of the unknown persons preferably employs relationship mapping.
[0051] Generation of a relationship map preferably begins from a pre-existing iterative relationship map, for example a precursor relationship map, represented by a diagram 202 , which is identical to diagram 104 . This precursor relationship map contains information on relationships of a known person or known persons in the previously analyzed composite image, in this case John, Peter, Greg and Sharon. This information is based on the inter-personal relationship data received from one or more social networks as well as inter-personal relationship data derived from the earlier instance of operation of the relationship mapping functionality of the present invention based on analysis of other composite images.
[0052] Diagram 202 indicates that John, a male, is known to have a strong social relationship with Sharon, a female, who in turn has a strong social relationship with Mike, a male. John is also indicated to have weak social relationships with Peter, Greg and Mike, who are males.
[0053] In accordance with a preferred embodiment of the present invention, candidate persons having at least a predetermined relationship with the known person, John, who uploaded the picture represented by line drawing 200 , are sought. This is preferably done by starting with the persons appearing in the precursor relationship map 202 . As noted above, it is a particular feature of the present invention that prioritization of the persons appearing in the precursor relationship map is carried out.
[0054] The prioritization preferably relies heavily on the strength of the relationship between the known person, John, and other persons in the relationship map 202 and gives much higher priority to persons having the strongest relationship with the known person, John. Thus in the present example, John is prioritized above all, as having the strongest relationship to himself. After John, Mike has the next highest priority, since Sharon is eliminated by her gender.
[0055] After Mike, Peter has a higher priority than Greg, notwithstanding that both of their relationship arrows are given the same numerical score, since the relationship between John and Greg is only known to be unidirectional.
[0056] Prioritization preferably is also based on a certainty metric. In this case, the certainty that John is one of the unknown persons in the composite image 200 initially is not particularly high. In view of this, a prioritization cut-off is implemented, such that Peter and Greg, who have relatively weak relationships with John, are not considered to be candidates. As noted above, prioritization is given expression in operation of the functionality of the present invention preferably by initially performing facial recognition on the persons having highest priority, starting with John.
[0057] Facial representation generation is performed on the unknown persons in the composite image represented by line drawing 200 . The resulting facial representation is compared with previously generated facial representations of the candidate persons in accordance with and in the order established by the above-described prioritization.
[0058] For example, facial representation generation is performed on the three unknown images within composite image represented by a line drawing 200 . Thereafter comparison of the facial representations of the three unknown persons is carried out in accordance with the prioritized list generated above. The priority/similarity threshold for each is evaluated, and thus Unknown 1 is recognized as John, Unknown 2 and Unknown 3 are yet to be recognized.
[0059] In accordance with a preferred embodiment of the present invention, following recognition of Unknown 1 as John, in order to recognize the remaining unknown persons in the composite image, an additional prioritization iteration is carried out. In this additional prioritization iteration, the identification of Unknown 1 as John increases the certainty metric for persons known to have a relationship with John and thus Peter is considered to be a candidate. Greg is still typically not considered to be a candidate since his relationship with John is unidirectional. Mike is typically not considered again inasmuch as a previous comparison of Mike with the generated unknown face representation generated a low similarity metric.
[0060] A new priority list includes Peter, based on his relationship with John, who is now known to be previously Unknown 1 in the composite image represented by line drawing 200 .
[0061] Facial representations of the remaining unknown persons in the composite image represented by line drawing 200 are compared with previously generated facial representations of the candidate persons in accordance with and in the order established by the revised prioritization.
[0062] For example, Unknown 2 is recognized as Peter and Unknown 3 is yet to be recognized.
[0063] In accordance with a preferred embodiment of the present invention, following recognition of Unknown 2 as Peter, in order to recognize the last unknown person in the composite image, a further prioritization iteration is carried out. In this further prioritization iteration, the identification of Unknown 2 as Peter indicates that there are two starting points for generation, of candidate lists, John and Peter, both of whom are known to be in the composite image. Two candidate list subsets may thus be provided and used to generate a single prioritized list by using weighted graph combination techniques, as known in the art.
[0064] At this stage a further relationship map is generated, as indicated by reference numeral 204 . In this relationship map, the indicated relationship between John and Peter is strengthened. Relationships between Unknown 3 , John and Peter are also indicated based on the composite image represented by line drawing 200 .
[0065] Unknown 3 may then be recognized in the future by comparing the facial representation of Unknown 3 with facial representations of persons who are subsequently indicated to have relationships with John or with the other persons appear in the relationship map 204 .
[0066] Reference is now made to FIG. 2 , which is simplified functional block diagram of a system for relationship mapping employing multi-dimensional context including facial recognition in accordance with a preferred embodiment of the present invention. As seen in FIG. 2 , the present invention utilizes one or more publicly available social network application program interfaces (APIs) 300 , such as the APIs provided by FACEBOOK®, MYSPACE® AND FLICKR®. Examples of such APIs include the Facebook API, Facebook Connect, Picasa Web Albums Data API and the Flickr Services API.
[0067] The system communicates interactively with the APIs 300 via widgets 302 which may be embedded within applications such as FACEBOOK®, MYSPACE® AND FLICKR®, or standalone applications such as local album indexers 304 . The system automatically receives updates from APIs 300 via crawlers 306 , such as image crawlers, video crawlers and relationship crawlers, such as those used by spammers. Elements 302 , 304 and 306 preferably include user interface functionality. The user interface functionality may be used to provide positive or negative feedback regarding whether a recognized person is indeed the named person. This feedback is communicated to relationship mapping coordination functionality 310 and used to strengthen or weaken the face representation. Additional user interface functionality includes search functionality operative to search the generated relationship map. Search terms include, for example, uniquely identified persons, an additional image of a person, relationships between various persons, other system generated attributes such as gender or facial representation resemblance and any suitable combination of the above. Search functionality can be provided directly via a user interface or indirectly by exposing the relationship mapper 322 information to social networks.
[0068] Standalone applications may include running on an end-user machine and performing some or all of the image attribute analysis, facial representation generation and facial representation comparison. In a preferred embodiment of the present invention, a local album indexer 304 performs image attribute analysis, facial representation generation and facial representation comparison operations, and communicates with the relationship mapping coordination functionality 310 to generate a unified facial representation from multiple images of a single person.
[0069] Relationship mapping coordination functionality is preferably responsive both to API sourced information from APIs 300 and to user inputs received via communicators such as widgets 302 , local album indexers 304 and crawlers 306 and coordinates operation of the various elements of the system which are described hereinbelow.
[0070] The heart of the system of the present invention preferably includes an expectation engine 320 which interfaces with a relationship mapper 322 , which in turn interfaces with a relationship map database 324 . These elements utilize information obtained by functionality 310 from face recognition functionality 326 and attribute analysis functionality 328 via an image analysis engine 330 . Preferably a video analysis engine 332 cooperates with interframe analysis functionality 334 and intraframe analysis functionality 336 , which provide information based on temporal sequences of frames in video content.
[0071] Relationship mapper 322 functionality preferably include providing access to a weighted graph of strengths of the relationships between various uniquely identified persons. Each node in the graph represents a single person and includes a list of unique identifiers that can be one or more of an email address, an internet identifier like OpenID or a list of IDs of specific social networks. In addition, the node preferably contains a facial representation generated from one or more images of the person, his or her gender and other information relating to the person. The relationship map is stored at least partially in memory and is preferably available persistently via relationship database 324 .
[0072] The expectation engine 320 preferably generates prioritized lists of candidate persons, listing persons expected to appear in a composite image, its associated data and social network data. Initially, the expectation engine queries the social networks via APIs 300 for a list of candidate persons having a temporal association with the known person based on visually-sensible information contained in the composite image as well as the non-visually sensible information typically available as meta-data.
[0073] Subsequently, the expectation engine functionality performs prioritization of the candidate persons expected to appear in the composite image by interfacing with relationship mapper 322 and by utilizing image attribute filtering provided by the image analysis engine 330 . The prioritization preferably relies heavily on the strength of relationship between the known person and other persons in the relationship map and gives much higher priority to persons having the strongest relationship with the known person. In a preferred embodiment, the expectation engine combines the weighted graphs associated with known persons in the composite image, as provided by relationship mapper 322 by utilizing weighted graph combination algorithms.
[0074] It will be appreciated by persons skilled in the art that the present invention is not limited to what has been particularly shown and described hereinabove. Rather, the scope of the invention includes both combinations and sub-combinations of various features described hereinabove as well as modifications and variations thereof which would occur to a person skilled in the art upon reading the foregoing description and which are not in the prior art. | A system and method for mapping interpersonal relationships, the method including processing a multiplicity of images and contextual information relating thereto including creating and prioritizing a list of a plurality of candidate persons having at least a predetermined relationship with at least one person connected to at least one image, using multi-dimensional information including visually sensible information in the multiplicity of images and contextual information relating thereto and searching the list of a plurality of candidate persons based at least in part on the prioritizing to select at least one of the candidate persons as having at least a predetermined relationship with the at least one person. | 6 |
This a continuation-in-part of U.S. patent application Ser. No. 413,273 filed on Sept. 27, 1989.
This invention relates to processes and apparatus for removing chemical contaminants from soil and more particularly, in certain embodiments, to processes and apparatus for (1) the removal from soil of volatile organic compounds, (2) continuous and simultaneous remediation of the treated soil and (3) the removal of ground water and suspended or dissolved contaminants. The present invention provides methods and apparatus for the extraction of contaminants which are not subject to limitations due to the depth at which a liquid layer is found in the soil being remediated.
BACKGROUND OF THE INVENTION
Contaminants may exist in subsurface soil in the liquid or vapor phase as discrete substances and mixed with and/or dissolved in ground water and soil gases. Such contaminants may be found and dealt with in accordance with this invention in the vadose (unsaturated) zone found between the surface of the earth and the water table, at the interface between the vadose zone and the water table, and in the saturated zone below the water table.
At many industrial and commercial facilities and at waste handling and disposal sites, soil and ground water are contaminated with suspended or water-soluble chemicals, or both. A variety of techniques have been used for removal of soil contaminants and remediation of affected soil. One common technique involves the excavation and off-site treatment of the soil. Another technique involves saturating the contaminated soil with water in situ, causing the contaminants to be slowly leached from the soil by the water. The contaminated water can then be removed.
Techniques have also been proposed for removing volatile organic contaminants from soil by vacuum extraction. For example, in U.S. Pat. No. 4,323,122, it was proposed that a vacuum be applied in a borehole at the level of the water table, the assumption being that a contaminant such as gasoline, which is lighter than water for example, would float on the water table and present a layer which could be drawn off by vacuum applied to the liquid at or around that level.
Others have suggested the possibility of venting soil above the water table (i.e., in the vadose zone) to cause vaporization of the contaminant in the soil, and then drawing off the contaminant in the vapor phase. Thus, conventional vacuum extraction systems are designed to clean the vadose zone by applying vacuum to draw air through the soil through wells having screening which does not extend below the water table. Ground water requiring treatment is in such processes conventionally removed by pumping from separate conventional water wells. In situations in which water does flow into vacuum extraction wells, it has been suggested that a second, liquid phase pump be placed either in the well or at the surface to remove the water through a second conduit. Thus, conventionally, water wells separate and apart from vacuum extraction wells may be required at a given site, and water pumps in addition to vacuum generation devices may be employed. Such extraction systems are therefore referred to as single phase extraction systems since contaminants are extracted in separate, single phases.
Processes and apparatus for two phase extraction of contaminants from the soil, in which contaminants are typically present in the vadose zone and below the water table have also been proposed. In accordance with the invention disclosed in U.S. patent application Ser. No. 413,237, filed on Sept. 27, 1989, a two phase vacuum extraction system, wherein a single vacuum device removes contaminants in both the liquid and vapor phase by way of a single conduit formed by the well casing can effectively remediate a site. The process disclosed involves the steps of providing a borehole in the contaminated area; placing a riser pipe in the borehole, the riser pipe preferably being constructed so as to admit fluids both from the vadose zone and from below the natural water table; applying a vacuum to the riser pipe so as to draw soil gases and entrained liquid into the riser pipe and to transport both the gases and the liquid to the surface; separating the liquid and the gases, and separately subjecting the separated liquid and gases to appropriate treatment. Treated water may be returned to the soil or disposed of in conventional ways. In one embodiment of this invention, the well casing is constructed with perforations (screening) extending below the natural water table and also upward into the unsaturated (vadose) zone. The unsaturated zone may be the natural vadose zone lying above the natural water table, or an expanded "artificial" vadose zone created when removal of the ground water through the extraction well causes local lowering of the water table. Placing of the screening so that it extends into the vadose zone allows soil gases, including contaminants in the vapor phase, to be drawn into the well under the influence of a vacuum generator. The gases, it has been found, entrain the liquid phase, so that both phases may be transported to the surface together in a common stream. At the surface, the two phases are separated in a vapor-liquid disengaging vessel, such as a cyclone separator, knock-out pot or other suitable component, and after separation the phases may individually be routed to systems for contaminant removal by further treatment steps. Suitable processes for contaminant removal include filtration, adsorption, air stripping, settling, flocculation, precipitation, scrubbing and the like.
As an alternative, to the above described process, U.S. patent application Ser. No. 413,273, filed on Sept. 27, 1989 also discloses a treatment well constructed so that screening is at all times is below the water table, even in the situation in which removal of water causes local depression of the water table. In such an arrangement, the fluid transported to the surface would predominantly be in the liquid phase, although it may still be necessary to provide vapor-liquid separation and individual phase treatment at the surface to deal with phase transformation which may occur as a result of turbulence and pressure reduction at the suction side of the vacuum device.
Two phase vacuum extraction in accordance with U.S. patent application Ser. No. 413,273, filed on Sept. 27, 1989 is an improvement over known soil and ground water remediation vacuum extraction techniques which simplifies equipment requirements and increases the rate of recovery of ground water. Unlike the prior art, water wells and pumps distinct from the extraction well are not required. A single vacuum device serves to remove contaminants in both the vapor and liquid phases, using a single conduit. However, a severe practical limitation to the system disclosed by U.S. patent application Ser. No. 413,273, filed on Sept. 27, 1989 exists in that, at best, a conventional vacuum pump can create a negative pressure of about one atmosphere (760 torr). Relating this fact to the hydrodynamic head of the well, one of ordinary skill will realize that when the riser pipe extends into liquid and the length of the riser pipe exceeds about thirty (30) feet, the vacuum pump will not withdraw soil gases and entrained liquid, since it will be unable to lift a column of liquid above to the soil surface. Therefore, at present, two phase extraction cannot be undertaken at sites where the surface of the water or liquid in the borehole is greater than about thirty feet beneath the soil surface. For similar reasons, in certain single phase extraction systems, the presence of a liquid layer makes the use of a single vacuum extraction system highly impractical.
SUMMARY OF THE INVENTION
It has now been found, however, that two phase extraction can be accomplished in wells of nearly any depth having water or other liquid therein where the liquid surface is at a level greater than thirty feet beneath the soil surface or using existing wells having screening below the water table at practically any depth. The present invention provides methods and apparatus which introduce a quantity of air or other gas into the liquid within the borehole via a priming tube, and thereby disperse the liquid into droplets which may be carried up the riser pipe by the effect of the vacuum pump.
The present invention provides apparatus for extracting materials from a borehole or the like having a liquid layer therein which comprises a riser pipe disposed within the borehole and extending at least partially into the liquid layer within the borehole. The borehole itself or other excavation such as a trench may be oriented in the vertical, horizontal or any direction. A vacuum source for extracting materials is connected to the riser pipe means. A priming tube for admitting a quantity of gas into the borehole is provided which extends at least partially into the liquid layer within the borehole. In operation, the vacuum source means creates a negative pressure within the riser pipe and the priming tube admits a quantity of gas into the liquid, thereby causing the liquid to be dispersed into droplets and extracted. In a preferred embodiment of the present invention, a priming valve means for controlling the quantity of gas admitted into the liquid via the priming tube is provided. In certain embodiments an air compressor or a source of gas is connected to the priming valve means. Most preferably, the priming tube is disposed substantially coaxially within the riser pipe, and the riser pipe is connected to the vacuum source by a fitting comprising at least three branches, most preferably a "tee" fitting. The priming valve is also preferably connected to the fitting and the priming tube is disposed within the fitting and connected to the priming valve. In certain embodiments, the priming valve is a regulating valve and the priming tube may be comprised of a flexible material. The apparatus of the present invention is operable either using a vacuum source which forms part of a single phase extraction system for removing contaminants or a two phase extraction system. In either a two phase or a single phase extraction system, the present invention permits the withdrawal of liquids or gases using vacuum extraction in cases where the riser pipe extends into a liquid layer which lies beneath the soil surface.
The present invention also provides methods of extracting materials from a borehole or the like having a liquid layer therein comprising the steps of placing a riser pipe means within the borehole and extending the riser pipe at least partially into the liquid layer within the borehole. The riser pipe is then connected to a vacuum source for extracting materials. By providing a priming tube for admitting a quantity of gas into the borehole and extending the priming tube means at least partially into the liquid layer within the borehole, extraction is facilitated when the vacuum source means is operated to create a negative pressure within the riser pipe. In this instance, the priming tube admits a quantity of gas into the liquid, thereby causing the liquid to be dispersed into droplets and extracted.
The methods of the present invention are applicable to methods wherein the vacuum source means is operated to extract materials in a single phase process as well as to those processes wherein the vacuum source means is operated to extract materials in a two phase process.
BRIEF DESCRIPTION OF THE DRAWINGS
There is seen in the drawings a form of the invention which is presently preferred, but it should be understood that the invention is not limited to the precise arrangements and instrumentalities illustrated.
FIG. 1 is a side elevation view, in cross-section, illustrating somewhat schematically an arrangement for two phase vacuum extraction for removal of contaminants from a contaminated area of the ground.
FIG. 2 is cross-sectional view, in side elevation, of an extraction well which may be used with the apparatus of FIG. 1.
FIG. 3 is a cross-sectional view, also in side elevation, of a primed two phase air inlet well intended for use in a two phase extraction system.
FIG. 4 is a cross-sectional view, in side elevation, of a primed two phase extraction well made in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, there is seen schematically a system, designated generally by the reference numeral 10, for two phase vacuum extraction and treatment substantially in accordance with the invention disclosed in U.S. patent application Ser. No. 413,273, filed on Sept. 27, 1989. Seen in FIG. 1 is a source 12 of volatile contaminants, creating a plume 14 of absorbed or suspended contaminants in the soil 16 of the vadose (unsaturated) zone. The contaminants making up the plume 14 tend to leach or percolate downwardly toward the natural water table 18. Components lighter than water and not dissolved are depicted by the reference numeral 20, and tend to float at the top of the water table. Dissolved contaminants and free-phase contaminants heavier than water tend to migrate downwardly in a plume 22 below the water table 18. Free-phase components 24 heavier than water may tend to be pooled at the aquitard 26.
An extraction well 28, which will be described in greater detail below, is sunk in the area of the plume 14 and extends through the vadose zone and below the natural water table 18. Spaced from the extraction well 25 are air inlet wells 30, and which will also be described in greater detail. Air inlet wells 30, it will be understood, are best disposed at spaced locations around the perimeter of the plume 14. Those skilled in the art will appreciate that the number and spacing of the air inlet wells 30 with respect to the plume 14 and extraction well 28 will depend upon the size of the plume 14, as well as the composition and permeability of the soil to be treated.
As indicated above, the present invention overcomes a limitation of the process illustrated in FIG. 1 in that it was previously unlikely to be effectively operable if the depth of the liquids in the well 28, either at the water table or floating on the water, exceeded about thirty feet. As shown in greater detail below, a priming tube 200 is provided which extends into the liquid at the bottom of the well. This tube 200 mixes air or other gas with the liquid and thus "primes" the two phase extraction system. In the context of the present invention, the term "priming" of an extraction system is defined as introducing sufficient gas into a liquid to enable the vacuum supplied by a vacuum extraction system 32 to withdraw a stream of liquid particles dispersed in the gas column above the surface of the liquid out of the well. The vacuum extraction system 32 may either be single phase or two phase. A valve 210 is preferably provided at the top of the priming tube 200 which permits the selective admission of air or other gas. As shown in phantom, in certain embodiments, apparatus 220 such as an air compressor or a source of gas other than air is also provided to facilitate the two phase extraction process.
Connected to the extraction well 28 is a vacuum extraction system 32. Gases removed by the vacuum extraction system 32 may be vented to atmosphere 34 if within acceptable environmental limits, or further processed such as by being incinerated or passed to a condenser, granular activated carbon filter, or other such component 36. The component 36 serves to remove contaminants from the extracted gases. Water extracted by the process may be treated by passing it through conventional systems for metals removal, volatile organic compound removal, or other steps of purification. The treated and purified water, if it is of sufficient purity at this stage, may be returned to a sewer or directly to the ground as indicated at 38. Contaminants may be stored in drums 40 for eventual destruction or further processing.
Referring now to FIG. 2, the extraction well 28 will be described in greater detail. The extraction well 28 in a preferred embodiment of the invention includes an elongated borehole 42, into which there is placed a riser pipe 44. The riser pipe 44 preferably includes an imperforate upper portion 46 and a perforate (screened) lower portion 48. In one operative example, the riser pipe 44 is of four inch diameter PVC pipe, capped at the bottom, and the screen is formed by a plurality of 0.010 inch slots. In the operative example of U.S. patent application Ser. No. 413,237 filed on Sept. 27, 1989, the riser pipe 44 was approximately twenty feet in length, with the lower fifteen feet comprising the slotted lower portion 48 and the upper five feet the imperforate upper portion 46. However, the riser pipe 44 used in the present invention may be any length and will most preferably include pipes having a length greater than thirty feet.
The imperforate upper portion of the riser pipe 46 is here shown to be associated with a concrete floor or deck, however, the system of the present invention may be constructed independently of such a floor or deck, e.g., in an outdoor setting. The imperforate end of the riser pipe 46 is provided with a suitable pipe fitting 52, enabling the riser pipe 44 to be coupled in fluid communication to the remainder of the vacuum extraction system 32 (not seen in FIG. 2) by a connecting pipe 86. The upper portion 46 of the riser pipe 44 is surrounded by a low permeability non-shrink grout 54 and by a seal 56. The area within the borehole 42 surrounding the slotted or screened lower portion 48 of the riser pipe 44 and part of the imperforate upper portion 46 above the screened or slotted lower portion 48 is packed with fine screened sand 74 or other permeable material such as gravel, to facilitate the flow of gas and liquid from the surrounding soil into the riser pipe 44 while preventing the collapse of the borehole walls. In a preferred embodiment, the extraction well 28 is constructed so that the screened lower portion 48 extends below the natural water table 18 and upwardly into the vadose zone. The vadose zone into which the screened lower portion 48 extends may be above the natural water table 18, or may be above the expanded artificial vadose zone created when prolonged removal of ground water through the extraction well causes local lowering of the water table as indicated by the reference numeral 18' in FIG. 2.
The priming tube 200 for introducing air or gas into the liquid at the bottom of the well is also shown in FIG. 2. Preferably, the priming tube 200 is provided with a valve 210 which permits the selective addition of air into the tube 200 and thus into the liquid at the lower end of the well. The valve 210 may be a simple on/off valve or may be capable of regulating the volume of air or other gas admitted to the priming tube 200. As will be explained in greater detail below, the priming valve 210 is attached to the end of the priming tube 200 which may be moved relative to the riser pipe 44. Thus, the priming tube is attached to the top of the well head in a manner which permits its insertion to a sufficient depth and also comprises means for retaining the priming tube at the selected depth. As indicated above, in certain embodiments, the priming tube 200 may be supplied with pressurized air or other pressurized gas, supplied by appropriate means 220 shown schematically in phantom in FIG. 2. Placement of the screened lower portion 48 of the riser pipe 44 as indicated allows soil gases (the vapor phase) to be drawn into the well under the influence of vacuum created by the extraction system 32 and to entrain the liquid phase so that both phases may be transported to the surface together. The introduction of air or other gases into the liquid at the bottom of the well by the priming tube 210 ensures entrainment even when the depth of the water table 18 exceeds about thirty feet, and generally tends to aid in the extraction at all depths regardless of where the screened interval begins and ends. The methods and apparatus of the present invention may be applied to nearly any existing well of borehole, no matter how constructed.
Alternatively, the extraction well 28 may be so constructed that the screening of the lower portion 48 is entirely submerged, i.e., disposed below the natural or actual water table, even after withdrawal of water from the aquifer under the influence of the vacuum extraction system 32. In the latter case, the fluid transported to the surface would be predominantly in the liquid phase if the system described in U.S. patent application Ser. No. 413,273 filed on Sept. 27, 1989 were utilized. However, the priming tube 100 provided by the present invention would again introduce air or other gas into the liquid and facilitate extraction in a two phase flow regime in those instances where the vacuum extraction system was unable to lift the liquid from the well.
Referring now to FIG. 3, there is seen an example of an air inlet well 30. The air inlet well 30 comprises a borehole 58, which receives a pipe 60. The pipe 60 in one operative embodiment comprises a four inch diameter PVC pipe, capped at the bottom, and having a screen of 0.010 inch slots. The pipe 60 is surrounded at its upper end by a cement collar 62, extending to the ground surface 64. Suitable caps 66 and covers 68 may be provided in association with the collar 62 to selectively cap or cover the injection well as desired. Surrounding a medial portion 70 of the pipe 60 within the borehole 58 is a non-shrink grout 72, which provides a gas-tight seal between the pipe 60 and the borehole 58. The slotted lower portion 74 of the pipe 60 is surrounded by gas-permeable packed sand 76. As will now be apparent, the pipe 60 facilitates the injection or admission of air into the zone surrounding the plume 14.
Further details of the priming tube 200 and associated priming valve 210 are shown in FIG. 4. As explained above, the present invention is preferably used in a conjunction with a borehole 42 having one or more portions of gas permeable packed sand or gravel 76 disposed therein. Disposed within the borehole is a riser pipe 44, which extends, in some applications, beneath the water table and thus terminates within a quantity of liquid. The priming tube 200 is preferably disposed within the riser pipe 44 and is of sufficient length to extend below the liquid surface. Near the soil surface, the riser pipe 44 is terminated by a pipe fitting 52, which is preferably further attached to a "tee" fitting 253. A pipe 86 connects one branch of the tee fitting to the vacuum extraction apparatus. The second branch of the tee fitting 253 is terminated by a cap or flange or bushing. The priming tube 200 is connected to the priming valve 210 and is disposed within the tee fitting 253, passing therethrough and into the interior of the riser pipe 44. As previously noted, the valve 210 may either draw ambient air or be connected to apparatus such as an air compressor or source of pressurized gas other than air (not shown in this view). The priming tube 200 is preferably affixed to the priming valve 210 through a nipple inside the cap or flange, or passes through an aperture in the cap or flange. The aperture may be adjustable by means of a clamp 263 and also provided with a seal such as a gasket or skirt which may be formed, for example, from a section of rubber tubing.
As will be readily understood by those of ordinary skill, the seal and clamp arrangement 263 may be provided to permit the depth of insertion of the priming tube 200 to be varied so that its lower open end is at an adequate depth below the surface of the liquid, thereby permitting the vacuum applied to overcome the liquid head above the lower end of the riser pipe 44 and inducing the inflow of air or gas and the subsequent establishment of a two phase flow regime. Alternatively, the priming valve 210 may be attached to a nipple disposed on the outside of the cap or flange aperture through which it communicates with the priming tube 200. Most preferably, however, the priming tube 200 will pass through a cap means by way of an aperture formed in the cap. The cap may comprise a bushing or flange, which cooperate with the clamp 263. Most preferably, the aperture will be adjustable so as to constrict around the priming tube. The aperture is thus capable of forming a seal, most preferably by providing a gasket or skirt which is adjustable using the clamp 263. Also, the constricting aperture functions to retain the priming tube 200 at the selected depth and permits it to be moved relative to the riser pipe 44 and to be secured in a particular location. The preferred apparatus described thus prevents air or gas leakage and allows adjustment of the depth of insertion of the priming tube 200 below the liquid surface.
Those of ordinary skill will also recognize that the construction illustrated represents one of many ways in which air or gas may be provided to the bottom of the well, numerous other methods and apparatus may be readily devised to accomplish the same goal. The embodiment depicted is preferred, however, since the use of a tee fitting 253 provides a convenient manner by which the riser pipe 44 may be connected to the vacuum extraction source 32 while permitting the priming tube 200 to be both disposed within the riser pipe 44 and connected to the priming valve 210 in a manner which also facilitates the incorporation of a clamp 263 which allows the depth to which the priming tube 200 extends to be adjusted.
Although the embodiments of the present invention described above are typically directed to remedial processes whereby volatile and other contaminants are removed from a contaminated zone of soil or from the aquifer, those of ordinary skill will realize that numerous other situations present themselves which make two phase material transfer a desireable process. For example, the present invention may be used to enhance the production of water from a low-yielding aquifer. Similarly, the production of low yielding oil wells can also be enhanced by a primed two phase extraction process.
Additionally, the two phases extracted by the present invention do not have to be liquid and gas. In certain clean up operations, such as the emptying of grain silos or ship holds used to transport grains or granular materials such as sand the present invention may be utilized to more efficiently empty such vessels. The priming tube would entrain the granular material in the air inside the tank or hold and permit it to be more effectively extracted by a vacuum system. Similarly, applications wherein the two "phases" are comprised of liquids having different specific gravities are also contemplated. For example, using the present invention, the efficient extraction of contaminants or liquid materials which are underwater, e.g., under the bed of the ocean or beneath an aquifer which rests on an aquitard, and which are heavier than water can now be achieved. The priming tube would again break up of entrain the heavier than water materials and permit them to be extracted.
Thus, the present invention may be embodied in many other specific forms without departing from its spirit and essential attributes. Accordingly, reference should be made to the appended claims rather than the foregoing specification as indicating the scope of the invention. | Methods and apparatus for vacuum extraction of contaminants from the ground which, in a preferred embodiment, involves vacuum withdrawal of liquid and gaseous phases as a common stream, separation of the liquid and gaseous phases, and subsequent treatment of the separated liquid and gases to produce clean effluent. A primed vacuum extraction employs a single vacuum generating device to remove contaminants in both the liquid stream and soil gases through a single well casing utilizing a priming tube which introduces air or other gas to the liquid collected at the bottom of a well. The present invention permits vacuum extraction of both liquids and gases from the subsurface by way of wells having a liquid layer which is more than thirty feet below the soil surface or in which a screened interval of the extraction pipe is entirely below the liquid surface. | 4 |
BACKGROUND OF THE INVENTION
[0001] Peroxisome Proliferator Activated Receptors (PPARs) are members of the nuclear hormone receptor superfamily, a large and diverse group of proteins that mediate ligand-dependent transcriptional activation and repression. Three subtypes of PPARs have been isolated: PPARα, PPARγ and PPARδ.
[0002] The expression profile of each isoform differs significantly from the others, whereby PPARα is expressed primarily, but not exclusively in liver; PPARγ is expressed primarily in adipose tissue; and PPARδ is expressed ubiquitously. Studies of the individual PPAR isoforms and ligands have revealed their regulation of processes involved in insulin resistance and diabetes, as well as lipid disorders, such as hyperlipidemia and dyslipidernia. PPARγ agonists, such as pioglitazone, can be useful in the treatment of non-insulin dependent diabetes mellitus. Such PPARγ agonists are associated with insulin sensitization.
[0003] PPARα agonists, such as fenofibrate, can be useful in the treatment of hyperlipidemia. Although clinical evidence is not available to reveal the utility of PPARδ agonists n humans, several preclinical studies suggest that PPARδ agonists can be useful in the treatment of diabetes and lipid disorders.
[0004] The prevalence of the conditions that comprise Metabolic Syndrome (obesity, insulin resistance, hyperlipidemia, hypertension and atherosclerosis) continues to increase. New pharmaceutical agents are needed to address the unmet clinical needs of patients.
[0005] PPARδ agonists have been suggested as a potential treatment for use in regulating many of the parameters associated with Metabolic Syndrome and Atherosclerosis. For example, in obese, non-diabetic rhesus monkeys, a PPARδ agonist reduced circulating triglycerides and LDL, decreased basal insulin levels and increased HDL (Oliver, W. R. et al. Proc Natl Acad Sci 98:5306-5311; 2001). The insulin sensitization observed with the use of a PPARδ agonist is thought to be in part due to decreased myocellular lipids (Dressel, U. et al. Mol Endocrinol 17:2477-2493; 2003).
[0006] Further, atherosclerosis is considered to be a disease consequence of dyslipidemia and may be associated with inflammatory disease. C-reactive protein (CRP) production is part of the acute-phase response to most forms of inflammation, infection and tissue damage. It is measured diagnostically as a marker of low-grade inflammation. Plasma CRP levels of greater than 3 mg/L have been considered predictive of high risk for coronary artery disease (J. Clin. Invest 111: 1085-1812, 2003).
[0007] PPARδ agonists are believed to mediate anti-inflammatory effects. Indeed, treatment of LPS-stimulated macrophages with a PPARδ agonist has been observed to reduce the expression of iNOS, IL-12, and IL-6 (Welch, J. S. et al. Proc Natl Acad Sci 100:6712-67172003).
[0008] It may be especially desirable when the active pharmaceutical agent selectively modulates a PPAR receptor subtype to provide an especially desirable pharmacological profile. In some instances, it can be desirable when the active pharmacological agent selectively modulates more than one PPAR receptor subtype to provide a desired pharmacological profile.
SUMMARY OF THE INVENTION
[0009] The present invention is directed to compounds represented by the following structural Formula I:
[0010] and stereoisomers, pharmaceutically acceptable salts, solvates and hydrates thereof, wherein:
(a) R1 is selected from the group consisting of hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkenyl, C 1 -C 8 heteroalkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C 3 -C 6 cycloalkylaryl-C 0-2 -alkyl, and, wherein C 1 -C 8 alkyl, C 1 -C 8 alkenyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, C 3 -C 6 cycloalkylaryl-C 0-2 -alkyl are each optionally substituted with from one to three substituents independently selected from R1′; (b) R1′, R26, R27, R28 and R31 are each independently selected from the group consisting of hydrogen, hydroxy, cyano, nitro, halo, oxo, C 1 -C 6 alkyl, C 1 -C 6 alkyl-COOR12, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkyloxy, C 3 -C 7 cycloalkyl, aryloxy, aryl-C 0-4 -alkyl, heteroaryl, heterocycloalkyl, C(O)R13, COOR14, OC(O)R15, OS(O) 2 R16, N(R17) 2 , NR18C(O)R19, NR20SO 2 R21, SR22, S(O)R23, S(O) 2 R24, and S(O) 2 N(R25) 2 ; R12, R13, R14, R15, R16, R17, R18, R19, R20, R2, R22, R23, R24 and R25 are each independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl and aryl; (c) V is selected from the group consisting of C 0 -C 8 alkyl and C 1-4 -heteroalkyl; (d) X is selected from the group consisting of a single bond, O, S, S(O) 2 and N; (e) U is an aliphatic linker wherein one carbon atom of the aliphatic linker is optionally replaced with O, NH or S, and wherein such aliphatic linker is optionally substituted with from one to four substituents each independently selected from R30; (f) W is N, O or S; (g) Y is selected from the group consisting of C, O, S, NH, and a single bond; (h) E is C(R3)(R4)A or A and wherein
(i) A is selected from the group consisting of carboxyl, tetrazole, C 1 -C 6 alkylnitrile, carboxamide, sulfonamide and acylsulfonamide; wherein sulfonamide, acylsulfonamide and tetrazole are each optionally substituted with from one to two groups independently selected from R 7 ; (ii) each R 7 is independently selected from the group consisting of hydrogen, C 1 -C 6 haloalkyl, aryl C 0 -C 4 alkyl and C 1 -C 6 alkyl; (iii) R3 is selected from the group consisting of hydrogen, C 1 -C 5 alkyl, and C 1 -C 5 alkoxy; and (iv) R4 is selected from the group consisting of H, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, aryloxy, C 3 -C 6 cycloalkyl, and aryl C 0 -C 4 alkyl, and R3 and R4 are optionally combined to form a C 3 -C 4 cycloalkyl, and wherein alkyl, alkoxy, aryloxy, cycloalkyl and aryl-alkyl are each optionally substituted with from one to three substituents each independently selected from R26;
(i) R8 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylenyl, and halo; (j) R9 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylenyl, halo, aryl-C 0 -C 4 alkyl, heteroaryl, C 1 -C 6 allyl, and OR29, and wherein aryl-C 0 -C 4 alkyl, heteroaryl are each optionally substituted with from one to three independently selected from R27; R29 is selected from the group consisting of hydrogen and C 1 -C 4 alkyl; (k) R10, R11 are each independently selected from the group consisting of hydrogen, hydroxy, cyano, nitro, halo, oxo, C 1 -C 6 alkyl, C 1 -C 6 alkylenyl, C 1 -C 6 alkyl-COOR12″, C 0 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkyloxy, C 3 -C 7 cycloalkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, C3-C6 cycloalkylaryl-C 0-2 -alkyl, aryloxy, C(O)R13′, COOR14′, OC(O)R15′, OS(O) 2 R16′, N(R17′) 2 , NR18′C(O)R19′, NR20′SO 2 R21′, SR22′, S(O)R23′, S(O) 2 R24′, and S(O) 2 N(R25′) 2 ; and wherein aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -alkyl are each optionally substituted with from one to three independently selected from R28; and wherein R10 and R11 optionally combine to form a 5 to 6 membered fused bicyclic ring with the phenyl to which they are bound; (l) R12′, R12″, R13′, R14′, R15′, R16′, R17′, R18′, R19′, R20′, R21′, R22′, R23′, R24′, and R25′ are each independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl and aryl; (m) R30 is selected from the group consisting of C 1 -C 6 alkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -alkyl, and wherein C 1 -C 6 alkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -alkyl are each optionally substituted with from one to three substituents each independently selected from R31; (n) R32 is selected from the group consisting of a hydrogen, halo, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, and C 1 -C 6 alkyloxo; and (o) ---- is optionally a bond to form a double bond at the indicated position.
[0030] A further embodiment of the present invention is a compound of the Formula Ia:
[0031] A further embodiment of the present invention is a compound of the Formula Ib:
wherein W 1 is O or S.
[0032] A further embodiment of the present invention is a compound of the Formula Ic:
[0033] A further embodiment of the present invention is a compound of the Formula II:
[0034] and stereoisomers, pharmaceutically acceptable salts, solvates and hydrates thereof, wherein:
(a) R1 is selected from the group consisting of hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkenyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -alkyl, and, wherein C 1 -C 8 alkyl, C 1 -C 8 alkenyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, C3-C6 cycloalkylaryl-C 0-2 -alkyl are each optionally substituted with from one to three substituents independently selected from R1′; (b) R1′, R26, R27, R28 and R31 are each independently selected from the group consisting of hydrogen, hydroxy, cyano, nitro, halo, oxo, C 1 -C 6 alkyl, C 1 -C 6 alkyl-COOR12, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkyloxy, C 3 -C 7 cycloalkyl, aryloxy, aryl-C 0-4 -alkyl, heteroaryl, heterocycloalkyl, C(O)R13, COOR14, OC(O)R15, OS(O) 2 R16, N(R17) 2 , NR18C(O)R19, NR20SO 2 R21, SR22, S(O)R23, S(O) 2 R24, and S(O) 2 N(R25) 2 ; R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25 are each independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl and aryl; (c) V is selected from the group consisting of C 0 -C 8 alkyl and C 1-4 -heteroalkyl; (d) X is selected from the group consisting of a single bond, O, S, S(O) 2 and N; (e) U is an aliphatic linker wherein one carbon atom of the aliphatic linker is optionally replaced with O, NH or S, and wherein such aliphatic linker is substituted with from one to four substituents each independently selected from R30; (f) Y is selected from the group consisting of C, O, S, NH and a single bond; (g) E is C(R3)(R4)A or A and wherein
(i) A is selected from the group consisting of carboxyl, tetrazole, C 1 -C 6 alkylnitrile, carboxamide, sulfonamide and acylsulfonamide; wherein sulfonamide, acylsulfonamide and tetrazole are each optionally substituted with from one to two groups independently selected from R 7 ; (II) each R 7 is independently selected from the group consisting of hydrogen, C 1 -C 6 haloalkyl, aryl C 0 -C 4 alkyl and C 1 -C 6 alkyl; (iii) R3 is selected from the group consisting of hydrogen, C 1 -C 5 alkyl, and C 1 -C 5 alkoxy; and (iv) R4 is selected from the group consisting of H, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, aryloxy, C 3 -C 6 cycloalkyl, and aryl C 0 -C 4 alkyl, and R3 and R4 are optionally combined to form a C 3 -C 4 cycloalkyl, and wherein alkyl, alkoxy, aryloxy, cycloalkyl and aryl-alkyl are each optionally substituted with from one to three substituents each independently selected from R26;
(h) R8 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylenyl, and halo; (i) R9 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylenyl, halo, aryl-C 0 -C 4 alkyl, heteroaryl, C 1 -C 6 allyl, and OR29, and wherein aryl-C 0 -C 4 alkyl, heteroaryl are each optionally substituted with from one to three independently selected from R27; R29 is selected from the group consisting of hydrogen and C 1 -C 4 alkyl; (j) R10, R11 are each independently selected from the group consisting of hydrogen, hydroxy, cyano, nitro, halo, oxo, C 1 -C 6 alkyl, C 1 -C 6 alkylenyl, C 1 -C 6 alkyl-COOR12″, C 0 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkyloxy, C 3 -C 7 cycloalkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, C3-C6 cycloalkylaryl-C 0-2 -alkyl, aryloxy, C(O)R13′, COOR14′, OC(O)R15′, OS(O) 2 R16′, N(R17′) 2 , NR18′C(O)R19′, NR20′SO 2 R21′, SR22′, S(O)R23′, S(O) 2 R24′, and S(O) 2 N(R25′) 2 ; and wherein aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -alkyl are each optionally substituted with from one to three independently selected from R28; and wherein R10 and R11 optionally combine to form a 5 to 6 membered fused bicyclic ring with the phenyl to which they are bound; (k) R12′, R12″, R13′, R14′, R15′, R16′, R17′, R18′, R19′, R20′, R21′, R22′, R23′, R24′, and R25′ are each independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl and aryl; (l) R30 is selected from the group consisting of C 1 -C 6 alkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -alkyl, and wherein C 1 -C 6 alkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -alkyl are each optionally substituted with from one to three substituents each independently selected from R31; (m) R32 is selected from the group consisting of a bond, hydrogen, halo, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, and C 1 -C 6 alkyloxo; and (n) ---- is optionally a bond to form a double bond at the indicated position.
[0053] Another embodiment of the present invention is a compound of the Formula III:
[0054] and stereoisomers, pharmaceutically acceptable salts, solvates and hydrates thereof, wherein:
(a) R1 is selected from the group consisting of hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkenyl, C 1 -C 8 heteroalkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -akyl, and, wherein C 1 -C 8 alkyl, C 1 -C 8 alkenyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, C3-C6 cycloalkylaryl-C 0-2 -alkyl are each optionally substituted with from one to three substituents independently selected from R1′; (b) R1′, R26, R27, R28 and R31 are each independently selected from the group consisting of hydrogen, hydroxy, cyano, nitro, halo, oxo, C 1 -C 6 alkyl, C 1 -C 6 alkyl-COOR12, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkyloxy, C 3 -C 7 cycloalkyl, aryloxy, aryl-C 0-4 -alkyl, heteroaryl, heterocycloalkyl, C(O)R13, COOR14, OC(O)R15, OS(O) 2 R16, N(R17) 2 , NR18C(O)R19, NR20SO 2 R21, SR22, S(O)R23, S(O) 2 R24, and S(O) 2 N(R25) 2 ; R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25 are each independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl and aryl; (c) V is selected from the group consisting of C 0 -C 8 alkyl and C 1-4 -heteroalkyl; (d) X is selected from the group consisting of a single bond, O, S, S(O) 2 and N; (e) U is an aliphatic linker wherein one carbon atom of the aliphatic linker is optionally replaced with O, NH or S, and wherein such aliphatic linker is optionally substituted with from one to four substituents each independently selected from R30; (f) Y is selected from the group consisting of O, S, NH, C, and a single bond; (g) E is C(R3)(R4)A; wherein
(i) A is selected from the group consisting of carboxyl, tetrazole, C 1 -C 6 alkylnitrile, carboxamide, sulfonamide and acylsulfonamide; wherein sulfonamide, acylsulfonamide and tetrazole are each optionally substituted with from one to two groups independently selected from R 7 ; (II) each R 7 is independently selected from the group consisting of hydrogen, C 1 -C 6 haloalkyl, aryl C 0 -C 4 alkyl and C 1 -C 6 alkyl; (iii) R3 is selected from the group consisting of C 1 -C 5 alkyl, and C 1 -C 5 alkoxy; and (iv) R4 is selected from the group consisting of H, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, aryloxy, C 3 -C 6 cycloalkyl, and aryl C 0 -C 4 alkyl, and R3 and R4 are optionally combined to form a C 3 -C 4 cycloalkyl, and wherein alkyl, alkoxy, aryloxy, cycloalkyl and aryl-alkyl are each optionally substituted with from one to three substituents each independently selected from R26;
with the proviso that when Y is O then R4 is selected from the group consisting of C 1 -C 5 alkyl, C 1 -C 5 alkoxy, aryloxy, C 3 -C 6 cycloalkyl, and aryl C 0 -C 4 alkyl, and R3 and R4 are optionally combined to form a C 3 -C 4 cycloalkyl, and wherein alkyl, alkoxy, cycloalkyl and aryl-alkyl are each optionally substituted with one to three each independently selected from R26;
(h) R8 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylenyl, and halo; (i) R9 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylenyl, halo, aryl-C 0 -C 4 alkyl, heteroaryl, C 1 -C 6 allyl, and OR29, and wherein aryl-C 0 -C 4 alkyl, heteroaryl are each optionally substituted with from one to three independently selected from R27; R29 is selected from the group consisting of hydrogen and C 1 -C 4 alkyl; (j) R10, R11 are each independently selected from the group consisting of hydrogen, hydroxy, cyano, nitro, halo, oxo, C 1 -C 6 alkyl, C 1 -C 6 alkylenyl, C l -C 6 alkyl-COOR12″, C 0 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkyloxy, C 3 -C 7 cycloalkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, C3-C6 cycloalkylaryl-C 0-2 -alkyl, aryloxy, C(O)R13′, COOR14′, OC(O)R15′, OS(O) 2 R16′, N(R17′) 2 , NR18′C(O)R19′, NR20′SO 2 R21′, SR22′, S(O)R23′, S(O) 2 R24′, and S(O) 2 N(R25′) 2 ; and wherein aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -alkyl are each optionally substituted with from one to three independently selected from R28; and wherein R10 and R11 optionally combine to form a 5 to 6 membered fused bicyclic ring with the phenyl to which they are bound; (k) R12′, R12″, R13′, R14′, R15′, R16′, R17′, R18′, R19′, R20′, R21′, R22′, R23′, R24′, and R25′ are each independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl and aryl; (l) R30 is selected from the group consisting of C 1 -C 6 alkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -alkyl, and wherein C 1 -C 6 alkyl, aryl-C 0-4 -alkyl, aryl-C 1-4 -heteroalkyl, heteroaryl-C 0-4 -alkyl, and C3-C6 cycloalkylaryl-C 0-2 -alkyl are each optionally substituted with from one to three substituents each independently selected from R31; (m) R32 is selected from the group consisting of a bond, hydrogen, halo, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, and C 1 -C 6 alkyloxo; and (n) ---- is optionally a bond to form a double bond at the indicated position.
[0073] In one embodiment, the present invention also relates to pharmaceutical compositions comprising at least one compound of the present invention, or a pharmaceutically acceptable salt, solvate, hydrate, or stereioisomer thereof, and a pharmaceutically acceptable carrier.
[0074] In another embodiment, the present invention relates to a method of selectively modulating a PPAR delta receptor comprising contacting the receptor with at least one compound represented by Structural Formula I, or a pharmaceutically acceptable salt, solvate, hydrate, or stereioisomer thereof.
[0075] In another embodiment, the present invention relates to a method of modulating one or more of the PPAR alpha, beta, gamma, and/or delta receptors.
[0076] In a further embodiment, the present invention relates to a method of making a compound represented by Structural Formula I.
[0077] The compounds of the present invention are believed to be effective in treating and/or preventing Metabolic Disorder, Type II diabetes, hyperglycemia, hyperlipidemia, obesity, coagaulopathy, hypertension, atherosclerosis, and other disorders related to Metabolic Disorder and cardiovascular diseases. Further, compounds of this invention can be useful for lowering fibrinogen, increasing HDL levels, treating renal disease, controlling desirable weight, treating demyelinating diseases, treating certain viral infections, and treating liver disease. In addition, the compounds can be associated with fewer clinical side effects than compounds currently used to treat such conditions.
DETAILED DESCRIPTION OF THE INVENTION
[0078] The terms used to describe the instant invention have the following meanings.
[0079] As used herein, the term “aliphatic linker” or “aliphatic group” is a non-aromatic, consisting solely of carbon and hydrogen and may optionally contain one or more units of unsaturation, e.g., double and/or triple bonds (also refer herein as “alkenyl” and “alkynyl”). An aliphatic or aliphatic group may be straight chained, branched (also refer herein as “alkyl”) or cyclic (also refer herein as “cycloalkyl). When straight chained or branched, an aliphatic group typically contains between about 1 and about 10 carbon atoms, more typically between about 1 and about 6 carbon atoms. When cyclic, an aliphatic typically contains between about 3 and about 10 carbon atoms, more typically between about 3 and about 7 carbon atoms. Aliphatics are preferably C 1 -C 10 straight chained or branched alkyl groups (i.e. completely saturated aliphatic groups), more preferably C 1 -C 6 straight chained or branched alkyl groups. Examples include, but are not limited to methyl, ethyl, propyl, n-propyl, iso-propyl, n-butyl, sec-butyl, and tert-butyl. Additional examples include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, cyclopentyl, cyclohexylyl and the like. Such aliphatic linker is optionally substituted with from one to four substituents each independently selected from R30. It can be preferred that aliphatic linker is substituted with from zero to two substituents each independently selected from R30. Further, it may be preferred that one carbon of the alphatic linker is replaced with an O, NH, or S. Finally, it may be preferred that the aliphatic linker is purely alkyl, with no carbon replaced with an O, NH, or S.
[0080] The term “alkyl,” unless otherwise indicated, refers to those alkyl groups of a designated number of carbon atoms of either a straight or branched saturated configuration. As used herein, “C 0 alkyl” means that there is no carbon and therefore represents a bond. Examples of “alkyl” include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, pentyl, hexyl, isopentyl and the like. Alkyl as defined above may be optionally substituted with a designated number of substituents as set forth in the embodiment recited above. As used herein, the term “alkyloxo” means an alkyl group of the designated number of carbon atoms with a “═O” substituent.
[0081] The term “alkenyl” or “alkylenyl” means hydrocarbon chain of a specified number of carbon atoms of either a straight or branched configuration and having at least one carbon-carbon double bond, which may occur at any point along the chain, such as ethenyl, propenyl, butenyl, pentenyl, vinyl, alkyl, 2-butenyl and the like. Alkenyl as defined above may be optionally substituted with designated number of substituents as set forth in the embodiment recited above.
[0082] The term “alkynyl” means hydrocarbon chain of a specified number of carbon atoms of either a straight or branched configuration and having at least one carbon-carbon triple bond, which may occur at any point along the chain. Example of alkynyl is acetylene. Alkynyl as defined above may be optionally substituted with designated number of substituents as set forth in the embodiment recited above.
[0083] The term “heteroalkyl” refers to a means a straight or branched hydrocarbon chain of a specified number of carbon atoms wherein at least one carbon is replaced by a heteroatom selected from the group consisting of O, N and S.
[0084] The term “cycloalkyl” refers to a saturated or partially saturated carbocycle containing one or more rings of from 3 to 12 carbon atoms, typically 3 to 7 carbon atoms. Examples of cycloalkyl includes, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, and the like. “Cycloalkyaryl” means that an aryl is fused with a cycloalkyl, and “Cycloalkylaryl-alkyl” means that the cycloalkylaryl is linked to the parent molecule through the alkyl. Cycloalkyl as defined above may be optionally substituted with a designated number of substituents as set forth in the embodiment recited above.
[0085] The term “halo” refers to fluoro, chloro, bromo and iodo.
[0086] The term “haloalkyl” is a C 1 -C 6 alkyl group, which is substituted with one or more halo atoms selected from F, Br, Cl and I. An example of a haloalkyl group is trifluoromethyl (CF 3 ).
[0087] The term “alkoxy” represents an alkyl group of indicated number of carbon atoms attached through an oxygen bridge, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, and the like. Alkoxy as defined above may be optionally substituted with a designated number of substituents as set forth in the embodiment recited above.
[0088] The term “haloalkyloxy” represents a C 1 -C 6 haloalkyl group attached through an oxygen bridge, such as OCF 3 . The “haloalkyloxy” as defined above may be optionally substituted with a designated number of substituents as set forth in the embodiment recited above.
[0089] The term “aryl” includes carbocyclic aromatic ring systems (e.g. phenyl), fused polycyclic aromatic ring systems (e.g. naphthyl and anthracenyl) and aromatic ring systems fused to carbocyclic non-aromatic ring systems (e.g., 1,2,3,4-tetrahydronaphthyl). “Aryl” as defined above may be optionally substituted with a designated number of substituents as set forth in the embodiment recited above.
[0090] The term “arylalkyl” refers to an aryl alkyl group which is linked to the parent molecule through the alkyl group, which may be further optionally substituted with a designated number of substituents as set forth in the embodiment recited above. When arylalkyl is arylCoalkyl, then the aryl group is bonded directly to the parent molecule. Likewise, arylheteroalkyl means an aryl group linked to the parent molecule through the heteroalkyl group.
[0091] The term “acyl” refers to alkylcarbonyl, arylcarbonyl, and heteroarylcarbonyl species.
[0092] The term “heteroaryl” group, as used herein, is an aromatic ring system having at least one heteroatom such as nitrogen, sulfur or oxygen and includes monocyclic, bicyclic or tricyclic aromatic ring of 5- to 14-carbon atoms containing one or more heteroatoms selected from the group consisting of O, N, and S. The “heteroaryl” as defined above may be optionally substituted with a designated number of substituents as set forth in the embodiment recited above. Examples of heteroaryl are, but are not limited to, furanyl, indolyl, thienyl (also referred to herein as “thiophenyl”) thiazolyl, imidazolyl, isoxazoyl, oxazoyl, pyrazoyl, pyrrolyl, pyrazinyl, pyridyl, pyrimidyl, pyrimidinyl and purinyl, cinnolinyl, benzofuranyl, benzothienyl, benzotriazolyl, benzoxazolyl, quinoline, isoxazolyl, isoquinoline and the like. The term “heteroarylalkyl” means that the heteroaryl group is linked to the parent molecule through the alkyl portion of the heteroarylalkyl.
[0093] The term “heterocycloalkyl” refers to a non-aromatic ring which contains one or more oxygen, nitrogen or sulfur and includes a monocyclic, bicyclic or tricyclic non-aromatic ring of 5 to 14 carbon atoms containing one or more heteroatoms selected from O, N or S. The “heterocycloalkyl” as defined above may be optionally substituted with a designated number of substituents as set forth in the embodiment recited above. Examples of heterocycloalkyl include, but are not limited to, morpholine, piperidine, piperazine, pyrrolidine, and thiomorpholine. As used herein, alkyl groups include straight chained and branched hydrocarbons, which are completely saturated.
[0094] When “----” is optionally a bond that forms a double bond in the five-membered heterocycle, the possible heterocycles include:
[0095] As used herein, the phrase “selectively modulate” means a compound whose EC 50 for the stated PPAR receptor is at least ten fold lower than its EC 50 for the other PPAR receptor subtypes.
[0096] PPARδ has been proposed to associate with and dissociate from selective co-repressors (BCL-6) that control basal and stimulated anti-inflammatory activities (Lee, C-H. et al. Science 302:453-4572003). PPARδ agonists are thought to be useful to attenuate other inflammatory conditions such as inflammation of the joints and connective tissue as occurs in rheumatoid arthritis, related autoimmune diseases, osteoarritis, as well as myriad other inflammatory diseases, Crohne's disease, and psoriasis.
[0097] When a compound represented by Structural Formula I has more than one chiral substituent it may exist in diastereoisomeric forms. The diastereoisomeric pairs may be separated by methods known to those skilled in the art, for example chromatography or crystallization and the individual enantiomers within each pair may be separated using methods familiar to the skilled artisan. The present invention includes each diastereoisomer of compounds of Structural Formula I and mixtures thereof.
[0098] Certain compounds of Structural Formula I may exist in different stable conformational forms which may be separable. Torsional asymmetry due to restricted rotation about an asymmetric single bond, for example because of steric hindrance or ring strain, may permit separation of different conformers. The present invention includes each conformational isomer of compounds of Structural Formula I and mixtures thereof.
[0099] Certain compounds of Structural Formula I may exist in zwitterionic form and the present invention includes each zwitterionic form of compounds of Structural Formula I and mixtures thereof.
[0100] “Pharmaceutically-acceptable salt” refers to salts of the compounds of the Structural Formula I which are considered to be acceptable for clinical and/or veterinary use. Typical pharmaceutically-acceptable salts include those salts prepared by reaction of the compounds of the present invention with a mineral or organic acid or an organic or inorganic base. Such salts are known as acid addition salts and base addition salts, respectively. It will be recognized that the particular counterion forming a part of any salt of this invention is not of a critical nature, so long as the salt as a whole is pharmaceutically-acceptable and as long as the counterion does not contribute undesired qualities to the salt as a whole. These salts may be prepared by methods known to the skilled artisan.
[0101] The term, “active ingredient” means the compounds generically described by Structural Formula I as well as the sterioisomers, salts, solvates, and hydrates,
[0102] The term “pharmaceutically acceptable” means that the carrier, diluent, excipients and salt are pharmaceutically compatible with the other ingredients of the composition. Pharmaceutical compositions of the present invention are prepared by procedures known in the art using well-known and readily available ingredients.
[0103] “Preventing” refers to reducing the likelihood that the recipient will incur or develop any of the pathological conditions described herein. The term “preventing” is particularly applicable to a patient that is susceptible to the particular pathological condition.
[0104] “Treating” refers to mediating a disease or condition and preventing, or mitigating, its further progression or ameliorate the symptoms associated with the disease or condition.
[0105] “Pharmaceutically-effective amount” means that amount of active ingredient that will elicit the biological or medical response of a tissue, system, or mammal. Such an amount can be administered prophylactically to a patient thought to be susceptible to development of a disease or condition. Such amount when administered prophylactically to a patient can also be effective to prevent or lessen the severity of the mediated condition. Such an amount is intended to include an amount which is sufficient to modulate a selected PPAR receptor or to prevent or mediate a disease or condition. Generally, the effective amount of a Compound of Formula I will be between 0.02 through 5000 mg per day. Preferably the effective amount is between 1 through 1,500 mg per day. Preferably the dosage is from 1 through 1,000 mg per day. A most preferable the dose can be from 1 through 100 mg per day.
[0106] The desired dose may be presented in a single dose or as divided doses administered at appropriate intervals.
[0107] A “mammal” is an individual animal that is a member of the taxonomic class Mammalia. The class Mammalia includes humans, monkeys, chimpanzees, gorillas, cattle, swine, horses, sheep, dogs, cats, mice, and rats.
[0108] Administration to a human is most preferred. The compounds and compositions of the present invention are useful for the treatment and/or prophylaxis of cardiovascular disease, for raising serum HDL cholesterol levels, for lowering serum triglyceride levels and for lower serum LDL cholesterol levels. Elevated triglyceride and LDL levels, and low HDL levels, are risk factors for the development of heart disease, stroke, and circulatory system disorders and diseases.
[0109] Further, the compound and compositions of the present invention may reduce the incidence of undesired cardiac events in patients. The physician of ordinary skill will know how to identify humans who will benefit from administration of the compounds and compositions of the present invention.
[0110] The compounds and compositions of the present invention can also be useful for treating and/or preventing obesity.
[0111] Further, these compounds and compositions are useful for the treatment and/or prophylaxis of non-insulin dependent diabetes mellitus (NIDDM) with reduced or no body weight gains by the patients. Furthermore, the compounds and compositions of the present invention are useful to treat or prevent acute or transient disorders in insulin sensitivity, such as sometimes occur following surgery, trauma, myocardial infarction, and the like. The physician of ordinary skill will know how to identify humans who will benefit from administration of the compounds and compositions of the present invention.
[0112] The present invention further provides a method for the treatment and/or prophylaxis of hyperglycemia in a human or non-human mammal which comprises administering an effective amount of active ingredient, as defined herein, to a hyperglycemic human or non-human mammal in need thereof.
[0113] The invention also relates to the use of a compound of Formula I as described above, for the manufacture of a medicament for treating a PPAR receptor mediated condition.
[0114] A therapeutically effective amount of a compound of Structural Formula I can be used for the preparation of a medicament useful for treating Metabolic Disorder, diabetes, treating obesity, lowering triglyceride levels, lowering serum LDL levels, raising the plasma level of high density lipoprotein, and for treating, preventing or reducing the risk of developing atherosclerosis, and for preventing or reducing the risk of having a first or subsequent atherosclerotic disease event in mammals, particularly in humans. In general, a therapeutically effective amount of a compound of the present invention typically reduces serum triglyceride levels of a patient by about 20% or more, and increases serum HDL levels in a patient. Preferably, HDL levels will be increased by about 30% or more. In addition, a therapeutically effective amount of a compound, used to prevent or treat NIDDM, typically reduces serum glucose levels, or more specifically HbA1c, of a patient by about 0.7% or more.
[0115] When used herein Metabolic Syndrome includes pre-diabetic insulin resistance syndrome and the resulting complications thereof, insulin resistance, non-insulin dependent diabetes, dyslipidemia, hyperglycemia obesity, coagulopathy, hypertension and other complications associated with diabetes. The methods and treatments mentioned herein include the above and encompass the treatment and/or prophylaxis of any one of or any combination of the following: pre-diabetic insulin resistance syndrome, the resulting complications thereof, insulin resistance, Type II or non-insulin dependent diabetes, dyslipidemia, hyperglycemia, obesity and the complications associated with diabetes including cardiovascular disease, especially atherosclerosis. In addition, the methods and treatments mentioned herein include the above and encompass the treatment and/or prophylaxis of any one of or any combination of the following inflammatory and autoimmune diseases: adult respiratory distress syndrome, rheumatoid arthritis, demyelinating disease, Chrohne's disease, asthma, systemic lupus erythematosus, psoriasis, and bursitis.
[0116] The compositions are formulated and administered in the same general manner as detailed herein. The compounds of the instant invention may be used effectively alone or in combination with one or more additional active agents depending on the desired target therapy. Combination therapy includes administration of a single pharmaceutical dosage composition which contains a compound of Structural Formula I, a stereoisomer, salt, solvate and/or hydrate thereof (“Active Ingredient”) and one or more additional active agents, as well as administration of a compound of Active Ingredient and each active agent in its own separate pharmaceutical dosage formulation. For example, an Active Ingredient and an insulin secretogogue such as biguanides, thiazolidinediones, sulfonylureas, insulin, or α-glucosidose inhibitors can be administered to the patient together in a single oral dosage composition such as a tablet or capsule, or each agent administered in separate oral dosage formulations. Where separate dosage formulations are used, an Active Ingredient and one or more additional active agents can be administered at essentially the same time, i.e., concurrently, or at separately staggered times, i.e., sequentially; combination therapy is understood to include all these regimens.
[0117] An example of combination treatment or prevention of atherosclerosis may be wherein an Active Ingredient is administered in combination with one or more of the following active agents: antihyperlipidemic agents; plasma HDL-raising agents; antihypercholesterolemic agents, fibrates, vitamins, aspirin, and the like. As noted above, the Active Ingredient can be administered in combination with more than one additional active agent.
[0118] Another example of combination therapy can be seen in treating diabetes and related disorders wherein the Active Ingredient can be effectively used in combination with, for example, sulfonylureas, biguanides, thiazolidinediones, α-glucosidase inhibitors, other insulin secretogogues, insulin as well as the active agents discussed above for treating atherosclerosis.
[0119] The Active Ingredients of the present invention, have valuable pharmacological properties and can be used in pharmaceutical compositions containing a therapeutically effective amount of Active Ingredient of the present invention, in combination with one or more pharmaceutically acceptable excipients. Excipients are inert substances such as, without limitation carriers, diluents, fillers, flavoring agents, sweeteners, lubricants, solubilizers, suspending agents, wetting agents, binders, disintegrating agents, encapsulating material and other conventional adjuvants. Proper formulation is dependent upon the route of administration chosen. Pharmaceutical formulations typically contain from about 1 to about 99 weight percent of the Active Ingredient of the present invention.
[0120] Preferably, the pharmaceutical formulation is in unit dosage form. A “unit dosage form” is a physically discrete unit containing a unit dose, suitable for administration in human subjects or other mammals. For example, a unit dosage form can be a capsule or tablet, or a number of capsules or tablets. A “unit dose” is a predetermined quantity of the Active Ingredient of the present invention, calculated to produce the desired therapeutic effect, in association with one or more pharmaceutically-acceptable excipients. The quantity of active ingredient in a unit dose may be varied or adjusted from about 0.1 to about 1500 milligrams or more according to the particular treatment involved. It may be preferred that the unit dosage is from about 1 mg to about 1000 mg.
[0121] The dosage regimen utilizing the compounds of the present invention is selected by one of ordinary skill in the medical or veterinary arts, in view of a variety of factors, including, without limitation, the species, age, weight, sex, and medical condition of the recipient, the severity of the condition to be treated, the route of administration, the level of metabolic and excretory function of the recipient, the dosage form employed, the particular compound and salt thereof employed, and the like.
[0122] Advantageously, compositions containing the compound of Structural Formula I or the salts thereof may be provided in dosage unit form, preferably each dosage unit containing from about 1 to about 500 mg be administered although it will, of course, readily be understood that the amount of the compound or compounds of Structural Formula I actually to be administered will be determined by a physician, in the light of all the relevant circumstances.
[0123] Preferably, the compounds of the present invention are administered in a single daily dose, or the total daily dose may be administered in divided doses, two, three, or more times per day. Where delivery is via transdermal forms, of course, administration is continuous.
[0124] Suitable routes of administration of pharmaceutical compositions of the present invention include, for example, oral, eyedrop, rectal, transmucosal, topical, or intestinal administration; parenteral delivery (bolus or infusion), including intramuscular, subcutaneous, intramedullary injections, as well as intrathecal, direct intraven-tricular, intravenous, intraperitoneal, intranasal, or intraocular injections. The compounds of the invention can also be administered in a targeted drug delivery system, such as, for example, in a liposome coated with endothelial cell-specific antibody.
[0125] Solid form formulations include powders, tablets and capsules.
[0126] Sterile liquid formulations include suspensions, emulsions, syrups, and elixirs.
[0127] Pharmaceutical compositions of the present invention can be manufactured in a manner that is itself known, e.g., by means of conventional mixing, dissolving, granulating, dragee-making, levigating, emulsifying, encapsulating, entrapping or lyophilizing processes.
[0128] The following pharmaceutical formulations 1 and 2 are illustrative only and are not intended to limit the scope of the invention in any way.
Formulation 1
[0129] Hard gelatin capsules are prepared using the following ingredients:
Quantity (mg/capsule) Active Ingredient 250 Starch, dried 200 Magnesium stearate 10 Total 460 mg
Formulation 2
[0130] A tablet is prepared using the ingredients below:
Quantity (mg/tablet) Active Ingredient 250 Cellulose, microcrystalline 400 Silicon dioxide, fumed 10 Stearic acid 5 Total 665 mg
[0131] The components are blended and compressed to form tablets each weighing 665 mg.
[0132] In yet another embodiment of the compounds of the present invention, the compound is radiolabelled, such as with carbon-14, or tritiated. Said radiolabelled or tritiated compounds are useful as reference standards for in vitro assays to identify new selective PPAR receptor agonists.
[0133] The compounds of the present invention can be useful for modulating insulin secretion and as research tools. Certain compounds and conditions within the scope of this invention are preferred. The following conditions, invention embodiments, and compound characteristics listed in tabular form may be independently combined to produce a variety of preferred compounds and process conditions. The following list of embodiments of this invention is not intended to limit the scope of this invention in any way.
[0134] Some preferred characteristics of compounds of formula I are:
(a) R3 is methyl; (b) R4 is hydrogen; (c) R3 and R4 are each hydrogen; (d) R3 and R4 are each methyl; (e) A is carboxyl; (f) X is —O—; (g) X is —S—; (h) X is a single bond; (i) U is CH(R30); (j) U is CH 2 CH(R30); (k) U is CH2CH(R30)CH2; (l) U is CH 2 N(R30)CH 2 ; (m) U is CH 2 OCH 2 ; (n) U is CH 2 CH 2 CH 2 ; (o) U is CH 2 ; (p) U is CH 2 NHCH 2 ; (q) U is CH 2 N(CH 3 )CH 2 ; (r) U is CH 2 N(CH(CH 3 ) 2 )CH 2 ; (s) U is CH 2 N(CH 2 CH 2 CH 3 )CH 2 ; (t) U is CH 2 N(CH 2 CH 3 )CH 2 ; (u) W is N; (v) W is O; (w) W is S; (x) R30 is CH 3 ; (y) R30 is phenyl; (z) R30 is CH 2 CH 2 CH 2 CH 3 ; (aa) R30 is CH 2 CH 2 CF 3 ; (bb) R30 is CH 2 CH═CH 2 ; (cc) R30 is CH(CH 3 ) 2 ; (dd) R30 is CH 2 CH 2 CH 3 ; (ee) R30 is CH 2 CH 3 ; (ff) R9 is methyl; (gg) R9 is hydrogen; (hh) R9 is C 1 -C 3 alkyl; (ii) R8 is methyl; (jj) R8 and R9 are each hydrogen; (kk) R10 is CF 3 ; (ll) R10 is haloalkyl; (mm) R10 is haloalkyloxy; (nn) R11 is hydrogen (oo) R10 and R11 are each hydrogen; (pp) R11 is haloalkyl; (qq) R10 and R11 combine to form a fused bicyclic; (rr) R10 and R11 combine to form a naphtyl substituent with the phenyl to which they are attached; (ss) R1 is optionally substituted C 2 -C 3 arylalkyl; (tt) R1 is substituted C 2 arylalkyl; (uu) R1 is C 1 -C 8 heteroalkyl; (vv) R1 is heteroalkyl wherein one of the carbon atoms is replaced with an oxygen; (ww) R1 is heteroalkyl wherein two of the carbon atoms is replaced with an oxygen; (xx) R1 is substituted with one R1′; (yy) R1 is C 1 -C 3 alkenyl; (zz) R1 is C 1 -C 4 alkyloxo; (aaa) R1 is C 1 -C 4 alkyl; (bbb) R32 is hydrogen; (ccc) ---- in the five membered ring each form a double bond at the designated position in Formula I; (ddd) V is a bond; (eee) V is C 1 -C 3 alkyl; (fff) V is CH 2 ; (ggg) V is CH 2 CH 2 ; (hhh) V is CH 2 CH 2 CH 2 ; (iii) Y is O; (jjj) Y is S; (kkk) Y is C; (lll) Y is C, NH, or a bond; (mmm) E is C(R3)(R4)A; (nnn) R3 is hydrogen; (ooo) R3 is C 1 -C 2 alkyl; (ppp) R4 is C 1 -C 2 alkyl; (qqq) R3 and R4 are each hydrogen; (rrr) R3 and R4 are each methyl; (sss) A is COOH; (ttt) Aliphatic linker is saturated; (uuu) Aliphatic linker is substituted with C 1 -C 3 alkyl; (vvv) Aliphatic linker is substituted with from one to three substituents each independently selected from R30; (www) Aliphatic linker is substituted with from one to two substituents each independently selected from R30; (xxx) Aliphatic linker is C 1 -C 3 alkyl; (yyy) Aliphatic linker is C 1 -C 2 alkyl; (zzz) Aliphatic linker is C 1 -C 3 alkyl and one carbon is replaced with an —O—; (aaaa) A compound of Formula IV:
(bbbb) A compound of Structural Formula V:
(cccc) A compound of Structural Formula VI:
(dddd) A compound of Structural Formula VII:
(eeee) A compound of Structural Formula VIII:
(ffff) A compound of Structural Formula VIIIa:
(gggg) A compound of Structural Formula IX:
(hhhh) A compound of Structural Formula X:
(iiii) A compound of Structural Formula XI:
(jjjj) A compound of Structural Formula XII:
(kkkk) A compound of Structural Formula XIII:
(llll) Aryl is a phenyl group; (mmmm) Aryl is a naphthyl group; (nnnn) A compound of Formula I that selectively modulates a delta receptor; (oooo) An Active Ingredient, as described herein, that is a PPAR coagaonist that modulates a gamma receptor and a delta receptor; (pppp) An Active Ingredient, as described herein, for use in the treatment of cardiovascular disease; (qqqq) An Active Ingredient, as described herein, for use in the treatment of Metabolic Disorder; (rrrr) An Active Ingredient for use in the control of obesity; (ssss) An Active Ingredient for use in treating diabetes; (tttt) An Active Ingredient that is a PPAR receptor agonist; (uuuu) A compound of Formula I selected from the group consisting of 2-Methyl-2-{4-[3-(5-naphthalen-2-ylmethyl-2H-[1,2,4]triazol-3-yl)-phenoxy}proprionic acid.
[0234] Compounds of Formula I are prepared by the reaction of either a carbonyl hydrazone 1a in the presence of a carbonitrile 1b or of a carbonyl hydrazone 1d in the presence of a carbonitrile 1c to give intermediates 2. The reaction to form the triazole core 2 occurs in the presence of a strong base, e.g., sodium, lithium, or potassium alkoxides or sodium, lithium or potassium hydroxides in a polar protic solvent such as lower molecular weight alkanols, e.g., methanol, ethanol, or n- or i-propanol at reaction temperatures from room temperature to the reflux temperature of the mixture. Compound 2 is alkylated with a primary or secondary alkyl halide R—Z, where R includes the definition of both R32 and R1 in the presence of a base, e.g., sodium, lithium, or potassium bicarbonate or carbonate in a polar aprotic solvent, e.g., acetonitrile, acetone, or DMF at from room temperature to the reflux temperature of the mixture. Catalytic KI may be added to facilitate the overall alkylation by in situ replacement of R—Z, if Z is Cl or Br, to the more reactive R—I alkyation reagent. The alkylation with R give a mixture of regio and therefore optical isomers of Formula I.
[0235] Since racemic mixtures of Formula I are separated and isolated by chiral chromatography to pure isomers, at times, the racemic mixtures of Formula I are required to have functional group adjustments, perhaps, lending the mixtures to optimum separation in the chiral chromatography procedure. Functional group adjustments anticipated here and appreciated by one skilled in manipulations of organic reactions include manipulations of carboxylic acid derivatives, if applicable, to either esters of low molecular weight such as methyl or ethyl esters or to esters with steric hindrance such as t-butyl esters. Alternately as appreciated by one skilled in the execution of synthetic methodologies, ester functionalities, if applicable, my be adjusted to the free carboxylic acids by saponification of lower molecular weight esters with sodium, lithium or potassium hydroxides in a polar protic solvents, such as, methanol or ethanol, or strong acid hydrolysis of hindered esters, e.g., t-butyl esters with TFA in a weakly polar aprotic solvent such as methylene chloride or dichloroethane.
[0236] Other functional group manipulations include the conversion of ketones or aldehydes, if applicable, to ketals and acetals, with lower molecular weight alkane-diols and strong acid, e.g., tosic acid and sulfuric acid. Alternately, acetals and ketals, if present, may be converted to the corresponding carbonyl compound with strong acid and hydrated lower alkanols or with BBr3 in dichloromethane or dichloroethane.
[0237] The starting materials for the above scheme may often be commercially available, particularly, for carbonitrile compounds 1c and 1b. Other carbonitriles of formula 1c and 1b may be prepared, as is common to one skilled in the art of organic manipulations, from 1) commercially available or known carboxylic acids by conversion to primary amides followed by dehydration with a Vilsmeier reagent or 2) commercially available or known carboxaldehydes by conversion to oximes followed by dehydration with a Vilsmeier reagent.
[0238] Hydrazones of the formula 1a and 1d are prepared from the corresponding carboxylic acids or acid halides and hydrazine in dichloromethane or dichloroethane in the presence of base such as, pyridine, triethylamine, or sodium, lithium, or potassium bicarbonate or carbonate. A particularly useful reference for the preparation of 1a or 1d is Xu, Yanping, et. al. J. Med. Chem. 46(24)(2003) p. 5121-5124, where analogous reactions may be applied to the synthesis of 1a or 1d using commercially available or known carboxylic acids.
Preparation 1 (Compound 1)
[0239]
EXAMPLE 2A (COMPOUND 2A)
[0240]
[0241] Take up the compound or preparation 1 [Xu, et. al. Loc. Sit. (2003)] (1.34 gm, 4 mmol) in methanol (30 mL). To this solution, add 4-methylbenzylnitrile (1.04 gm, 8 mmole), followed by sodium methoxide (75 mg). Heat the reaction at reflux (˜80° C.) with stirring for 24 h. Dilute the mixture with ethyl acetate (50 mL). Wash the ethyl acetate with water (3×60 mL), dried (Na 2 SO 4 ), and concentrate on a rotovap to give an oily residue. Purify the residue on a silica column to give Example 2A as an oil (670 mg). m/z: M+1450.
EXAMPLES 2B-2D
[0242] Synthesize Examples 2B to 2D shown in the following Table according to the procedure for example 2A, from preparation 1 using appropriate nitrile shown in Table below.
Example R Nitrile Used (m/z) M + 1 2B Phenethyl 2-Phenylpropionitrile 450 2C Naphthylmethyl 2-Naphthylacetonitrile 486 2D 3-(4-Chlorophenyl)-3-ethoxypropyl 4-(4-Chlorophenyl)-4-ethoxybutyronitrile 542
EXAMPLE 3A
[0243]
[0244] Take up the compound of Example 2A (120 mg) in 50% TFA-dichloromethane (5 mL). Stir this mixture at room temperature for 18 h. Remove the solvent on a rotovap and dry the residue under high vacuum to give an oil (101 mg). m/z: 394 (M+1).
EXAMPLES 3B-3D
[0245] Synthesize examples 3B to 3C shown in the following Table according to the procedure for Example 3A, using TFA mediated hydrolysis of appropriate t-butyl esters of Examples 2B to 2D.
Example R (m/z) M + 1 3B 394 3C 430 3D 486
EXAMPLE 4A
[0246]
[0247] Add 2-ethoxyethylbromide (0.1 mL) to a solution of 2A (70 mg) in anhydrous DMF (1.5 mL) followed by anhydrous powdered K 2 CO 3 . Heat the reaction mixture at 50° C. with stirring for 18 h. Dilute the mixture with ethyl acetate (30 mL) and wash the ethyl acetate with water (3×30 mL). Dry the ethyl acetate layer (Na 2 SO 4 ) and concentrate on a rotovap to give an oily residue. Purify the residue on a silica column to give approximate 40-60 regio-isomeric mixture of Example 4A as an oil (62 mg). m/z: 522 (M+1).
EXAMPLES 4B TO 4F
[0248] Synthesize Compounds 4B to 4F shown in the following Table according to the procedure for 4A from 2A using appropriate alkylbromide as shown in Table below.
Example R Alkylbromide Used (m/z) M + 1 4B 2-(2-methoxy)ethoxyethyl 2-(2-methoxy)ethoxyethylbromide 552 4C 3-tetrahydropyranoxypropyl 3-tetrahydropyranoxypropylbromide 592 4D 6-tetrahydropyranoxyhexyl 6-tetrahydropyranoxyhexylbromide 634 4E 4-t-butylbenzyl 4-t-butylbenzylbromide 596 4F 2-Oxobutyl 1-Bromobutan-2-one 520
EXAMPLE 5A
[0249]
[0250] Take up the triazole mixture Example 4A (61 mg) in 50% TFA-dichloromethane (4 mL). Stir this mixture at room temperature for 4 h. Remove the solvent on a rotovap and dry the residue under high vacuum to give regioisomeric mixture Example 5A an oil (30 mg). m/z: 466 (M+1)
EXAMPLES 5B TO 5F
[0251] Synthesize Example 5B to 5F shown in the following Table according to the procedure for 5A, by TFA mediated hydrolysis of tert-butyl esters Examples 4E to 4C.
Example R (m/z) M + 1 5B 496 5C 452 5D 494 5E 540 5F 464
EXAMPLES 6 AND 7
[0252] Add conc. H 2 SO 4 to a solution of mixture Example-5A (70 mg) in methanol (25 mL). Stir the reaction mixture at room temperature for 18 h. Remove the solvent to a small volume and dilute the residue with ethyl acetate (30 mL). Wash the ethyl acetate layer with water (3×30 mL), dry (Na 2 SO 4 ), and concentrate on a rotovap to give an oily residue (71 mg). Purify the residue on a chiral HPLC column to give pure examples 6 and 7.
EXAMPLE 6
[0253] (15 mg), m/z: 480 (M+1).
EXAMPLE 7
[0254] (19 mg), m/z: 480 (M+1).
EXAMPLE 8
[0255]
[0256] Take up the triazole ester Example 6 (15 mg) in methanol (2 mL). Add 2N aqueous NaOH (1 mL) to this solution. Stir the mixture at room temperature for 2 h. Evaporate the solvent on the rotovap and dissolve the residue in water (5 mL). Acidify the solution to pH ˜3 with 0.1 M aqueous HCl to give a milky solution. Extract the mixture with CH 2 Cl 2 (3×10 mL). Dry the combined CH 2 Cl 2 layers (Na 2 SO 4 ), concentrate on a rotovap, and then dry under high vacuum to give Example 8 (11 mg). m/z: 466 (M+1).
EXAMPLE 9
[0257]
[0258] Synthesize example 9 according to the procedure for example 8 by NaOH mediated hydrolysis of ester example 6. m/z: 466 (M+1).
EXAMPLE 9a
[0259]
[0260] Synthesize Example 9a using the general method for Example 3A and Scheme I. m/z: 436.3.
EXAMPLE 10
2-Methyl-2-(4-{3-[5-(4-trifluoromethyl-phenyl)-2H-[1,2,4]triazol-3-yl]-propyl}-phenoxy)-propionic acid tert-butyl ester
[0261]
[0262] Add 4-(trifluoromethyl)benzonitrile (0.51 g, 3.0 mol) and potassium tert-butoxide (0.023 g, 0.21 mmol) to a solution of 2-[4-(3-Hydrazinocarbonyl-propyl)-phenoxy]-2-methyl-propionic acid tert-butyl ester (0.5 g, 1.5 mmol) in MeOH (5 mL). Stir the mixture at reflux overnight. Add an additional 0.2 equivalents of potassium tert-butoxide and stir the reaction for 24 h. Quench the crude with water, remove the MeOH in vacuo, and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuo. Purify the crude by Biotage (Hexane/EtOAc 4:1) yielding 0.32 g (44%) of the title compound, example 10 as a pale yellow oil. MS Data (ES + ) m/z 490.6 [M+H]
EXAMPLE 11
2-Methyl-2-(4-{3-[5-(4-trifluoromethyl-phenyl)-2H-[1,2,4]triazol-3-yl]-propyl}-phenoxy)-propionic acid
[0263]
[0264] Add TFA (0.31 mL, 3.98 mmol) to a solution of example 10 (0.65 g, 1.33 mmol) in CH 2 Cl 2 (6.5 ml). Stir the mixture at room temperature overnight. By TLC, a significant amount of starting material remains. Remove the solvent and residual TFA in vacuo. Purify the crude material by flash column chromatography (Hexane/EtOAc 2:1 and 1:1) yielding 0.16 g (28%) of example 10 as a white solid, and 0.4 g of the starting material recovered. MS Data (ES + ) m/z 434.3 [M+H].
R30a is R30 or H.
[0265] Add BnBr (1.1 mmol) and Ag 2 O (1.1 mmol) to a solution of commercial starting material (1.0 mmol) in EtOAc (5 mL/mmol). Reflux the mixture overnight. Follow the reaction by TLC (Hexane/EtOAC 1:1). Filter the reaction through celite and remove the solvent under vacuum. Purify the crude material by flash chromatography (Hexane and Hexane/EtOAc 20%) to obtain a compound of formula A of scheme 2.
[0266] Dissolve the benzyl derivative compound of formula A of scheme 2 (1.0 mmol) in EtOH (0.8 M). Then, add hydrazine monohydrate (3.0 mmol). Stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 4:1). Remove the solvent under vacuum. Dissolve the residue in EtOAc and wash with water. Dry and concentrate the organic layer. Use the crude material without further purification. Add 4-(trifluoromethyl)benzonitrile (2.0 mol) and potassium tert-butoxide (0.6 mmol) to a solution of acylhydrazine a compound of formula B of scheme 2 (1.0 mmol) in MeOH (2.4 M). Stir the mixture at reflux 24 h. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude material with water, remove the MeOH in vacuo and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude material by Biotage (Hexane/EtOAc 4:1) to obtain a compound of formula C of scheme 2.
[0267] Triazole alkylation: Add powdered KOH (2.2 mmol), R—I (Br)(2.0 mmol) and Bu 4 NBr (0.2 mmol) to a solution of the corresponding triazole derivate compound C of scheme 2 (1.0 mmol) in THF (5 mL/mmol). Stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude material by Biotage (Hexane/EtOAc 7:1 and 4:1) to obtain a compound of formula D of scheme 2.
[0268] Add Pd (C)(10-20% in weight) and NH 4 + COO − (10-20 mmol) to a solution of triazole compound of formula D of scheme 2 (1.0 mmol) in EtOH (5 mL/mmol). Stir the mixture at 80° C. overnight. Follow the reaction by TLC. Filter the reaction through celite and remove the solvent under vacuum. Purify the crude material by Biotage (Hexane/EtOAc 1:1) to obtain a compound of formula E of scheme 2.
[0269] Add K 2 CO 3 (1.1 mmol) and 4-fluoro-nitrobenzene (1.0 mmol) to a solution of the corresponding triazole derivate (C) of scheme 2a (1.0 mmol) in DMSO (20 mL/mmol) and stir the mixture to 90° C. overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the reaction with ice/water and add DCM. Extract again with 20% DCM/MeOH. Combine the organic layers and dry with MgSO 4 , and concentrate in vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 9:1) to obtain formula D of scheme 2A.
[0270] Add Pd (C)(10% in weight) to a solution of the triazole derivate formula D of scheme 2a (1.0 mmol) in EtOH (5 mL/mmol). Stir the mixture with and in an atmosphere of hydrogen overnight. Follow the reaction by TLC. Filter the solution mixture through celite and the remove the solvent under vacuum. Purify the crude (formula E of scheme 2A) without further purification.
[0271] Add 2N HCl solution (10.0 mmol) to a solution of the corresponding triazole derivate formula E of scheme 2A (1.0 mmol) in a mixture solvent (THF/CH 3 COOH 8:1) (8 mL/mmol) at 0° C. and stir the mixture for 5 minutes at this temperature. Then, add NaNO 2 (1.0 mmol) in water (0.32 M) and then 3% H 2 O 2 solution. Stir the reaction at 0° C. for 30 minutes and then for 1 hour at room temperature. Then, add EtOAc and extract the mixture with water. Dry the organic layers with MgSO 4 and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 9:1) to obtain compound of formula F of scheme 2A (Yield 17%).
[0272] Add Pd (C)(10-20% in weight) and NH 4 + COO − (10-20 mmol) to a solution of a compound of formula F of scheme 2A (1.0 mmol) in EtOH (5 mL/mmol). Stir the mixture at 80° C. overnight. Follow the reaction by TLC. Filter the reaction through celite and remove the solvent under vacuum. Purify the crude by Biotage (Hexane/EtOAc 1:1) to obtain compound F of scheme 2a.
[0273] Mitsounobu reaction: Add the head piece (2 mmol), Bu 3 P (2.0 mmol) and TMAD (2.0 mmol) to a solution of triazole derivate compound E of scheme 2 (1.0 mmol) in THF/DCM mixture (1:1)(10 mL/mmol). Stir the mixture at room temperature for 10-20 min. Follow the reaction by TLC. Remove the solvent under vacuum and then, add water and diethyl ether. Separate the organic layer and stir with a 2N NaOH solution for 10 min. Extract the mixture, dry the organic layer with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 9:1) to obtain compound F of scheme 2.
[0274] Add 2N KOH solution (10 mmol) to a solution of triazole derivate compound F of scheme 2 (1.0 mmol) in EtOH/THF mixture (1:1)(10 mL/mmol) and stir the mixture at room temperature overnight. Follow the reaction by TLC. Remove the solvent under vacuum and then, add water and EtOAc. Add 1N HCl solution until the pH is 5-7. Extract the mixture, wash the organic layer with water, separate, dry with MgSO 4 , and concentrate in vacuum. Obtain the compound G of scheme 2.
SYNTHESIS OF EXAMPLE 13
Preparation 2
[0275]
[0276] Add BnBr (72.7 mL, 0.61 mol, 1.1 eq) and Ag 2 O (141.6 g, 0.61 mol, 1.1 eq) to a solution of methyl glycolate (50 g, 0.56 mol) in EtOAc (300 mL) and stir the mixture to reflux overnight. Follow the reaction by TLC (Hexane/EtOAC 1:1). Filter the reaction through celite and remove the solvent under vacuum. The oil is passed adsorbed onto flash silica. Place on top of a pad of flash silica (500 g) and elute with 20% ethyl acetate/hexane to give 75.8 g (75% yield) of a colorless oil.
Preparation 3
[0277]
[0278] Dissolve preparation 2 (7.5 g, 41.6 mmol) in EtOH (100 mL). Then, add hydrazine monohydrate (6.05 mL, 124.9 mmol) and stir the mixture at room temperature overnight. Follow the reaction is by TLC (hexane/EtOAc 4:1). Remove the solvent under vacuum and dissolve the residue in EtOAc and wash with water. Dry the organic layer and concentrate and use the crude without further purification.
Preparation 4
[0279]
[0280] Add 4-(trifluoromethyl)benzonitrile (14.2 g, 83.2 mmol) and potassium tert-butoxide (2.8 g, 25 mmol) to a solution of preparation 3 in MeOH (100 mL) and stir mixture is at reflux for 24 h. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water, remove the MeOH in vacuum, and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 4:1) to obtain 11.2 g (81% yield) of preparation 4 as a white solid.
Preparation 5
[0281]
[0282] Add powdered KOH (0.37 g, 6.6 mmol), EtI (0.48 mL, 6.0 mmol) and Bu 4 NBr (0.19 g, 0.6 mmol) to a solution of preparation 4 (1.0 g, 3.0 mmol) in THF (15 mL), and stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuo. Purify the crude by flash chromatography (Hexane/EtOAc 9:1) to obtain 1.09 g (99% yield) of preparation 5 as a white solid.
Preparation 6
[0283]
[0284] Add Pd (C)(20% in weight) and NH 4 + COO − (1.83 g, 10.0 mmol) to a solution of preparation 5 (1.05 g, 2.9 mmol) in EtOH (25 mL) and stir the mixture at 80° C. for 6 hours. Follow the reaction by TLC (Hexane/EtOAc 4:1). Filter the reaction through celite and remove the solvent under vacuum to obtain 0.88 g of preparation 6 as a white solid that is used without further purification.
Preparation 7
[0285]
[0286] Add the headpiece (1.38 g, 5.8 mmol), Bu 3 P (1.44 mL, 5.8 mmol) and TMAD (0.99 g, 5.8 mmol) to a solution of preparation 6 (0.88 g, 2.9 mmol) in THF/DCM mixture (1:1)(15+15 mL) and stir the mixture at room temperature for 1 h. Follow the reaction by TLC (Hexane/EtOAc 1:1). Remove the solvent under vacuum. Then, add water and diethyl ether. Separate the organic layer, and stir with 2N NaOH solution for 10 min. Extract the mixture and dry the organic layer with MgSO 4 , and concentrate in vacuo. Purify the crude by Biotage [40+S] (Hexane/EtOAc 9:1) to obtain 0.99 g (70% yield) of preparation 7 as a white solid. MS Data (ES + ) m/z 492.3 [M+H]. 350 mg (fraction B) of impure compound were reserved.
EXAMPLE 13
[0287]
[0288] Add 2N KOH solution (10 mL, 19.9 mmol) to a solution of preparation 7 (0.98 g, 1.99 mmol) in EtOH/THF mixture (1:1)(10+10 mL), and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 1:1). Remove the solvent under vacuum. Then, add water and Et 2 O and stir the mixture for 2 min. Isolate the organic layer and add 1N HCl solution over aqueous phase until pH 5-7. Filter the white solid precipitate and wash with water. Dry under vacuum to obtain: 0.80 g (87% yield) of Example 13 (Purity 97%). MS Data (ES + ) m/z 464.2 [M+H].
[0289] Prepare Examples 12 and 14-34 by a similar procedure for the preparation of Example 13.
Example Structure LC/MS [M + 1] 12 464.4 13 464.2 14 478.1 15 450.4 16 478.3 17 450.0 18 466.0 19 498.0 20 436.1 21 511.9 22 475.9 23 450.1 24 492.3 25 478.3 26 478.1 27 464.2 28 464.2 29 512.2 30 526.2 31 452.2 32 490.1 33 492.3 34 494.2
[0290]
General Procedure for Scheme 3
[0291] Add K 2 CO 3 (3.0 mmol) and compound of formula A of scheme 3 (1.0 mmol) to a solution of the bromoesther derivate (compound of formula H of scheme 3)(1.2 mmol) in MeCN (5 mL/mmol). Stir the mixture at reflux overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Remove the solvent under vacuum and then, add water and EtOAc. Extract the mixture, dry the organic layer with MgSO 4 , and concentrate in vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 6:1) to obtain compound B of scheme 3.
[0292] Dissolve ester compound of formula B of scheme 3 (1.0 mmol) in EtOH (0.8 M). Then, add hydrazine monohydrate (3.0 mmol). Stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 4:1). Remove the solvent under vacuum. Dissolve the residue in EtOAc and wash with water. Dry the organic layer and concentrate. Use the crude without further purification. Add 4-(trifluoromethyl)benzonitrile (2.0 mol) and potassium tert-butoxide (0.6 mmol) to a solution of acylhydrazine compound of formula C of scheme 3 (1.0 mmol) in EtOH (2.4 M). Stir the mixture at reflux 24 hours. Follow the reaction by TLC (hexane/EtOAc 4:1). Quench the crude with water, remove the MeOH in vacuo, and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 6:1) to obtain the compound of formula F of scheme 3 as a colorless oil.
[0293] Add 2N KOH solution (10 mmol) to a solution of triazole derivate compound of formula F of scheme 3 (1.0 mmol) in EtOH/THF mixture (1:1)(10 mL/mmol). Stir the mixture at room temperature overnight. Follow the reaction by TLC. Remove the solvent under vacuum. Then, add water and EtOAc. Add 1N HCl solution until pH 5-7. Extract the mixture, wash the organic layer with water, separate, dry with MgSO 4 , and concentrate in vacuum. Obtain the products of the compound of formula G of scheme 3 as white solids.
Synthesis of Example 36
Preparation 8
[0294]
[0295] Add K 2 CO 3 (9.23 g, 66.9 mmol) and headpiece (5.0 g, 22.3 mmol) to a solution of commercially available bromoesther derivate (2.54 mL, 26.8 mmol) in MeCN (100 mL) and stir the mixture at reflux overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Remove the solvent under vacuum. Then, add water and EtOAc. Extract the mixture and dry the organic layer with MgSO 4 and concentrate in vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 19:1) to obtain preparation 8 as a colorless oil (6.59 g).
Preparation 9
[0296]
[0297] Dissolve preparation 8 (6.59 g, 22.3 mmol) in EtOH (30 mL). Then, add hydrazine monohydrate (4.32 mL, 89.2 mmol) and stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 4:1). Remove the solvent under vacuum. Dissolve the residue in EtOAc and wash with water. Dry the organic layer and concentrate. Use the crude preparation 9 without further purification.
Preparation 10
[0298]
[0299] Add 4-(trifluoromethyl)benzonitrile (4.72 g, 27.6 mmol) and potassium tert-butoxide (0.93 g, 8.3 mmol) to a solution of acylhydrazine preparation 9 (3.22 g, 10.9 mmol) in EtOH (50 mL) and stir the mixture at reflux 24 h. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water, remove the MeOH in vacuo and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 9:1 to 6:1) obtain preparation 10 as a white solid (2.28 g obtained, 47% yield two steps).
EXAMPLE 36
[0300]
[0301] Add 2N KOH solution (2.7 mL, 4.5 mmol) to a solution of preparation 10 (200 mg, 0.45 mmol) in EtOH/H mixture (1:1)(8 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC. Remove the solvent under vacuum. The, add water and EtOAc. Add 1N HCl solution until pH 5-7. Extract the mixture and wash the organic layer with water, separate, dry with MgSO 4 , and concentrate in vacuum. Obtain example 36 as white solids (164 mg, 87% yield).
[0302] Prepare Examples 35, 37 and 38 by a similar procedure for the preparation of Example 36.
Example Structure LC/MS [M + 1] 35 436.1 36 421.1 37 450.2 38 436.1 38a
[0303]
General Procedure for Scheme 4
[0304] Add 4-(trifluoromethyl)benzonitrile (3.0 mol) and potassium tert-butoxide (0.21 mmol) to a solution of a compound of formula A of scheme 4 (1.5 mmol) in MeOH (5 mL) and stir the mixture at reflux overnight. Add an additional 0.2 equivalents of potassium tert-butoxide and stir the reaction for 24 hours. Quench the crude with water, remove the MeOH in vacuo, and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 4:1) yielding a compound of formula B of scheme 4.
R=Alkyl group
[0305] Triazole alkylation: Add powdered KOH (2.2 mmol), R—I (Br)(2.0 mmol) and Bu 4 NBr (0.2 mmol) to a solution of the corresponding triazole compound of formula B of scheme 4 (1.0 mmol) in THF (5 mL/mmol) and stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 7:1 and 4:1) to obtain a compound of formula C of scheme 4.
R=Aryl group (Ph and p-CF 3 -Ph)
[0306] Coupling reaction: Add aryliodine (1.0 mmol), K 2 CO 3 (2.0 mmol), Cu(OAc) 2 (0.01 mmol) and trans-1,2-diaminocyclohexane (0.07 mmol) to a solution of the corresponding triazole derivate compound of formula B of scheme 4 (1.2 mmol) in anhydrous dioxane (5 mL/mmol) under N 2 . Stir the mixture to 110° C. overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Filter the reaction through celite and extract the organic layer with water. Extract the aqueous layer with EtOAc (2×), separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 9:1) to obtain compound of formula C of scheme 4.
R=Aryl group (o-F-Ph)
[0307] Add K 2 CO 3 (1.1 mmol) and 3,4-difluoro-nitrobenzene (1.0 mmol) to a solution of the corresponding triazole compound of formula B (1.0 mmol) in DMSO (20 mL/mmol) and stir the mixture to 90° C. overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with ice/water and add DCM. Extract a second extraction with 20% DCM/MeOH. Combine the organic layers, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 9:1) to obtain a compound of formula Ba of scheme 4a.
[0308] Add Pd (C)(10% in weight) to a solution of triazole derivate (1.0 mmol) in alcohol (5 mL/mmol). Stir the mixture with and in an atmosphere of hydrogen overnight. Follow the reaction by TLC. Filter the solution mixture through celite and remove the solvent under vacuum and use the crude without further purification.
[0309] Add 2N HCl solution (10.0 mmol) to a solution of the corresponding triazole compound Bb of scheme 4a (1.0 mmol) in a mixture solvent (THF/CH 3 COOH 8:1)(8 mL/mmol) at 0° C. Stir the mixture 5 minutes at this temperature and add NaNO 2 (1.0 mmol) in water (0.32 M) and then 3% H 2 O 2 solution (0.56 mL). Stir the reaction at 0° C. for 30 min and 1 hour at room temperature. Then, add EtOAc and extract the mixture with water. Dry the organic layer with MgSO 4 and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 9:1) to obtain compound C of scheme 4a.
[0310] Add TFA (excess) to a solution of compound of formula C of scheme 4 (1.0 mmol) in CH 2 Cl 2 (5 ml) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 1:1). Remove the solvent and residual TFA in vacuum. Dissolve the residue in DCM and wash with a saturated solution of NaHCO 3 . Dry the organic layer with MgSO 4 and concentrate in vacuum. Obtain the compound of formula D of scheme 4.
[0311] Add I 2 (2.0 mmol) and AgSO 4 (2.0 mmol) to a solution of the corresponding triazole compound of formula D of scheme 4 (1.0 mmol) in EtOH (8 mL/mmol) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 7:1 and 4:1) to obtain a compound of formula E of scheme 4.
[0312] Add MeB(OH) 2 (3.0 mmol), CsF (3.0 mmol) and PdCl 2 (dppf)(0.16 mmol) to a solution of the corresponding triazole compound of formula E of scheme 4 (1.0 mmol) in anhydrous Dioxane (10 mL/mmol) under N 2 . Stir the mixture to 80° C. overnight. Follow the reaction by LC/MS. Cool the reaction, filter through celite, and remove the solvent under vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 7:1 and 4:1 mixtures) to obtain a compound formula F of scheme 4.
[0313] Add TFA (excess) to a solution of a compound of formula F of scheme 4 (1.0 mmol) in CH 2 Cl 2 (5 ml) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 1:1). Remove the solvent and residual TFA in vacuum. Dissolve the residue in DCM and wash with saturated solution of NaHCO 3 . Dry the organic layer with MgSO 4 and concentrate in vacuum. Obtain a compound of formula G of scheme 4.
SYNTHESIS OF EXAMPLE 47
Preparation 11
[0314]
[0315] Add 4-(trifluoromethyl)benzonitrile (0.51 g, 3.0 mol) and potassium tert-butoxide (0.023 g, 0.21 mmol) to a solution of A above (0.5 g, 1.5 mmol) in MeOH (5 mL) and stir the mixture at reflux overnight. Add an additional 0.2 equivalents of potassium tert-butoxide and stir the reaction for 24 h. Quench the crude with water, remove the MeOH in vacuo and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuo. Purify the crude by Biotage (Hexane/EtOAc 4:1) yielding 0.32 g (44%) preparation 11 as a pale yellow oil. MS Data (ES + ) m/z 490.6 [M+H].
Preparation 12
[0316]
[0317] Add powdered KOH (0.14 g, 2.45 mmol), MeI (0.14 mL, 2.3 mmol) and Bu 4 NBr (0.05 g, 0.15 mmol) to a solution of preparation 11 (0.75 g, 1.5 mmol) in THF (5 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuo. Purify the crude by flash chromatography (Hexane/EtOAc 9:1) to obtain 0.51 g (66% yield) of preparation 12 a white solid.
Preparation 13
[0318]
[0319] Add I 2 (0.2 g, 0.8 mmol) and AgSO 4 (0.25 g, 0.8 mmol) to a solution of preparation 12 (0.25 g, 0.5 mmol) in EtOH (5 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 9:1) to obtain 0.15 g (48% yield) of preparation 13 as a white solid.
Preparation 14
[0320]
[0321] Add MeB(OH) 2 (0.04 g, 0.71 mmol), CsF (0.11 g, 0.71 mmol) and PdCl 2 (dppf) (0.03 g, 0.04 mmol) to a solution of the preparation 13 (0.15 g, 0.24 mmol) in anhydrous Dioxane (2 mL) under N 2 and stir the mixture to 80° C. overnight. Follow the reaction by LC/MS. Cool and then filter the reaction through celite and remove the solvent under vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 4:1 mixtures) to obtain 0.09 g (72% yield) of preparation 14 as a white solid.
EXAMPLE 47
[0322]
[0323] Add TFA (excess) to a solution of preparation 14 (0.09 g, 0.17 mmol) in CH 2 Cl 2 (5 ml) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Remove the solvent and residual TFA in vacuum. Dissolve the residue in DCM and wash with saturated solution of NaHCO 3 . Dry the organic layer with MgSO 4 and concentrate in vacuum. Obtain example 47 as a solid, 0.05 g (92% yield).
[0324] Prepare Examples 39-46 and 48-52 by a similar procedure for the preparation of example 47.
Example Structure LC/MS [M + 1] 39 434.3 40 448.1 41 578.2 42 Confirmed by 1 H-NMR 43 492.0 44 Confirmed by 1 H-NMR 45 Confirmed by 1 H-NMR 46 552.5 47 428.3 48 528.3 49 556.2 50 476.2 51 592.3 52 524.2
[0325]
R in scheme 5 is R1 or R32.
General Procedure for Scheme 5
[0326] Add I 2 (1.1 mmol) and AgSO 4 (1.1 mmol) to a solution of a compound of formula A of scheme 5 (1.0 mmol) in EtOH (8 mL/mmol) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 9:1) to obtain a compound of formula B of scheme 5.
[0327] Add MeB(OH) 2 (3.0 mmol), CsF (3.0 mmol) and PdCl 2 (dppf)(0.16 mmol) to a solution of a compound of formula B of scheme 5 (1.0 mmol) in anhydrous Dioxane (10 mL/mmol) under N 2 and stir the mixture to 80° C. overnight. Follow the reaction by LC/MS. Cool, filter the reaction through celite, and remove the solvent under vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 19:1 mixtures) to obtain a compound of formula C of scheme 5.
[0328] Dissolve the compound of formula C of scheme 5 (1.0 mmol) in EtOH (0.8 M). Then, add hydrazine monohydrate (3.0 mmol) and stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 4:1). Remove the solvent under vacuum. Dissolve the residue in EtOAc and wash with water. Dry the organic layer and concentrate and use the crude without further purification. Add 4-(trifluoromethyl)benzonitrile (2.0 mol) and potassium tert-butoxide (0.6 mmol) to a solution of acylhydrazine compound of formula D of scheme 5 (1.0 mmol) in MeOH (2.4 M). Stir the mixture at reflux 24 hours. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water, remove the MeOH in vacuo, and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 4:1 and 2:1) to obtain a compound of formula E of scheme 5.
[0329] Add TFA (excess) to a solution of compound of formula E of scheme 5 (1.0 mmol) in CH 2 Cl 2 (5 ml) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 1:1). Remove the solvent and residual TFA in vacuum. Dissolve the residue in DCM and wash with a saturated solution of NaHCO 3 . Dry the organic layer with MgSO 4 and concentrate in vacuum. Obtain the compound of formula F of scheme 5 as a pure solid.
[0330] Add powdered KOH (2.2 mmol), R—I (Br)(2.0 mmol) and Bu 4 NBr (0.2 mmol) to a solution of the corresponding triazole derivate compound of formula E of scheme 5 (1.0 mmol) in THF (5 mL/mmol) and stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×), separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 7:1 and 4:1) to obtain compound of formula G of scheme 5 as a white solid.
[0331] Add TFA (excess) to a solution of compound of formula G of scheme 5 (1.0 mmol) in CH 2 Cl 2 (5 ml) and stir the mixture at room temperature- overnight. Follow the reaction by TLC (Hexane/EtOAc 1:1). Remove the solvent and residual TFA in vacuum. Dissolve the residue in DCM and wash with a saturated solution of NaHCO 3 . Dry the organic layer with MgSO 4 and concentrate in vacuum. Obtain compound of formula H of scheme 5 as a solid.
Synthesis of Example 54
Preparation 15
[0332]
[0333] Add I 2 (18.2 g, 71.4 mmol), and AgSO 4 (22.2 g, 71.4 mmol) to a solution of the corresponding triazole derivate (compound A above)(20 g, 64.4 mmol) in EtOH (65 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 9:1) to obtain preparation 15 as a white solid (m=15.8 g, Yield 56%).
Preparation 16
[0334]
[0335] Add MeB(OH) 2 (3.48 g, 58.2 mmol), CsF (13.8 g, 91.0 mmol) and PdCl 2 (dppf) (4.75 g, 5.82 mmol) to a solution of preparation 15 (15.8 g, 36.4 mmol) in anhydrous Dioxane (40 mL4) under N 2 and stir the mixture to 80° C. overnight. Follow the reaction by LC/MS. Cool and then filter the reaction through celite and remove the solvent under vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 19:1 mixtures) to obtain 7.75 g (66% yield) of preparation 16 as a white solid.
Preparation 17
[0336]
[0337] Dissolve preparation 16 (7.75 g, 24.04 mmol) in EtOH (50 mL). Then, add hydrazine monohydrate (4.66 mL, 96.2 mmol). Stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 9:1). Remove the solvent under vacuum. Dissolve the residue in EtOAc and wash with water. Dry the organic layer and concentrate. Preparation 17 is used without further purification.
Preparation 18
[0338]
[0339] Add 4-(trifluoromethyl)benzonitrile (8.2 g, 48.08 mmol) and potassium tert-butoxide (1.62 g, 14.42 mmol) to a solution of preparation 17 (24.04 mmol) in EtOH (50 mL) and stir the mixture at reflux for 48 hours. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water and remove the MeOH in vacuo and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 4:1 and 2: 1) to obtain 2.5 g (22% yield) of preparation 18.
Preparation 19
[0340]
[0341] Add powdered KOH (0.065 g, 1.16 mmol), PrI (0.10 mL, 1.04 mmol) and Bu 4 NBr (0.033 g, 0.10 mmol) to a solution of preparation 18 (0.25 g, 0.52 mmol) in THF (5 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuo. Purify the crude by flash chromatography (Hexane/EtOAc 9:1) to obtain 0.13 g (48% yield) of preparation 19.
EXAMPLE 54
[0342]
[0343] Add TFA (excess) to a solution of preparation 19 (0.09 g, 0.17 mmol) in CH 2 Cl 2 (5 ml) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 1:1). Remove the solvent and residual TFA in vacuum. Dissolve the residue is in DCM and wash with a saturated solution of NaHCO 3 . Dry the organic layer with MgSO 4 and concentrate in vacuum. Obtain example 54 as a solid, 0.06 g (72% yield).
[0344] Prepare Example 53 by a similar procedure for the preparation of example 54.
Example Structure LC/MS [M + 1] 53 448.4 54 490.3
[0345]
R in scheme 6 is R1 or R32.
General Procedure for Scheme 6
[0346] Add BnBr (72.7 mL, 0.61 mol, 1.1 eq) and Ag 2 O (141.6 g, 0.61 mol, 1.1 eq) to a solution of methyl glycolate (50 g, 0.56 mol) in EtOAc (300 mL) and stir the mixture to reflux overnight. Follow the reaction by TLC (Hexane/EtOAC 1:1). Filter the reaction through celite and remove the solvent under vacuum. Pass adsorb the oil onto flash silica and place on top of a pad of flash silica (500 g) and elute with 20% ethyl acetate/hexane to give 75.8 g (75% yield) of compound A of scheme 6.
[0347] Dissolve the benzyl derivate compound of formula A of scheme 6 (1.0 mmol) in EtoH (0.8 M) and then add hydrazine monohydrate (3.0 mmol). Stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Remove the solvent under vacuum. Dissolve the residue in EtOAc and wash with water. Dry the organic layer and concentrate and use the crude without further purification. Add 4-(trifluoromethyl)benzonitrile (2.0 mol) and potassium tert-butoxide (0.6 mmol) to a solution of acylhydrazine compound of formula B of scheme 6 (1.0 mmol) in MeOH (2.4 M) and stir the mixture at reflux for 24 hours. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water, remove the MeOH in vacuum, and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 4:1) and obtain the compound C of scheme 6.
R═Me or MeOCH 2 CH 2
[0348] Triazole alkylation: Add powdered KOH (2.2 mmol), R—I (Br) (2.0 mmol) and Bu 4 NBr (0.2 mmol) to a solution of the corresponding triazole compound (C) of scheme 6 (1.0 mmol) in THF (5 mL/mmol) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 4:1) to obtain compound of formula D of scheme 6.
[0349] Add Pd (C) (10-20% in weight) and NH 4 + COO − (10-20 mmol) to a solution of triazole compound of formula D of scheme 6 (1.0 mmol) in EtOH (5 mL/mmol) and stir the mixture at 80° C. overnight. Follow the reaction by TLC. Filter the reaction through celite and remove the solvent under vacuum. Purify the crude by Biotage (Hexane/EtOAc 1:1) to obtain compound of formula E of scheme 6.
[0350] Add NaH (2.1 mmol, 60%) to a solution of triazole derivate compound of formula E of scheme 6 (1.0 mmol) in anhydrous DMF (10 mL) at 0° C., stir the mixture at room temperature for 15 minutes, cool to 0° C., and add the benzyl bromide (compound F of scheme 6) (1.5 mmol) in anhydrous DMF (5 mL). Stir the reaction at room temperature for 30 min, add MeOH, and then add water. Remove the MeOH in vacuum and extract the aqueous layer with EtOAc. Wash the organic layer with water and brine, dry over MgSO 4 , filter, and concentrate under reduced pressure. Purify the crude by Biotage (Hexane/EtOAc 4:1) to obtain compound of formula G of scheme 6.
[0351] Add 2N KOH solution (10 mmol) to a solution of triazole derivate compound of formula G of scheme 6 (1.0 mmol) in EtOH/THF mixture (1:1) (10 mL/mmol) and stir the mixture at room temperature overnight. Follow the reaction by TLC. Remove the solvent under vacuum and then, add water and EtOAc. Add 1N HCl solution until pH 5-7. Extract the mixture and wash the organic layer with water, separate, dry with MgSO 4 , and concentrate in vacuum. Obtain the products of compound of formula H of scheme 6 as white solids.
SYNTHESIS OF EXAMPLE 55
Preparation 19
[0352]
[0353] Add BnBr (72.7 mL, 0.61 mol, 1.1 eq) and Ag 2 O (141.6 g, 0.61 mol, 1.1 eq) to a solution of methyl glycolate (50 g, 0.56 mol) in EtOAc (300 mL) and stir the mixture to reflux overnight. Follow the reaction by TLC (Hexane/EtOAC 1:1). Filter the reaction through celite and remove the solvent under vacuum. The oil is passed adsorbed onto flash silica. Place on top of a pad of flash silica (500 g) and elute with 20% ethyl acetate/hexane to give 75.8 g (75% yield) of preparation 19 as a colorless oil.
Preparation 20
[0354]
[0355] Dissolve preparation 19 (7.5 g, 41.6 mmol) in EtOH (100 mL). Then, add hydrazine monohydrate (6.05 mL, 124.9 mmol) and stir the mixture at room temperature overnight. Follow the reaction by TLC (hexane/EtOAc 4:1). Remove the solvent under vacuum. Dissolve the residue in EtOAc and wash with water. Dry the organic layer and concentrate. Use preparation 20 without further purification.
Preparation 21
[0356]
[0357] Add 4-(trifluoromethyl)benzonitrile (14.2 g, 83.2 mmol) and potassium tert-butoxide (2.8 g, 25 mmol) to a solution of preparation 20 in MeOH (100 mL) and stir the mixture at reflux for 24 hours. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water, remove the MeOH in vacuum and extract the aqueous layer with EtOAc. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by flash chromatography (Hexane/EtOAc 4:1) to obtain 11.2 g (81% yield) of preparation 21 as a white solid.
Preparation 22
[0358]
[0359] Add powdered KOH (0.27 g, 4.8 mmol), MeI (0.28 mL, 4.5 mmol) and Bu 4 NBr (0.09 g, 0.3 mmol) to a solution of preparation 21 (1.0 g, 3.0 mmol) in THF (15 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/EtOAc 4:1). Quench the crude with water and add EtOAc. Extract the aqueous layer with EtOAc (2×). Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by Biotage (Hexane/EtOAc 4:1) to obtain preparation 22 (1.04 g).
Preparation 23
[0360]
[0361] Add Pd (C) (10-20% in weight) and NH 1 + COO − (1.89 g, 30 mmol) to a solution of preparation 22 (1.04 g, 3.0 mmol) in EtOH (15 mL) and stir the mixture at 80° C. overnight. Follow the reaction by TLC. Filter the reaction through celite and remove the solvent under vacuum. Purify the crude by Biotage (Hexane/EtOAc 1:1) to obtain preparation 23 (0.59 g, 76% yield).
[0362] Add NaH (0.091 g, 2.29 mmol, 60%) to a solution of preparation 23 (0.28 g, 1.09 mmol) in anhydrous DMF (10 mL) at 0° C. and stir the mixture at room temperature for 15 minutes. Cool again at 0° C. and add the benzyl bromide compound A (0.68 g, 1.63 mmol) in anhydrous DMF (5 mL) and stir the reaction at room temperature for 30 min. Add MeOH and then add water. Remove the MeOH in vacuum and extract the aqueous layer with EtOAc. Wash the organic layer with water and brine, dry over MgSO 4 , filter and concentrate under reduced pressure. Purify the crude by Biotage (Hexane/EtOAc 4:1) to obtain preparation 24 as white solids (0.39 g, 70% yield).
EXAMPLE 55
[0363]
[0364] Add 2N KOH solution (1.05 mL, 2.1 mmol) to a solution of preparation 24 (0.1 g, 0.21 mmol) in EtOH/THF mixture (1:1) (2 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC. Remove the solvent under vacuum and then, add water and EtOAc. Add 1N HCl until pH 5-7. Extract the mixture and wash the organic layer with water, separate, dry with MgSO 4 , and concentrate in vacuum. Example 55 is obtained as white solids (65 mg, 69% yield).
[0365] Prepare Example 56 by a similar procedure for the preparation of example 55.
Example Structure LC/MS [M + 1] 55 450.1 56 494.2
[0366]
Preparation 25
[0367]
[0368] Slurry sodium hydride (369 mg, 9.2 mmol) in DMF (25 ml) at 0° C., and then add 4-methoxyphenol (1.15 g, 9.2 mmol) in one portion. After stirring for 30 min., add ethyl 2-bromopropionate (1.391 g, 7.7 mmol) in one portion and allow the reaction to warm to room temperature overnight. Quench the reaction with 1N HCl and extract with ethyl acetate. Combine the organic layers, dry over MgSO 4 , and evaporate. Purify the residue via silica gel chromatography (30% ethyl acetate in hexanes) to give the 983.1 mg of preparation 25 as a thick, clear oil (57.2%). MS=225 (M+H + ); 242 (M+NH 4 + ).
Preparation 26
[0369]
[0370] Dissolve preparation 26 (983 mg, 4.4 mmol) in methanol (10 ml) and add to this 1N NaOH (10 ml). Stir at room temperature for 12 hrs. Then, evaporate the solvent, dissolve the residue in 1N HCl (20 ml), and extract with ethyl acetate. Combine the organics, dry over MgSO 4 , and evaporate. Use this crude product (767.5 mg, 89%) without further purification. MS=195 (M−H − ); 214 (M+NH 4 + ).
Preparation 27
[0371]
[0372] Dissolve preparation 26 (100 mg, 0.5 mmol) in dichloromethane (10 ml) and add EDC (117 mg, 0.6 mmol) followed by HOBT (83 mg, 0.6 mmol) and stir for for 5 min. Then, add 4-(trifluoromethyl)benzhydrazine (104 mg, 0.5 mmol) in one portion followed by pyridine (0.124 ml, 1.5 mmol) and stir at room temperature overnight. After this time, wash the reaction with saturated sodium bicarbonate solution and 1N HCl. Dry the organics over MgSO 4 and evaporate. Purify the residue via silica gel chromatography (50% ethyl acetate in hexanes) to give the 127.8 mg of preparation 27 as white solid (65.6%). MS=383 (M+H + ); 381 (M−H − ).
Preparation 28
[0373]
[0374] Dissolve the preparation 27 (127 mg, 0.33 mmol) in toluene (5 ml). To this add Lawesson's reagent (134 mg, 0.33 mmol) and the heat the reaction to reflux for 2 hrs. After this time, cool the reaction and dilute with 20 ml of ethyl acetate. Wash with saturated bicarbonate solution and dry the organics over MgSO 4 and evaporate. Purify. the residue via silica gel chromatography (15% ethyl acetate in hexanes) to give the 103.8 mg of preparation 28 as a white solid (82.2%). MS=381 (M+H + ).
Preparation 29
[0375]
[0376] Dissolve preparation 28 (100 mg, 0.26 mmol) in dichloromethane (5 ml). This is then cooled to 0° C. and add boron tribromide (0.788 ml, 0.79 mmol). After 2 hrs, quench the reaction with saturated bicarb and extract with 20 ml of ethyl acetate. The organics are dried over MgSO 4 and evaporated. This gave 87.2 mg of preparation 29 as an off white solid (98.4%). MS=337 & 338 (M+H + ).
Preparation 30
[0377]
[0378] Dissolve 2-(4-hydroxy-2-methyl-phenoxy)-2-methyl-propionic acid ethyl ester (73.6 mg, 0.31 mmol) in DMF. To this add sodium hydride (12.4 mg, 0.31 mmol) and stir at room temperature for 5 min. After this time preparation 29 (87 mg, 0.26 mmol) is added in one portion and the reaction continued for 2 hrs. Quench the reaction with saturated ammonium chloride and extract with ethyl acetate. Dry the organics over MgSO 4 and evaporate. Purify the residue via silica gel chromatography (15% ethyl acetate in hexanes) to give the 59.7 mg of preparation 30 as a clear oil (46.8%). MS=495 (M+H + ).
EXAMPLE 57
[0379]
Racemic
[0380] Dissolve preparation 30 (59 mg, 0.12 mmol) in methanol (2 ml). To this, add 1N NaOH solution (2 ml). After 12 hrs the reaction is brought to pH=6 with 1N HCl solution and extracted ethyl acetate. Dry the organics over MgSO 4 and evaporate. Purify the residue via silica gel chromatography (50% ethyl acetate in hexanes) then reverse phase HPLC (40-90% gradient @ 140 ml/min for 30 min on a 50×250 mm, mm, C18 Symmetry column) to give the 7.1 mg of example 57 as a white solid (12.7%). MS=467 (M+H + ).
Preparation 31
[0381]
[0382] Place 4-(Trifluoromethyl)benzhydrazide (5 g, 24.5 mmol) in a round bottom flasked equipped with a short path reflux condenser. Add to this was trimethyl orthoformate (4 ml, 36.7 mmol) followed by p-toluene sulfonic acid (46.6 mmg, 0.24 mmol). Heat to 100° C. and distill off the methanol. After 2 hrs, no more methanol is collected the pressure of the system is lowered to 300 microns to remove the unused trimethyl orthoformate. Cool the residual solid and dissolve in ethyl acetate. Wash with saturated bicarbonate solution and combine the organics, dry over MgSO 4 , and evaporate. Use the crude product (5.2 g, 99%) without further purification. MS=215 (M+H + ).
Preparation 32
[0383]
[0384] Dissolve preparation 31 (500 mg, 2.3 mmol) in THF and cool to −78° C. To this, add t-BuLi (1.5 ml, 1.7 M soln) and stir for 30 min. After this time, add acetaldehyde (0.157 ml, 2.8 mmol) and allow the reaction to slowly warm to room temperature over 6 hrs. After this time, quench the reaction with saturated ammonium chloride solution and then extract with ethyl acetate. Dry the combined organics over MgSO 4 and evaporate. Purify the residue via silica gel chromatography (20% ethyl acetate in hexanes) to give 24 mg of preparation 32 as white solid (3.9%).
Preparation 33
[0385]
[0386] Dissolve preparation 32 (24 mg, 0.09 mmol) in toluene (2 ml) and add 2-(4-hydroxy-2-methyl-phenoxy)-2-methyl-propionic acid ethyl ester (26.5 mg, 0.11 mmol). Bubble nitrogen into this mixture for 15 min. After this time, add ADDP (35.1 mg, 0.135 mmol) followed by Bu3P (0.034 ml, 0.135 mmol) and stir the reaction for 18 hrs at room temperature. After this time, dilute the reaction in 20 ml of ethyl acetate and wash with brine. Dry the organics over MgSO4 and evaporate. Purify the residue via silica gel chromatography (20% ethyl acetate in hexanes) to give 24.4 mg of preparation 33 as a white solid (54.9%). MS=479 (M+H + ).
EXAMPLE 58
[0387]
Racemic
[0388] Dissolve the preparation 33 (59 mg, 0.12 mmol) in methanol (2 ml). To this, add 1N NaOH solution (2 ml). After 12 hrs the reaction is brought to pH=6 with 1N HCl solution and extracted ethyl acetate. Dry the organics over MgSO 4 and evaporate. Purify the residue via silica gel chromatography (50% ethyl acetate in hexanes) then reverse phase HPLC (40-90% gradient @ 140 ml/min for 30 min on a 50×250 mm, mm, C18 Symmetry column) to give the 8.6 mg of example 58 as a white solid (9.5%). MS=451 (M+H + ).
EXAMPLE 59
[0389]
[0390] Example 59 can be made by one of ordinary skill in the art using the same procedure as example 57 using 2-(4-hydroxymethyl-phenoxy)-2-methyl-propionic acid ethyl ester (162 mg, 0.67 mmol) as the nucleophile and 2-bromomethyl-5-(4-trifluoromethyl-phenyl)-[1,3,4]thiadiazole (200 mg, 0.62 mmol) as the electrophile (as described in preparation 30) and then doing the saponification as described in example 57. After purification via silica gel chromatography (20% ethyl acetate in hexanes), 60.2 mg (21.5%) of example 59 is obtained as a thick oil. MS=451 (M−H − ).
EXAMPLE 60
[0391]
[0392] Example 60 can be made by one of ordinary skill in the art using the same procedure as example 57 using 2-Methyl-2-(4-methylaminomethyl-phenoxy)-propionic acid ethyl ester (171 mg, 0.67 mmol) as the nucleophile and 2-bromomethyl-5-(4-trifluoromethyl-phenyl)-[1,3,4]thiadiazole (200 mg, 0.62 mmol) as the electrophile (as described in preparation 30) and then doing the saponification as described in example 57. After purification via silica gel chromatography (10% methanol in dichloromethane), 75.3 mg (26.3%) of example 60 is obtained as a thick oil. MS=464 (M−H − ).
EXAMPLE 61
[0393]
[0394] Example 61 can be made by one of ordinary skill in the art using the same procedure as example 57 using 2-(4-Ethylaminomethyl-phenoxy)-2-methyl-propionic acid ethyl ester (180.6 mg, 0.67 mmol) as the nucleophile and 2-bromomethyl-5-(4-trifluoromethyl-phenyl)-[1,3,4]thiadiazole (200 mg, 0.62 mmol) as the electrophile (as described in preparation 30) and then doing the saponification as described in example 57. After purification via silica gel chromatography (10% methanol in dichloromethane), 24.3 mg (8.3%) of example 61 is obtained as a thick oil. MS=478 (M−H − ).
Preparation 34
[0395]
[0396] Dissolve preparation 31 (500 mg, 2.3 mmol) in THF and cool to −78° C. To this, add t-BuLi (1.5 ml, 1.7 M soln) and stir for 30 min. After this time, add propianaldehyde (0.202 ml, 2.8 mmol) and allow the reaction to slowly warm to room temperature over 6 hrs. After this time, quench the reaction with saturated ammonium chloride solution and then extract with ethyl acetate. Dry the combined organics over MgSO 4 and evaporate. Purify the residue via silica gel chromatography (20% ethyl acetate in hexanes) to give 99.8 mg of preparation 34 as white solid (15.7%).
Preparation 35
[0397]
[0398] Dissolve preparation 34 (99 mg, 0.36 mnmol) in toluene (5 ml) and add 2-(4-hydroxy-2-methyl-phenoxy)-2-methyl-propionic acid ethyl ester (105 mg, 0.43 mmol). Bubble nitrogen into this mixture for 15 min. After this time, add ADDP (139 mg, 0.54 mmol) followed by Bu 3 P (111.5 mg, 0.54 mmol) and stir the reaction for 18 hrs at room temperature. After this time, dilute the reaction in 20 ml of ethyl acetate and wash with brine. Dry the organics over MgSO4 and evaporate. Purify the residue via silica gel chromatography (20% ethyl acetate in hexanes) to give 63.0 mg of preparation 35 as a white solid (34.8%). MS=493 (M+H + ).
EXAMPLE 62
[0399]
Racemic
[0400] Dissolve the preparation 35 (63 mg, 0.13 mmol) in methanol (2 ml). To this is then added 1N NaOH solution (2 ml). After 12 hrs the reaction is brought to pH=6 with 1N HCl solution and extracted ethyl acetate. The organics are dried over MgSO 4 and evaporated. Purify the residue via silica gel chromatography (50% ethyl acetate in hexanes) then reverse phase HPLC (40-90% gradient @ 140 ml/min for 30 min on a 50×250 mm, mm, C18 Symmetry column) to give the 9.7 mg of example 62 as a white solid (16.3%). MS=465 (M+H + ).
Preparation 36
[0401]
[0402] Add p-trifluoromethyl benzoyl chloride (11.3 mL, 76 mmol) to a 0° C. solution of the acyl hydrazine (compound 1 above) (13.7 g, 76 mmol) in CH 2 Cl 2 (200 mL) and pyridine (20 mL) over 15 min and stir the reaction for 30 min. Then, pour into 5N HCl (200 mL). Extract the solution with Et 2 O (250 mL) and EtOAc (250 mL). Wash the combined organic extracts with H 2 O (200 mL) followed by brine (200 mL), dry over Na 2 SO 4 , filter, and concentrate. Titrate the crude semisolid with 10% Et 2 O/hexanes, precipitating out the desired Preparation 36 (23.4 g, 88%) as a white solid. 1 H NMR (CDCl 3 ) δ 10.64 (s, 1H), 10.07 (s, 1H), 8.09 (m, 2H), 7.93 (m, 2H), 7.40 (m, 5H), 4.64 (s, 2H), 4.11 (s, 2H).
Preparation 37
[0403]
[0404] Heat a solution of Preparation 36 (12.0 g, 34.1 mmol) and Lawesson's reagent (16.5 g, 40.9 mmol) in toluene (200 mL) to reflux for 4 hr, then cool to room temperature and pour into H 2 O (400 mL). Extract the mixture with Et 2 O (200 mL) and EtOAc (400 mL). Wash the combined organic extracts with brine (250 mL), dry over Na 2 SO 4 , filter, and concentrate. Purification of the crude product by MPLC (0% to 10% to 15% to 20% EtOAc/hexanes gradient) affords Preparation 37 (11.2 g, 93%) as a clear oil. 1 H NMR (CDCl 3 ) δ 8.10 (d, J=8.4 Hz, 2H), 7.75 (d, J=8.4 Hz, 2H), 7.37 (m, 5H), 4.99 (s, 2H), 4.70 (s, 2H).
Preparation 38
[0405]
[0406] Add a solution of BBr3 (42 mL, 1 M in CH 2 Cl 2 , 42 mmol) over 15 min. to a 0° C. solution of Preparation 37 (9.8 g, 27.9 mmol) in CH 2 Cl 2 (120 mL). After an additional 15 min at 0° C., pour the contents into ½ satd. NaHCO 3 (500 mL). Extract the mixture with Et 2 O (250 mL) and EtOAc (300 mL). Wash the combined organic extracts with brine (250 mL), dry over Na 2 SO 4 , filter, and concentrate to afford a white solid. Titrate the crude product with 10% Et2O/hexanes, precipitating out the desired Preparation 38 (7.0 g, >95%) as a white solid. 1 H NMR (CDCl 3 ) δ 8.09 (d, J=8.4 Hx, 2H), 7.60 (d, J=8.4 Hz, 2H), 5.16 (s, 2H), 2.40-2.60 (br s, 1H).
Preparation 39
[0407]
[0408] Bubble nitrogen gas through a solution of Preparation 38 (0.125 g, 0.48 mmol) and phenol compound 2 (0.119 g, 0.50 mmol) in toluene (5 mL) for 10 min. Cool the solution to 0° C. and add tri-n-butyl phosphine (0.180 mL, 0.72 mmol) followed by (1,1′)-azodicarbonyl-dipiperidine (ADDP) (0.182 g, 0.72 mmol). After 5 min, allow the reaction to warm to room temperature and is stir for 16 hours. Then, pour the reaction mixture into ½ satd. NaHCO 3 (25 mL). Extract the mixture with Et 2 O (25 mL) and EtOAc (25 mL). Wash the combined organic extracts with brine (25 mL), dry over Na 2 SO 4 , filter, and concentrate. Purification of the crude product by MPLC (0% to 5% to 8% to 12% EtOAc/hexanes) affords preparation 39 (0.138 g, x %) as a white foam. 1 H NMR (CDCl 3 ) δ 8.11 (d, J=8.4 Hz, 2H), 7.77 (d, J=8.4 Hz, 1H), 6.72 (s, 1H), 6.65 (m, 1H), 6.56 (d, J=3.2 Hz, 1H), 5.48 (s, 2H), 4.27 (q, J=7.2 Hz, 2H), 2.19 (s, 3H), 1.55 (s, 6H), 1.32 (t, J=7.2 Hz, 3H).
EXAMPLE 63
[0409]
[0410] Heat a solution of Preparation 39 (0.138 g, 0.29 mmol) in EtOH (5 mL) and 2 N NaOH (1 mL) to 40° C. for 1 h. Pour the mixture into 1 N HCl (20 mL) and extract with Et 2 O (20 mL) and EtOAC (2×20 mL). Wash the combined organic extracts with brine (25 mL), dry over Na 2 SO 4 , filter, and concentrate. Purification of the crude product by column chromatography (35% EtOAc/2% HOAc in hexanes) affords example 59 (0.102 g, 77%) as a white solid. LRMS 453.1 (M++H).
Preparation 40
[0411]
Preparation 40
[0412] The reaction is run according to preparation 39. The reaction of Preparation 38 (0.125 g, 0.48 mmol) and phenol compound 3 (above) (0.112 g, 0.50 mmol) affords Preparation 40 (0.124 g, 55%) as a white foam. 1 H NMR (CDCl 3 ) δ 8.08 (d, J=8.2 Hz, 2H), 7.74 (d, J=8.2 Hz, 2H), 6.89 (m, 2H), 6.75 (m, 2H), 5.47 (s, 2H), 4.23 (q, J=7.2 Hz, 2H), 1.52 (s, 6H), 1.27 (t, J=7.2 Hz, 3H).
EXAMPLE 64
[0413]
[0414] The reaction is run according to that for example 63. Hydrolysis of preparation 40 (0.124 g, 0.27 mmol) affords example 60 (0.082 g, 69%) as a white foam. LRMS 439.1 (M++H).
Preparation 41
[0415]
[0416] Bubble HCl (g) through a 0° C. solution of p-trifluoromethylbenzonitrile (5.50 g, 32.1 mmol) in EtOH (9.4 mL, 161 mmol) and toluene (50 mL) for 30 min. Remove the cooling bath and maintain the solution at room temperature for 16 h. Concentration of the mixture affords the intermediate imidate salt, which is added to o-xylenes (165 mL). Add the acyl hydrazine compound 1 (procedure for preparation 36) (5.78 g, 32.1 mmol) as a solution in o-xylenes (10 mL). Add Et 3 N (4.47 mL, 32.1 mmol) dropwise over 30 min, stir the solution for 2 hours, heat to reflux for 2.5 hours, cool to room temperature and maintain for 16 hours. Pour the solution into ½ satd. NaHCO 3 (250 mL) and extract with EtOAc (2×200 mL). Wash the combined organic extracts with brine (250 mL), dry over Na 2 SO 4 , filter, and concentrate. Purification of the crude product by column chromatography (0% to 15% to 20% to 25% to 35% EtOAc/hexanes) affords preparation 41 (0.53 g, 5%) as a white solid. 1 H NMR (CDCl 3 ) δ 7.79 (d, J=8.0 Hz, 2H), 7.72 (d, J=8.0 Hz, 2H), 7.30-7.40 (m, 5H), 4.83 (s, 2H), 4.70 (s, 2H).
Preparation 42
[0417]
[0418] Expose a 40° C. solution of Preparation 41 (0.53 g, 1.59 mmol) and 10% Pd—C (0.10 g) in MeOH (30 mL) and THF (10 mL) to 40 psi H2 (g) for 24 h. Flushing of the mixture with N2 (g) followed by filtration through celite provides a clear solution, which is concentrated to afford preparation 42 (0.24 g, 62%) as a white solid. 1 H NMR (CDCl 3 ) δ 8.18 (d, J=8.0 Hz, 2H), 7.70 (d, J=8.0 Hz, 2H), 5.00 (s, 2H).
Preparation 43
[0419]
[0420] Preparation 43 is produced from preparation 42 (0.050 g, 0.20 mmol) and phenol 2 (0.051 g, 0.21 mmol) according to Preparation 39, affording preparation 43 (0.072 g, 76%) as a clear oil. 1 H NMR (CDCl 3 ) δ 8.20 (d, J=8.4 Hz, 2H), 7.78 (d, J=8.4 Hz, 2H), 6.85 (s, 1H), 6.68 (m, 2H), 5.27 (s, 2H), 4.25 (q, J=7.2 Hz, 2H), 2.22 (s, 3H), 1.54 (s, 6H), 1.28 (t, J=7.2 Hz, 3H).
Example 65
[0421]
[0422] Example 65 is produced from preparation 43 according to the procedure for making example 63, affording example 65 (0.070 g, >95%) as a white solid. LRMS 455.1 (M++H).
[0423] Prepare Example 66 by a method according to Scheme 4 and prepare Example 67 by a method according to Scheme 2.
Example Structure LC/MS [M + 1] 66 476.2 67 478.3
[0424] Prepare Examples 68-73 by the method described in Scheme 2 and prepare Examples 74-76 described in Scheme 6a andlor 6b.
Example Structure LC/MS [M + 1] 68 526.2 71 498.1 74 449.1 75 477.2 76 491.2
[0425]
General Procedure for Scheme 11
[0426] Suspend the hydrazide compound A (100 mmol) in trimethylortoformate (150 mmol) and p-toluenesulfonic acid monohydrate (1.5 mmol) to a round bottomed flask equipped with a standard distillation apparatus. Heat to 90° C. until formation of a precipitate is observed, then to 120° C. Distill the methanol. Follow the reaction by HPLC and TLC (Hex/AcOEt 1:1). Dissolve the yellow oil in AcOEt and wash with water, brine, dry with MgSO 4 and concentrate in vacuum. Purify the crude by SiO 2 chromatography (Hex/AcOEt 9:1 to 7:3) to obtain a compound of formula B of Scheme 11.
[0427] Add nBuLi (1.6M in hexane) dropwise (10 mmol) under N 2 atmosphere to a cooled (−78° C.) solution of the oxadiazole compound B (10 mmol) in THF (33 mL). After 40 min, add MgBr 2 .Et 2 O (10 mmol), warm the cooling bath to −45° C. and stir the resulting slurry at −45° C. for additional 1.5 h. Add the aldehyde (9 mmol) in THF (11 mL), raise the reaction temperature to −20° C. and stir for additional 2.5 h at this temperature. Follow the reaction by HLPC and TLC (Hex/AcOEt 8:2). Quench the crude material with a NH 4 Cl solution and add AcOEt. Extract the aqueous layer twice with AcOEt. Separate the organic layer, wash it with water, brine, dry with MgSO 4 , filter and concentrate in vacuum. Purify the crude material by SiO 2 chromatography (Hex/AcOEt 95:5 to 85:15) to obtain a compound of formula C of Scheme 11.
[0428] Mitsounobu reaction: Add to a solution of oxadiazole C (1.0 mmol) and the phenol (compound D) (2 mmol) in toluene (20 mL), degassed several times, Bu 3 P (2.0 mmol) and ADDP (2.0 mmol) to 0° C. Stir the mixture at room temperature overnight. Follow the reaction by TLC. Remove the solvent under vacuum, triturate the residue with diethyl ether and filter off the precipitate obtained. Wash the filtrate with a 2N NaOH solution, water, brine, dry over MgSO4, and concentrate in vacuum. Purify the crude by SiO 2 chromatography (Hexane/AcOEt 95:5 to 85:15) to obtain compound E of Scheme 11.
[0429] Hydrolysis: Add a 2N KOH solution (1.5 mL) to a solution of oxadiazole C (1.0 mmol) in EtOH/THF mixture (1:1) (40 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hex/AcOEt 1:1) and HPLC. Add AcOEt and water and adjust the pH to 6 by addition a 6N HCl solution. Separate the two phases, extract the aqueous layer twice with AcOEt, wash the organic layer with water, brine, dry over MgSO 4 , filter and concentrate in vacuum. Purify the crude by ISCO (Hex-TFA 0.05%/acetone 9:1 to 85:15) to obtain the acid compound F of Scheme 11.
Preparation of Head H2
[0430]
[0431] Dissolve the p-benzyloxyphenol (300 mmol) in CH 3 CN (750 mL), add Cs 2 CO 3 (360 mmol) portionwise, followed by the bromoderivative. Reflux the resulting mixture overnight. Cool, filter through a plug of Celite, and concentrate in vacuum. Purify by SiO 2 chromatography (Hex/AcOEt 8:2) to obtain the compound H1 in 94% yield.
[0432] Add Pd—C (10% in weight) to a solution of H1 (282 mmol) in EtOH (940 mL). Stir the mixture under H 2 atmosphere at room temperature overnight. Filter through a plug of Celite, remove the solvent and purify by Biotage (Hex/AcOEt 7:3) to obtain the compound H2 in 64% yield.
Preparation of Head H4
[0433]
[0434] Dissolve the starting aldehyde (45 mmol) in THF:EtOH (95:5 mL), cool to 0° C., and add NaBH 4 portionwise until the starting material is not detected by TLC. Quench at 0° C. with a 1N HCl and add AcOEt. Adjust the pH to 6. Separate the two phases, extract twice with AcOEt. Wash with water, brine, dry over MgSO 4 filter and concentrate under vacuum. Purify by SiO 2 chromatography to obtain the alcohol H3 in 95% yield.
[0435] Add Pd—C (10% in weight) to a solution of H3 (42.7 mmol) in EtOH (430 mL). Stir the mixture under H 2 atmosphere at room temperature for 6 h. Filter through a plug of Celite, remove the solvent and purify by SiO 2 chromatography (Hex/AcOEt 7:3) to obtain the compound H4 in 76% yield.
Preparation of Head H7
[0436]
[0437] Dissolve the thiol (100 mmol) in MeOH (170 mL), cool to 0° C. and add I 2 (0.5 mmol) and NaHCO 3 (2.8 mmol) portionwise. Stir the resulting mixture at room temperature overnight. Remove the solvent under vacuum and purify the residue by SiO 2 chromatography to obtain the compound H5 in 83% yield.
[0438] Dissolve the disulfide H5 (70 mmol) in CH 3 CN (110 mL), add Cs 2 CO 3 (3.5 mmol), stir for 10 minutes and then add the bromoderivative (210 mmol). Reflux overnight. Follow the reaction by TLC (Hexane/AcOEt 7:3). Cool to room temperature, filter through a plug of Celite, concentrate in vacuum and purify the residue by SiO 2 chromatography (Hexane to Hexane/AcOEt 4:1) to obtain the compound H6 in 51% yield.
[0439] Dissolve H6 (6 mmol) in THF:EtOH (16:5 mL), add NaBH 4 portionwise at 0° C. until starting material was not detected. Quench with a 1N HCl solution to 0° C. and add AcOEt. Adjust the pH to 4. Separate the two phases, extract twice with AcOEt. Wash with water, brine, dry over MgSO 4 , filter and concentrate. Purify by SiO 2 chromatography (Hex to Hex/AcOEt95:5) to obtain H7 in 99% yield.
Preparation 52
[0440] Suspend the hydrazide (5 g) in trimethylortoformate (4.0 ml) and p-toluenesulfonic acid monohydrate (47 mg) to a round bottomed flask equipped with a standard distillation apparatus. Heat to 90° C. until formation of a precipitate is observed, then to 120° C. Distill the methanol to obtain a yellow oil. Dissolve the yellow oil in AcOEt and wash with water, brine, dry with MgSO 4 and concentrate in vacuum. Purify the crude by SiO 2 chromatography (Hex/AcOEt 9:1 to 7:3) to obtain preparation 52 as a white solid. (95%).
Preparation 53
[0441]
[0442] Add nBuLi (1.51 ml, 1.7M in pentane) dropwise, under N 2 atmosphere to a cooled (−78° C.) solution of preparation 52 (500 mg) in THF (20 mL). After 40 min, add MgBr 2 .Et 2 O (10 mmol), warm the cooling bath to −45° C. and stir the resulting slurry at −45° C. for additional 1.5 h. Add aectaldehyde (0.157 ml) in THF (10 mL), raise the reaction's temperature to −20° C. and stir for additional 2.5 h at this temperature. Quench the crude material with a NH 4 Cl solution and add AcOEt. Extract the aqueous layer twice with AcOEt. Separate the organic layer, wash it with water, brine, dry with MgSO 4 , filter and concentrate in vacuum. Purify the crude material by SiO 2 chromatography (Hex/AcOEt 95:5 to 85:15) to obtain preparation 53. (22%)
Preparation 54
[0443] Mitsounobu reaction: Add to a solution of preparation 53 (24 mg) and the phenol (26.5 mg) in toluene (2 mL), degassed several times, Bu 3 P (0.035 ml) and ADDP (35 mg) to 0° C. Stir the mixture at room temperature overnight. Remove the solvent under vacuum, triturate the residue with diethyl ether and filter off the precipitate obtained. Wash the filtrate with a 2N NaOH solution, water, brine, dry over MgSO4, and concentrate in vacuum. Purify the crude by SiO 2 chromatography (Hexane/AcOEt 95:5 to 85:15) to obtain preparation 54. (55%).
EXAMPLE 77
[0444]
[0445] Add a 2N KOH solution (1.5 mL) to a solution of preparation 54 (24 mg) in EtOH/THF mixture (1:1) (4 mL) and stir the mixture at room temperature overnight. Add AcOEt and water and adjust the pH to 6 by addition a 1N HCl solution. Separate the two phases, extract the aqueous layer twice with AcOEt, wash the organic layer with water, brine, dry over MgSO 4 , filter and concentrate in vacuum. Purify the crude by Purify the crude by SiO 2 chromatography (Hexane/AcOEt 95:5 to 85:15) to obtain example 77. (90%).
[0446] Prepare Examples 78, 81, 84, 85, and 88-90 using a similar procedure to prepare example 77.
Example Structure LC/MS [M + 1] 77 451 78 478.5 81 492.5 84 494.5 85 518.4 88 532.4 89 534.5 90 512.5
[0447]
General Procedure for Scheme 12
[0448] Add the commercial ester starting material (10 mmol) to a suspension of the phenol A (10 mmol) and the K 2 CO 3 in CH 3 CN (10 mL). Reflux the mixture overnight. Follow the reaction by TLC (Hexane/AcOEt 9:1). Cool, filter through a plug of Celite and remove the solvent under vacuum. Purify the crude material by SiO 2 chromatography (Hexane to Hex/AcOEt 9:1) to obtain a compound of formula B of Scheme 12.
[0449] Dissolve the methyl ester B (10 mmol) in EtOH (12.5 mL). Then, add hydrazine monohydrate (40 mmol). Stir the mixture at room temperature overnight. Follow the reaction by TLC (Hexane/AcOEt 9:1). Remove the solvent under vacuum. Dissolve the residue in AcOEt and wash with water. Dry the organic layer over MgSO 4 and concentrate. Use the crude material without further purification.
[0450] Dissolve the hydrazide C (10 mmol) in THF (25 mL). Add Et 3 N at 0° C. and stir the resulting solution for 5 min, then add the acid chloride (11 mmol) at −30° C. dropwise. Stir the mixture at this temperature for 45 min and then at room temperature overnight. Follow the reaction by HPLC and TLC (Hex/AcOEt 1:1). Quench the crude material with water and add AcOEt. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude material by SiO 2 chromatography (Hex/AcOEt 9:1 to 7.3) to obtain a compound of formula D of Scheme 12.
[0451] Dissolve the compound D (10 mmol) in toluene (100 mL), add the Lawesson's reagent (20.0 mmol). Reflux the mixture for 4 h. Follow the reaction by TLC (Hexane/AcOEt 4:1). Remove the solvent under vacuum. Purify the residue by SiO 2 chromatography (Hex to Hex/AcOEt 85:15) to obtain a compound of formula E in Scheme 12.
[0452] Add 2N KOH solution (1.5 mL) to a solution of thiodiazole E (1.0 mmol) in EtOH/THF mixture (1:1) (40 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hex/AcOEt 1:1) and HPLC. Add AcOEt and water and adjust the pH to 6 by addition a 6N HCl solution. Separate the two phases, extract the aqueous layer twice with AcOEt, wash the organic layer with water, brine, dry over MgSO 4 , filter and concentrate in vacuum. Purify the crude by ISCO (Hex-TFA 0.05%/acetone 9:1 to 85:15) to obtain the acid F of Scheme 12.
EXPERIMENTAL PROCEDURE FOR EXAMPLE 91
Preparation 55
[0453]
[0454] Add the commercial starting material (167 mg) to a suspension of the phenol A (224 mg) and the K 2 CO 3 in CH 3 CN (10 mL). Reflux the mixture overnight. Cool, filter through a plug of Celite and remove the solvent under vacuum. Purify the crude material by SiO 2 chromatography (Hexane to Hex/AcOEt 9:1) to obtain preparation 55 in a yield 95%.
Preparation 56
[0455]
[0456] Dissolve the preparation 55 (300 mg) in EtOH (12.5 mL). Then, add hydrazine monohydrate (190 mg). Stir the mixture at room temperature overnight. Remove the solvent under vacuum, dissolve the residue in AcOEt and wash with water. Dry the organic layer over MgSO 4 and concentrate. Use the crude material without further purification.
Preparation 57
[0457]
[0458] Dissolve preparation 56 (300 mg) in THF (25 mL). Add Et 3 N at 0° C. and stir the resulting solution for 5 min, then add the commercially available acid chloride (160 mg) at −30° C. dropwise. Stir the mixture at this temperature for 45 min and then at room temperature overnight. Quench the crude material with water and add AcOEt. Separate the organic layer, dry with MgSO 4 , and concentrate in vacuum. Purify the crude material by SiO 2 chromatography (Hex/AcOEt 9:1 to 7.3) to obtain preparation 57 which yields 60% for the two steps.
Preparation 58
[0459]
[0460] Dissolve preparation 57 (127 mg) in toluene (5 mL) and add the Lawesson's reagent (134 mg). Reflux the mixture for 4 h. Remove the solvent under vacuum and purify the residue by SiO 2 chromatography (Hex to Hex/AcOEt 85:15) to obtain preparation 58 in 60% yield.
EXAMPLE 91
[0461]
[0462] Add a 2N KOH solution (1.5 mL) to a solution of preparation 58 (24 mg) in EtOH/THF mixture (1:1) (4 mL) and stir the mixture at room temperature overnight. Add AcOEt and water and adjust the pH to 6 by addition a 1N HCl solution. Separate the two phases, extract the aqueous layer twice with AcOEt, wash the organic layer with water, brine, dry over MgSO 4 , filter and concentrate in vacuum. Purify the crude by SiO 2 chromatography to obtain example 91. (90%).
[0463] Prepare Example 94 using a similar procedure to prepare example 91.
Example Structure LC/MS [M + 1] 91 494.5 94 508.6
[0464]
EXPERIMENTAL PROCEDURE FOR SCHEME 13
[0465] Add the hydrazide (100 mmol), trimethylortoformate (150 mmol) and p-toluenesulfonic acid monohydrate (1.5 mmol) to a round bottomed flask-equipped with a standard distillation apparatus. Heat to 90° C. until a precipitate is obtained, then heat to 120° C. Distill the methanol to obtain an oil. Follow the reaction by HPLC and THC (Hex/AcOEt 1:1). Dissolve the oil in AcOEt and wash with water, brine, dry with MgSO 4 , and concentrate in vacuum. Purify the crude by SiO 2 chromatography (Hex/AcOEt 9:1 to 7:3) to obtain an oxadiazole compound of formula A of Scheme 13.
[0466] Add nBuLi (1.6M in hexane) dropwise (10 mmol) under N 2 atmosphere to a cooled (−78° C.) solution of the oxadiazole (10 mmol) in THF (33 mL). After 40 min, add MgBr 2 .Et 2 O (10 mmol), warm the cooling bath to −45° C. and stir the resulting slurry at −45° C. for additional 1.5 h. Add the aldehyde (9 mmol) in THF (11 mL), raise the reaction's temperature to −20° C. and stir for additional 2.5 h at this temperature. Follow the reaction by HLPC and TLC (Hex/AcOEt 8:2). Quench the crude material with a NH 4 Cl solution and add AcOEt. Extract the aqueous layer twice with AcOEt. Separate the organic layer, wash it with water, brine, dry with MgSO 4 , filter and concentrate in vacuum. Purify the crude material by SiO 2 chromatography (Hex/AcOEt 95:5 to 85:15) to obtain a compound of formula B of Scheme 13.
[0467] To a solution of oxadiazole B (1.0 mmol) and the bromoderivative C (1.1 mmol) in CH 3 CN (2.5 mL), add Cs 2 CO 3 (1.3 mmol), and stir at room temperature the resulting mixture overnight. Follow the reaction by TLC (Hexane/AcOEt 4:1). Filter through a plug of Celite. Remove the solvent under vacuum. Purify the crude by SiO 2 chromatography (Hexane/AcOEt 95:5 to 85:15) to obtain compound D of Scheme 13.
[0468] Add 2N KOH solution (1.5 mL) to a solution of oxadiazole D (1.0 mmol) in EtOH/THF mixture (1:1) (40 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hex/AcOEt 1:1) and HPLC. Add AcOEt and water and adjust the pH to 6 by addition a 6N HCl solution. Separate the two phases, extract the aqueous layer twice with AcOEt, wash the organic layer with water, brine, dry over MgSO 4 , filter and concentrate in vacuum. Purify the crude by ISCO (Hex-TFA 0.05%/acetone 9:1 to 85:15) to obtain the acid E of Scheme 13.
Preparation of the Bromoderivative
[0469]
Preparation of Head H9
[0470]
[0471] Dissolve the phenol (154 mmol) in EtOH (513 mL), add K 2 CO 3 (600 mmol) and MgSO 4 and then, the bromoderivative (231 mmol). Reflux the resulting mixture overnight. Cool, filter through a plug of Celite, concentrate in vacuum. Purify by SiO 2 chromatography (Hex/AcOEt 8:2) to obtain the compound H8 in 53% yield.
[0472] Dissolve H8 (13 mmol) in CH 2 Cl 2 (130 mL) at 0 20 C., add CBr 4 and then PPh 3 portionwise. Stir the mixture at 0° C. for 2 hours. Follow the reaction by TLC (Hex/AcOEt 4:1). Remove the solvent. Purify the residue by SiO 2 chromatography (Hexane/AcOEt 9:1) to obtain H9 in 95% yield.
EXPERIMENTAL PROCEDURE FOR EXAMPLE 97
Preparation 59
[0473]
[0474] Suspend the hydrazide (5 g) in trimethylortoformate (4.0 ml) and p-toluenesulfonic acid monohydrate (47 mg) to a round bottomed flask equipped with a standard distillation apparatus. Heat to 90° C. until formation of a precipitate is observed, then to 120° C. Distill the methanol to obtain a yellow oil. Dissolve the yellow oil in AcOEt and wash with water, brine, dry with MgSO 4 and concentrate in vacuum. Purify the crude by SiO 2 chromatography (Hex/AcOEt 9:1 to 7:3) to obtain preparation 59 as a white solid. (95%).
[0475] Preparation 60
[0476] Add nBuLi (1.51 ml, 1.7M in pentane) dropwise, under N 2 atmosphere to a cooled (−78° C.) solution of the oxadiazole (500 mg) in THF (20 mL). After 40 min, add MgBr 2 .Et 2 O (10 mmol), warm the cooling bath to −45° C. and stir the resulting slurry at −45° C. for additional 1.5 h. Add butyraldehylde (0.157 ml) in THF (10 mL), raise the reaction's temperature to −20° C. and stir for additional 2.5 h at this temperature. Quench the crude material with a NH 4 Cl solution and add AcOEt. Extract the aqueous layer twice with AcOEt. Separate the organic layer, wash it with water, brine, dry with MgSO 4 , filter and concentrate in vacuum. Purify the crude material by SiO 2 chromatography (Hex/AcOEt 95:5 to 85:15) to obtain preparation 60. (25%).
Preparation 61
[0477]
[0478] To a solution of preparation 60 (80 mg) and the bromoderivative (217 mg) in CH 3 CN (5 mL), add Cs 2 CO 3 (213 mg), and stir at room temperature the resulting mixture overnight. Filter through a plug of Celite. Remove the solvent under vacuum. Purify the crude by SiO 2 chromatography (Hexane/AcOEt 95:5 to 85:15) to obtain preparation 61 in yield 90%.
EXAMPLE 97
[0479]
[0480] Add a 2N KOH solution (1.5 mL) to a solution of preparation 61 (24 mg) in EtOH/THF mixture (1:1) (4 mL) and stir the mixture at room temperature overnight. Add AcOEt and water and adjust the pH to 6 by addition a 1N HCl solution. Separate the two phases, extract the aqueous layer twice with AcOEt, wash the organic layer with water, brine, dry over MgSO 4 , filter and concentrate in vacuum. Purify the crude by Purify the crude by SiO 2 chromatography to obtain example 97. (85%).
[0481] Prepare Example 100 using a similar procedure to prepare example 97.
Example Structure LC/MS [M + 1] 97 492.5 100 512.5
[0482]
EXPERIMENTAL PROCEDURE FOR SCHEME 14
[0000] For W=O:
[0483] Slurry the commercially available hydrazide (1 eq) in DCM and then add the acid chloride (1.1 eq) followed by the triethyl amine (2 eq). Stir under nitrogen at room temperature for 12 hrs. Then quench the reaction with 1N HCl and extract with DCM. Dry the organic layer over MgSO 4 and evaporate. Recrystalize the solid recrystalized from EtOAc.
[0484] Dissolve this material in pyridine and add tosyl chloride (1.5 eq.) and reflux the mixture refluxed for 18 hrs. Cool the reaction, dilute with ethyl acetate, and wash with 1N HCl, sat. bicarb, and water. Dry the organics over MgSO 4 and evaporate. Purify the residue via column chromatography (20% ethyl acetate in hexanes) to obtain the compound of formula A in scheme 14.
[0485] Dissolve this material in DCM and cool to 0° C. Add BBr 3 (3 eq) over 10min. Allow the reaction to warm to room temperature over 2 hrs. Dilute the reaction with ethyl acetate and wash with sat. bicarb. and 1N HCl. Dry the organic over MgSO 4 and evaporate.
[0486] Dissolve the solid in DCM and add PBr 3 (1.2 eq). Stir this at room temperature for 2 hrs, wash with water, dry the organics over MgSO 4 , and evaporate to give compound of formula B or scheme 14 without purification.
[0000] ForW=S:
[0487] Slurry the hydrazide (1 eq) in DCM and add the acid chloride (1. 1 eq) followed by the triethyl amine (2 eq). Stir this under nitrogen at room temperature for 12 hrs. Quench the reaction with 1N HCl and extract with DCM. Dry the organic layer over MgSO 4 and evaporate. Recrystalize the solid from EtOAc.
[0488] Dissolve this material in pyridine, add tosyl chloride (1.5 eq.), and reflux the mixture for 18 hrs. Cool the reaction, dilute with ethyl acetate, and wash with 1N HCl, sat. bicarb, and water. Dry the organics over MgSO 4 and evaporate. Purify the residue via column chromatography (20% ethyl acetate in hexanes) to obtain the compound of formula A of scheme 14.
[0489] Dissolve the material in DCM and cool to 0° C. Add BBr 3 (3 eq) over 10 min. Then, allow the reaction to warm to room temperature over 2 hrs. Dilute the reaction with ethyl acetate and wash with sat. bicarb. and 1N HCl. Dry the organic over MgSO 4 and evaporate.
[0000] Synthesis of Compound D:
[0490] Dissolve the appropriate amine headpiece (compound of formula C) in DMP and cool to 0° C. Add to this NaH (1 eq) and stir for 30 min. Add compound B (0.9 eq) and allow the reaction to slowly warm to room temperature. After complete comsumption of the starting material, quench the reaction with sat. ammonium chloride and extract with ethyl acetate. Dry the organic over MgSO 4 and evaporate. Purify the residue via column chromatography (20% ethyl acetate in hexanes) to give the compound of formula D of scheme 14.
[0000] Synthesis of Compound E:
[0491] Add 1N NaOH solution (1.5 mL) to a solution of compound of formula D (1.0 mmol) in MeOH/THF mixture (1:1) (40 mL) and stir the mixture at room temperature overnight. Follow the reaction by TLC (Hex/AcOEt 1:1) and HPLC. Add AcOEt and water and adjust the pH to 6 by addition a 1N HCl solution. Separate the two phases, extract the aqueous layer twice with AcOEt, wash the organic layer with water, brine, dry over MgSO 4 , filter and concentrate in vacuum. This residue is then purified via column chromatography (30% ethyl acetate in hexanes) to give the product E.
EXPERIMENTAL PROCEDURE FOR EXAMPLE 104
Preparation 62
[0492]
[0493] Slurry 4-trifluoromethylbenzhydrazine (1 g) in DCM (25 ml) and add to this mixture the benzyloxyacetyl chloride (0.837 ml), followed by the triethyl amine (1.37 ml). Stir this under nitrogen at room temperature for 12 hrs. Then, quench the reaction with 1N HCl and extract with DCM. Dry the organic layer over MgSO 4 and evaporate. Recrystalize the solid from EtOAc. (93%).
[0494] Dissolve this material in toluene and add Lawsen's reagent (3 g) and reflux the mixture for 18 hrs. Then, cool the reaction and dilute with ethyl acetate and wash with 1N HCl, sat. bicarb, and water. Dry the organics over MgSO 4 and evaporate. Purify this residue via column chromatography (20% ethyl acetate in hexanes) to give preparation 62 as a pale yellow solid. (80%).
Preparation 63
[0495]
[0496] Dissolve preparation 62 (100 mg) in DCM (5 ml) and cool to 0° C. Add to this BBr 3 (0.788 ml)) over 10 min. Allow the reaction to warm to room temperature over 2 hrs. Dilute the reaction with ethyl acetate and wash with sat. bicarb. and 1N HCl. Dry the organic over MgSO 4 and evaporate to give preparation 63 as an off white solid. (98%)
Preparation 64
[0497]
[0498] Dissolve the headpiece (429 mg) in acetonitrile (20 ml) and cool to 0° C. Add to this CsCO 3 (1 g), and preparation 63 (500 mg) and allow the reaction to slowly warm to room temperature. After complete comsumption of the starting material, quench the reaction with sat. ammonium chloride and extract with ethyl acetate. Dry the organic over MgSO 4 and evaporate. Purify the residue via column chromatography (20% ethyl acetate in hexanes) to give preparation 64. (62%)
EXAMPLE 104
[0499]
[0500] Add a 2N KOH solution (1.5 mL) to a solution of preparation 64 (24 mg) in EtOH/THF mixture (1:1) (4 mL) and stir the mixture at room temperature overnight. Add AcOEt and water and adjust the pH to 6 by addition a 1N HCl solution. Separate the two phases, extract the aqueous layer twice-with AcOEt, wash the organic layer with water, brine, dry over MgSO 4 , filter and concentrate in vacuum. Purify the crude by SiO 2 chromatography (Hexane/AcOEt 95:5 to 85:15) to give the example 104. (80%).
[0501] Prepare Examples 105-112 using a similar procedure to prepare example 104.
Example Structure LC/MS [M + 1] 104 492 105 476 106 492 107 452 108 450 109 448 110 494 111 476 112 464
EXAMPLE 113
Lysine Salt of Example 3C
[0502]
[0503] Add 7 mL of MeOH to a vial containing 203 mg of Example 3c and heat to approximately 60° C. Then, add 0.5 mL of L-lysine (in water) at a 1 molar equivalence. Cool to room temperature. Evaporate to dryness under nitrogen. Add 7 mL of isopropyl alcohol which results in a solid suspension. Heat the vial to approximately 80° C. Add water until soluble (2 mL total). Allow the vial to cool to room temperature overnight and the isolate the solid by vacuum filtration. Thermal: Onset 227.8° C.
EXAMPLE 114
[0504] Slurry Example 3C (2.00 g, 0.00455 m) in 20.0 mL IPA and heat to 70° C. Filter the hot cloudy/hazy solution and rinse with 1.5 mL EPA, and heat the resulting filtrate to 70° C. In a separate vessel, slurry L-lysine (681 mg, 0.00466 m, 1.0 eq.; Aldrich 97%) in water (2.00 mL) and heat briefly at 50° C. in a water bath to dissolve to a clear solution. Add the solution of L-lysine dropwise to the free acid solution at 70° C. over 35 minutes. Stir the thick slurry for an additional 5 hours at 70° C., then remove from heat and allow to cool down to room temperature for 1 hour. Further cool the resulting slurry in an ice bath for one hour, filter, rinse with cold IPA, and dry under vacuum/40° C. overnight to give the L-lysine salt of Example 3C as a white crystalline solid (2.44 g, 91 weight% yield). Thermal: Onset 227.6° C.
EXAMPLE 115
[0505] Slurry Example 114 (0.50 g, 0.00087 m) in MeOH (13 mL) and water (3.0 mL) and heat to 60° C. Concentrate the solution under vacuum and which results in removal of approximately 6.0 g weight solvent. Heat the solution at 60° C. and add IPA (10 mL) dropwise over 10 minutes, maintaining the temperature at 60° C. during the addition. Concentrate the solution again which results in removal of approximately 8.4 g solvent. Then, add additional IPA (10 mL) dropwise over 10 minutes at 60° C. Concentrate the slurry under vacuum which results in removal of approximately 4.9 g solvent, and add a final amount of IPA (5 mL) (hot) over 5 minutes. Heat the slurry briefly at 60° C., allow to cool to room temperature, then cool with an ice bath for 1 hour. Filter, rinse with IPA, and dry overnight under vacuum at 40° C. to obtain a white crystalline product (404 mg; HPLC: 97.4 area %, 81 weight % yield, 86.6 HPLC area % corrected yield). Thermal: Onset 220.19° C.
EXAMPLE 116
[0506] Slurry the HCl salt of Example 3C (2.00 g, 0.0043 m) (the free base form could probably be used) in water (15 mL), CH 2 Cl 2 (15 mL) and MeOH (5 mL). Add 5N NaOH (1.80 mL, 2.1 eq.) until pH=11. Separate the layers and extract the aqueous layer with additional CH 2 Cl 2 (15 mL). Combine and discard the organic layers. Add fresh CH 2 Cl 2 (15 mL) to the aqueous, and add 1N HCl (15 mL) with vigorous stirring. Separate the layers , extract the aqueous layer with additional CH 2 Cl 2 (15 mL) and combine the organic layers. Add EtOAc (5 mL) and MeOH (5 mL) to the cloudy organic layer to prevent inadvertent premature crystallization of the HCl salt, then dry the organic layer with Na 2 SO 4 , filter, rinse, and concentrate under vacuum to a weight of 11 g milky solution. Seed the solution with starting material and stir at room temperature as the product crystallizes. Filter and rinse with CH 2 Cl 2 then dry overnight under vacuum/room temperature to yield white birefringent solid (669 mg, 33 wt % yield, 38% yield HPLC corrected, HPLC: 98.1 area % pure). Thermal: Onset 162.44° C.
[0000] Separation of Racemic Mixtures
[0507] Isomers of racemic mixtures of examples were separated by HPLC.
Retention Retention Time Time (min) (min) Racemic Isomer 1 Isomer 2 Example HPLC conditions Example Example 68 Chiralpak AD(250 × 4.6 mm), 6.7 9.0 hexane-TFA (0.05%)(A)/IPA(B) Example Example Gradient - 20 to 60% B in 69 70 15 min 71 Chiralpak AD(250 × 4.6 mm), 9.9 17.1 hexane-TFA (0.05%)(A)/IPA(B) Example Example Gradient - 20 to 60% B in 72 73 15 min 78 Chiralpak AD(250 × 20 mm), 7.2 11.4 hexane(A)/IPA(B) 70/30 Example Example Isocratic mode 79 80 81 Chiralpak AD(250 × 4.6 mm), 8.1 10.4 hexane-TFA (0.05%)(A)/IPA(B) Example Example 75/25 Isocratic mode 82 83 85 Chiralpak AD(250 × 4.6 mm), 7.2 12.3 hexane-TFA (0.05%)(A)/IPA(B) Example Example 75/25 Isocratic mode 86 87 91 Chiralpak AD(250 × 4.6 mm), 11.5 18.1 hexane-TFA (0.05%)(A)/ Example Example Ethanol(B) 75/25 Gradient mode 92 93 94 Chiralpak AD(250 × 20 mm), 10.5 15.5 hexane(A)/IPA(B) 70/30 Example Example Isocratic mode 95 96 97 Chiralpak AD(250 × 4.6 mm), 15.7 18.7 hexane-TFA (0.05%)(A)/IPA(B) Example Example 95/5 Isocratic mode 98 99 100 Chiralpak OD(250 × 4.6 mm), 8.7 11.3 hexane-TFA (0.05%)(A)/IPA(B) Example Example 75/25 Isocratic mode 101 102
Biological Assays
[0000] Binding and Cotransfection Studies
[0508] The in vitro potency of compounds in modulating PPARα receptors are determined by the procedures detailed below. DNA-dependent binding (ABCD binding) is carried out using SPA technology with PPAR receptors. Tritium-labeled PPARα agonists are used as radioligands for generating displacement curves and IC 50 values with compounds of the invention. Cotransfection assays are carried out in CV-1 cells. The reporter plasmid contained an acylCoA oxidase (AOX) PPRE and TK promoter upstream of the luciferase reporter cDNA. Appropriate PPARs are constitutively expressed using plasmids containing the CMV promoter. For PPARα, interference by endogenous PPARγ in CV-1 cells is an issue. In order to eliminate such interference, a GAL4 chimeric system is used in which the DNA binding domain of the transfected PPAR is replaced by that of GAL4, and the GAL4 response element is utilized in place of the AOX PPRE. Cotransfection efficacy is determined relative to PPARα agonist reference molecules. Efficacies are determined by computer fit to a concentration-response curve, or in some cases at a single high concentration of agonist (10 μM).
[0509] These studies are carried out to evaluate the ability of compounds of the invention to bind to and/or activate various nuclear transcription factors, particularly huPPARα (“hu” indicates “human”). These studies provide in vitro data concerning efficacy and selectivity of compounds of the invention. Furthermore, binding and cotransfection data for compounds of the invention are compared with corresponding data for marketed compounds that act on huPPARα.
[0510] The binding and cotransfection efficacy values for compounds of the invention which are especially useful for modulating a PPAR receptor, are ≦100 nM and≧50%, respectively.
Evaluation of Triglyceride Reduction and HDL Cholesterol Elevation in HuapoAI Transgenic Mice
[0511] Compounds of the present invention are studied for effects upon HDL and triglyceride levels in human apoAI mice. For each compound tested, seven to eight week old male mice, transgenic for human apoAI (C57BL/6-tgn(apoa1m)1 rub, Jackson Laboratory, Bar Harbor, Me.) are acclimated in individual cages for two weeks with standard chow diet (Purina 5001) and water provided ad libitum. After the acclimation, mice and chow are weighed and assigned to test groups (n=5) with randomization by body weight. Mice are dosed daily by oral gavage for 8 days using a 29 gauge, 1½ inch curved feeding needle (Popper & Sons). The vehicle for the controls, test compounds and the positive control (fenofibrate 100 mg/kg) is 1% carboxymethylcellulose (w/v) with 0.25% tween 80 (w/v). All mice are dosed daily between 6 and 8 a.m. with a dosing volume of 0.2 ml. Prior to termination, animals and diets are weighed and body weight change and food consumption are calculated. Three hours after last dose, mice are euthanized with CO 2 and blood is removed (0.5-1.0 ml) by cardiac puncture. After sacrifice, the liver, heart, and epididymal fat pad are excised and weighed. Blood is permitted to clot and serum is separated from the blood by centrifugation.
[0512] Cholesterol and triglycerides are measured colorimetrically using commercially prepared reagents (for example, as available from Sigma #339-1000 and Roche #450061 for triglycerides and cholesterol, respectively). The procedures are modified from published work (McGowan M. W. et al., Clin Chem 29:538-542,1983; Allain C. C. et al., Clin Chem 20:470-475,1974. Commercially available standards for triglycerides and total cholesterol, respectively, commercial quality control plasma, and samples are measured in duplicate using 200 μl of reagent. An additional aliquot of sample, added to a well containing 200 μl water, provided a blank for each specimen. Plates are incubated at room temperature on a plate shaker and absorbance is read at 500 nm and 540 nm for total cholesterol and triglycerides, respectively. Values for the positive control are always within the expected range and the coefficient of variation for samples is below 10%. All samples from an experiment are assayed at the same time to minimize inter-assay variability.
[0513] Serum lipoproteins are separated and cholesterol quantitated by fast protein liquid chromatography (FPLC) coupled to an in line detection system. Samples are applied to a Superose 6 HR size exclusion column (Amersham Pharmacia Biotech) and eluted with phosphate buffered saline-EDTA at 0.5 ml/min. Cholesterol reagent (Roche Diagnostics Chol/HP 704036) at 0.16 ml/min mixed with the column effluent through a T-connection and the mixture passed through a 15 m×0.5 mm id knitted tubing reactor immersed in a 37 C water bath. The colored product produced in the presence of cholesterol. is monitored in the flow strem at 505 nm and the analog voltage from the monitor is converted to a digital signal for collection and analysis. The change in voltage corresponding to change in cholesterol concentration is plotted vs time and the area under the curve corresponding to the elution of very low density lipoprotein (VLDL), low density lipoprotein (LDL) and high density lipoprotein (HDL) is calculated using Perkin Elmer Turbochrome software.
[0514] Triglyceride Serum Levels in Mice Dosed with a Compound of the Invention is Compared to Mice Receiving the Vehicle to identify compounds which could be particularly useful for lowering triglycerides. Generally, triglyceride decreases of greater than or equal to 30% (thirty percent) compared to control following a 30 mg/kg-dose suggests a compound that can be especially useful for lowering triglyceride levels.
[0515] The percent increase of HDLc serum levels in mice receiving a compound of the invention is compared to mice receiving vehicle to identify compounds of the invention that could be particularly useful for elevating HDL levels. Generally, and increase of greater than or equal to 25% (twenty five percent) increase in HDLc level following a 30 mg/kg dose suggests a compound that can be especially useful for elevating HDLC levels.
[0516] It may be particularly desirable to select compounds of this invention that both lower triglyceride levels and increase HDLc levels. However, compounds that either lower triglyceride levels or increase HDLc levels may be desirable as well.
Evaluation of Glucose Levels in db/db Mice
[0517] The effects upon plasma glucose associated with administering various dose levels of different compounds of the present invention and the PPAR gamma agonist rosiglitazone (BRL49653) or the PPAR alpha agonist fenofibrate, and the control, to male db/db mice, are studied.
[0518] Five week old male diabetic (db/db) mice [for example, C57B1 Ks/j-m +/+Lepr(db), Jackson Laboratory, Bar Harbor, Me. ] or lean littermates are housed 6 per cage with food and water available at all times. After an acclimation period of 2 weeks, animals are individually identified by ear notches, weighed, and bled via the tail vein for determination of initial glucose levels. Blood is collected (100 μl) from unfasted animals by wrapping each mouse in a towel, cutting the tip of the tail with a scalpel, and milking blood from the tail into a heparinized capillary tube. Sample is discharged into a heparinized microtainer with gel separator and retained on ice. Plasma is obtained after centrifugation at 4° C. and glucose measured immediately. Remaining plasma is frozen until the completion of the experiment, when glucose and triglycerides are assayed in all samples. Animals are grouped based on initial glucose levels and body weights. Beginning the following morning, mice are dosed daily by oral gavage for 7 days. Treatments are test compounds (30 mg/kg), a positive control agent (30 mg/kg) or vehicle [1% carboxymethylcellulose (w/v)/0.25% Tween80 (w/v); 0.3 ml/mouse]. On day 7, mice are weighed and bled (tail vein) 3 hours after dosing. Twenty-four hours after the 7 th dose (i.e., day 8), animals are bled again (tail vein). Samples obtained from conscious animals on days 0, 7 and 8 are assayed for glucose. After the 24-hour bleed, animals are weighed and dosed for the final time. Three hours after dosing on day 8, animals are anesthetized by inhalation of isoflurane and blood obtained via cardiac puncture (0.5-0.7 ml). Whole blood is transferred to serum separator tubes, chilled on ice and permitted to clot. Serum is obtained after centrifugation at 4° C. and frozen until analysis for compound levels. After sacrifice by cervical dislocation, the liver, heart and epididymal fat pads are excised and weighed.
[0519] Glucose is measured calorimetrically using commercially purchased reagents. According to the manufacturers, the procedures are modified from published work (McGowan, M. W., Artiss, J. D., Strandbergh, D. R. & Zak, B. Clin Chem, 20:470-5 (1974) and Keston, A. Specific colorimetric enzymatic analytical reagents for glucose. Abstract of papers 129th Meeting ACS, 31C (1956).); and depend on the release of a mole of hydrogen peroxide for each mole of analyte, coupled with a color reaction first described by Trinder (Trinder, P. Determination of glucose in blood using glucose oxidase with an alternative oxygen acceptor. Ann Clin Biochem, 6:24 (1969)). The absorbance of the dye produced is linearly related to the analyte in the sample. The assays are further modified in our laboratory for use in a 96 well format. The commercially available standard for glucose, commercially available quality control plasma, and samples (2 or 5 μl/well) are measured in duplicate using 200 μl of reagent. An additional aliquot of sample, pipetted to a third well and diluted in 200 μl water, provided a blank for each specimen. Plates are incubated at room temperature for 18 minutes for glucose on a plate shaker (DPC Micormix 5) and absorbance read at 500 nm on a plate reader. Sample absorbances are compared to a standard curve (100-800 for glucose). Values for the quality control sample are always within the expected range and the coefficient of variation for samples is below 10%. All samples from an experiment are assayed at the same time to minimize inter-assay variability.
Evaluation of the Effects of Compounds of the Present Invention upon A y Mice Body Weight, Fat Mass, Glucose and Insulin Levels
[0000] Female A y Mice
[0520] Female A y mice are singly housed, maintained under standardized conditions (22° C., 12 h light:dark cycle), and provided free access to food and water throughout the duration of the study. At twenty weeks of age the mice are randomly assigned to vehicle control and treated groups based on body weight and body fat content as assessed by DEXA scanning (N=6). Mice are then dosed via oral gavage with either vehicle or a Compound of this invention (50 mg/kg) one hour after the initiation of the light cycle (for example, about 7 A.M.) for 18 days. Body weights are measured daily throughout the study. On day 14 mice are maintained in individual metabolic chambers for indirect calorimetry assessment of energy expenditure and fuel utilization. On day 18 mice are again subjected to DEXA scanning for post treatment measurement of body composition.
[0521] The results of p.o. dosing of compound for 18 days on body weight, fat mass, and lean mass are evaluated and suggest which compounds of this invention can be especially useful for maintaining desirable weight and/or promoting desired lean to fat mass.
[0522] Indirect calorimetry measurements revealing a significant reduction in respiratory quotient (RQ) in treated animals during the dark cycle [0.864±0.013 (Control) vs. 0.803±0.007 (Treated); p <0.001] is indicative of an increased utilization of fat during the animals' active (dark) cycle and can be used to selected especially desired compounds of this invention. Additionally, treated animals displaying significantly higher rates of energy expenditure than control animals suggest such compounds of this invention can be especially desired.
[0000] Male KK/A y Mice
[0523] Male KK/A y mice are singly housed, maintained under standardized conditions (22° C., 12 h light:dark cycle), and provided free access to food and water throughout the duration of the study. At twenty-two weeks of age the mice are randomly assigned to vehicle control and treated groups based on plasma glucose levels. Mice are then dosed via oral gavage with either vehicle or a Compound of this invention (30 mg/kg) one hour after the initiation of the light cycle (7 A.M.) for 14 days. Plasma glucose, triglyceride, and insulin levels are assessed on day 14.
[0524] The results of p.o. dosing of compound for 14 days on plasma glucose, triglycerides, and insulin are evaluated to identify compounds of this invention which may be especially desired.
[0000] Method to Elucidate the LDL-Cholesterol Total-Cholesterol and Triglyceride Lowering Effect
[0525] Male Syrian hamsters (Harlan Sprague Dawley) weighing 80-120 g are placed on a high-fat cholesterol-rich diet for two to three weeks prior to use. Feed and water are provided ad libitum throughout the course of the experiment. Under these conditions, hamsters become hypercholesterolemic showing plasma cholesterol levels between 180-280 mg/dl. (Hamsters fed with normal chow have a total plasma cholesterol level between 100-150 mg/dl.) Hamsters with high plasma cholesterol (180 mg/dl and above) are randomized into treatment groups based on their total cholesterol level using the GroupOptimizeV211.xls program.
[0526] A Compound of this invention is dissolved in an aqueous vehicle (containing CMC with Tween 80) such that each hamster received once a day approx. 1 ml of the solution by garvage at doses 3 and 30 mg/kg body weight. Fenofibrate (Sigma Chemical, prepared as a suspension in the same vehicle) is given as a known alpha-agonist control at a dose of 200 mg/kg, and the blank control is vehicle alone. Dosing is performed daily in the early morning for 14 days.
[0527] Quantification of Plasma Lipids:
[0528] On the last day of the test, hamsters are bled (400 μl) from the suborbital sinus while under isoflurane anesthesia 2 h after dosing. Blood samples are collected into heparinized microfuge tubes chilled in ice bath. Plasma samples are separated from the blood cells by brief centrifugation. Total cholesterol and triglycerides are determined by means of enzymatic assays carried out automatically in the Monarch equipment (Instrumentation Laboratory) following the manufacturer's precedure. Plasma lipoproteins (VLDL, LDL and HDL) are resolved by injecting 25 μl of the pooled plasma samples into an FPLC system eluted with phosphate buffered saline at 0.5 ml/min through a Superose 6 HR 10/30 column (Pharmacia) maintained room temp. Detection and characterization of the isolated plasma lipids are accomplished by postcolumn incubation of the effluent with a Cholesterol/HP reagent (for example, Roche Lab System; infused at 0.12 ml/min) in a knitted reaction coil maintained at 37° C. The intensity of the color formed is proportional to the cholesterol concentration and is measured photometrically at 505 nm.
[0529] The effect of administration of a Compound of this invention for 14 days is studied for the percent reduction in LDL level with reference to the vehicle group. Especially desired compounds are markedly more potent than fenofibrate in LDL-lowering efficacy. Compounds of this invention that decrease LDL greater than or equal to 30% (thirty percent) compared to vehicle can be especially desired.
[0530] The total-cholesterol and triglyceride lowering effects of a Compound of this invention is also studied. The data for reduction in total cholesterol and triglyceride levels after treatment with a compound of this invention for 14 days is compared to the vehicle to suggest compounds that can be particularly desired. The known control fenofibrate did not show significant efficacy under the same experimental conditions.
[0000] Method to Elucidate the Fibrinogen-Lowering Effect of PPAR Modulators
[0000] Zucker Fatty Rat Model:
[0531] The life phase of the study on fibrinogen-lowering effect of compounds of this invention is part of the life phase procedures for the antidiabetic studies of the same compounds. On-the last (14 th ) day of the treatment period, with the animals placed under surgical anesthesia, ˜3 ml of blood is collected, by cardiac puncture, into a syringe containing citrate buffer. The blood sample is chilled and centrifuged at 4° C. to isolate the plasma that is stored at −70° C. prior to fibrinogen assay.
[0000] Quantification of Rat Plasma Fibrinogen:
[0532] Rat plasma fibrinogen levels are quantified by using a commercial assay system consists of a coagulation instrument following the manufacturer's protocol. In essence, 100 μl of plasma is sampled from each specimen and a 1/20 dilution is prepared with buffer. The diluted plasma is incubated at 37° C. for 240 seconds. Fifty microliters of clotting reagent thrombin solution (provided by the instrument's manufacturer in a standard concentration) is then added. The instrument monitors the clotting time, a function of fibrinogen concentration quantified with reference to standard samples. Compounds that lower fibrinogen level greater than vehicle can be especially desired.
[0533] Cholesterol and triglyceride lowering effects of compounds of this invention are also studied in Zucker rats.
[0000] Method to Elucidate the Anti-Body Weight Gain and Anti-Appetite Effects of Compounds of this Invention
[0000] Fourteen-Day Study in Zucker Fatty Rat 1 or ZDF Rat 2 Models:
[0534] Male Zucker Fatty rats, non-diabetic (Charles River Laboratories, Wilmington, Mass.) or male ZDF rats (Genetic Models, Inc, Indianapolis, Ind.) of comparable age and weight are acclimated for 1 week prior to treatment. Rats are on normal chow and water is provided ad libitum throughout the course of the experiment.
[0535] Compounds of this invention are dissolved in an aqueous vehicle such that each rat received once a day approximately 1 ml of the solution by garvage at doses 0.1, 0.3, 1 and 3 mg/kg body weight. Fenofibrate (Sigma Chemical, prepared as a suspension in the same vehicle) a known alpha-agonist given at doses of 300 mg/kg, as well as the vehicle are controls. Dosing is performed daily in the early morning for 14 days. Over the course of the experiment, body weight and food consumption are monitored. Using this assay, compounds of this invention are identified to determine which can be associated with a significant weight reduction.
[0000] Method to Elucidate the Activation of the PPAR Delta Receptor in vivo
[0536] This method is particularly useful for measuring the in vivo PPARdelta receptor activation of compounds of this invention that are determined to possess significant in vitro activity for that receptor isoform over the PPAR gamma isoform.
[0537] Male PPARa null mice (129s4 SvJae-PPARa<tm1Gonz> mice; Jackson Laboratories) of 8-9 weeks of age are maintained on Purina 5001 chow with water ad libitum for at least one week prior to use. Feed and water are provided ad libitum throughout the course of the experiment. Using the GroupOptimizeV211.xls program, mice are randomized into treatment groups of five animals each based on their body weight.
[0538] Compounds of this invention are suspended in an aqueous vehicle of 1% (w/v) carboxymethylcellulose and 0.25% Tween 80 such that each mouse receives once a day approx. 0.2 ml of the solution by gavage at doses ranging from 0.2 to 20 mg/kg body weight. A control group of mice is included in each experiment whereby they are dosed in parallel with vehicle alone. Dosing is performed daily in the early morning for 7 days.
[0539] On the last day of dosing, mice are euthanized by CO 2 asphyxiation 3 hours after the final dose. Blood samples are collected by heart draw into EDTA-containing microfuge tubes and chilled on ice. Liver samples are collected by necropsy and are flash-frozen in liquid nitrogen and stored at −80 degrees Celsius. For RNA isolation from liver, five to ten mg of frozen liver is placed in 700 μof 1× Nucleic Acid Lysis Solution (Applied Biosystems Inc., Foster City, Calif.) and homogenized using a hand-held tissue macerator (Biospec Products Inc., Bartlesville, Okla.). The homogenate is filtered through an ABI Tissue pre-filter (Applied Biosystems Inc., Foster City, Calif.) and collected in a deep well plate on an ABI 6100 Nucleic Acid prep station (Applied Biosystems Inc., Foster City, Calif.). The filtered homogenate is then loaded onto an RNA isolation plate and the RNA Tissue-Filter-DNA method is run on the ABI 6100. The isolated RNA is eluted in 150 μl of RNase free water. For quality assessment, 9 μl of the isolated RNA solution is loaded onto a 1% TBE agarose gel, and the RNA is visualized by ethidium bromide fluorescence.
[0540] Complementary DNA (cDNA) is synthesized using the ABI High Capacity Archive Kit (Applied Biosystems Inc., Foster City, Calif.). Briefly, a 2× reverse transcriptase Master Mix is prepared according to the manufacturer's protocol for the appropriate number of samples (RT Buffer, dNTP, Random Primers, MultiScribe RT (50U/μl), RNase free water). For each reaction, 50 μl of 2× RT Master Mix is added to 50 μl of isolated RNA in a PCR tube that is incubated in a thermocycler (25° C. for 10 minutes followed by 37° C. for 2 hours). The resultant cDNA preparation is diluted 1:100 in dH2O for analysis by real-time PCR. Also, a standard curve of cDNA is diluted 1:20, 1:100, 1:400, 1:2000, 1:10,000 for use in final quantitation.
[0541] A real-time PCR Master Mix for mouse Cyp4A1 gene expression is mixed to contain:
1× Taqman Universal PCR Master Mix (Applied Biosystems Inc., Foster City, Calif.) 6 micromolar final concentration Forward primer; Qiagen/Operon Technologies, Alameda, Calif.) 6 micromolar final concentration Reverse primer (Qiagen/Operon Technologies, Alameda, Calif.) 0.15 micromolar final concentration Probe (5′ 6-FAM and 3′ Tamra-Q; Qiagen/Operon Technologies, Alameda, Calif.) RNase free water to 10 microliters
[0547] A real-time PCR Master Mix for the 18S ribosomal RNA control gene expression is mixed to contain
1× Taqman Universal PCR Master Mix (Applied Biosystems Inc., Foster City, Calif.) 0.34 micromolar Probe/Primer TaqMan® Ribosomal RNA Control Reagents #4308329 Applied Biosystems Inc., Foster City, Calif.) RNase free water to 10 microliters
[0551] For the real-time PCR analysis, 6 ul of the respective Master Mix solution (either Cyp4A1 or 18S) and 4 ul either of diluted cDNA or of Standard Curve samples is added to individual wells of a 384-well plate (n=2 for Standards; n=4 for unknowns). Reactions are performed using the ABI 7900 HT standard universal RT-PCR cycling protocol. Data are analyzed using SDS 2.1 (Applied Biosystems Inc., Foster City, Calif.). Average quantity and standard deviation are calculated automatically for each individual sample, according to the standard curve values. Using Microsoft Excel 2000, mean values for each group of five individual mice is calculated. The mean value of each compound-treated group is divided by the mean value of the vehicle-treated group. The fold induction over the vehicle group is determined by assigning the vehicle group to the value of 1.0, and the fold change of the mean value for each group is expressed as fold-induction versus vehicle (1.0). Data are plotted using Jandel SigmaPlot 8.0.
Monkey Studies
[0000] Efficacy Studies
[0552] Compounds of the invention may be examined in a dyslipidemic rhesus monkey model. After an oral dose-escalation study for 28 days in obese, non-diabetic rhesus monkeys a determination of HDL-c elevation is made with each dose and compared with pretreatment levels. LDL cholesterol is also determined with each dose. C-reactive protein levels are measured and compared to pretreatment levels.
[0553] Compound of Formula 1 may be shown to elevate plasma HDL-cholesterol levels in an African Green Monkey model in a manner similar to that described above in rhesus monkeys.
[0554] Two groups of monkeys are placed in a dose-escalating study that consists of one week of baseline measurements, 9 weeks of treatments (vehicle, Compound of Formula I), and four weeks of washout. During baseline, monkeys in all three groups are administered vehicle once daily for seven days. Test compound of Formula I, is administered in vehicle once daily for three weeks, then at a greater concentration (double the dose may be desired) once daily for three weeks, and then a still greater concentration (double the most recent dose may be desired) once daily for three weeks. At the completion of treatment, monkeys in both groups are administered vehicle once daily and monitored for an additional six weeks.
[0555] Animals are fasted overnight and then sedated for body weight measurements and blood collection at weeks 1 (vehicle), 2, 3, 4, 6, 7, 9, 10, 12, and 14 of the study.
[0000] Parameters to Measured, for Example:
[0000]
Body weight
Total plasma cholesterol
HDL
LDL
Triglycerides
Insulin
Glucose
PK parameters at week 4, 7, and 10 (plasma drug concentration at last week of each dose)
ApoAI
ApoAII
ApoB
ApoCIII
Liver enzymes (SGPT, SGOT, ▭GT)
Complete blood count
Additionally, other measures may be made, as appropriate, and consistent with the stated study design.
EQUIVALENTS
[0570] While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims. | The present invention is directed to compounds represented by the following structural formula, Formula (I): wherein: (a) X is selected from the group consisting of a single bond, O, S, S(O) 2 and N; (b) U is an aliphatic linker; (c) Y is selected from the group consisting of O, C, S, NH and a single bond; (d) W is N, O or S; (e) E is C(R3)(R4)A or A and wherein; (f) A is selected from the group consisting of carboxyl, tetrazole, C 1 -C 6 alkylnitrile, carboxamide, sulfonamide and acylsufonamide. The other substituents are defined in the claims; the compounds are modulators of peroxisome proleferator activated receptors (PPARs) and are useful for the treatment of diabetes and other metabolic disorders. | 0 |
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0001] This invention was made with government support under Contract Number W909MY-12-C-0018 awarded by the US Army Contracting Command, Subcontract Number SA-04, awarded by Banc 3, Inc. under Prime Contract No. W909MY-12-D-0005-0002 awarded to Banc 3, Inc. by the US Army and Subcontract Number SA-05, awarded by Banc 3, Inc. under Prime Contract No. W909MY-12-D-0005-0002 awarded to Banc 3, Inc. by the US Army. The government has certain rights in the invention.
BACKGROUND
[0002] The present disclosure relates to a micro-machined optical mirror switch and a method for fabricating the same. More particularly, the present disclosure relates to a silicon-based, micro-machined optical mirror switch with a fast response speed and a method for fabricating the same.
[0003] Micro-Electro-Mechanical Systems (MEMS) is a fast growing manufacturing technology that produces ultra-fine mechanical devices at a very low cost. MEMS benefits from the economics of scale by employing the batch fabrication established in the semiconductor industry. Moreover, MEMS can be constructed using single-crystal silicon, which is an ideal material for mechanical devices, partly because single-crystal silicon has virtually no hysteresis and hence almost no energy dissipation. Further, single-crystal silicon is less prone to fatigue damages, and thus allows for a prolonged service lifetime. For example, single-crystal silicon may sustain over trillions of mechanical flexing cycles without breaking.
[0004] MEMS based moving mirrors have been widely used in communication components such as switches and attenuators and extensively use in digital light projectors (DLPs) and laser scanners. However, conventional MEMS mirror switches are limited in switching speed. There is an acute need to have fast MEMS optical mirrors for fast optical switches supporting the insatiable growth of internet bandwidth and other applications such as micro-scanners, laser Q-switching, optical shutters, etc. Fast optical MEMS mirror finds extensive applications in telecommunications, astrophysics, biology, medical imaging, etc.
SUMMARY
[0005] In light of the above, the present disclosure provides a MEMS optical mirror switch that is optimized to achieve a significantly increased electrical response speed. For example, the fast electrical response speed may be achieved by operating the MEMS optical mirror switch in a near breakdown field region.
[0006] In one aspect, the mirror switch of the present disclosure includes a substrate defining a gap space, and a mirror assembly disposed on the substrate and deflectable in the gap space, the mirror assembly including a free end cantilever and a reflector on the cantilever, wherein the cantilever is anchored on the substrate adjacent a side of the gap space through an elastic member. The mirror device may further include a stop spring at an end of the cantilever opposing the elastic member. The mirror switch may further include an insulating layer disposed between the substrate and the mirror assembly. The mirror switch may further include a first electrode electrically coupled to the substrate, and a second electrode electrically coupled to the mirror assembly. The mirror switch may further include a highly reflective coating layer on the reflector. The mirror switch may further include a stop spring at an end of the cantilever opposing the elastic member. The mirror assembly of the mirror switch may further include an obstacle disposed adjacent a side of the gap space proximate the stop spring. The substrate of the mirror switch may include a plurality of apertures, the apertures opening the gap space to an exterior of the switchable optical mirror device.
[0007] The mirror assembly is switchable between a neutral state and a deflected state in response to an electrical voltage applied to the mirror assembly. In one embodiment, the cantilever may be substantially parallel to the substrate when the mirror assembly is at the neutral state. In an altemative embodiment, the cantilever may be substantially parallel to the substrate when the mirror assembly at the deflected state.
[0008] A number of other embodiments and fabrication of the mirror switch of the present disclosure are also disclosed herein below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The present disclosure is to be read in conjunction with the accompanying drawings, in which:
[0010] FIG. 1 illustrates a sectional view of a mirror switch at an OFF state, in accordance with one embodiment of the present disclosure;
[0011] FIG. 2 illustrates a sectional view of a mirror switch at an ON state, in accordance with one embodiment of the present disclosure;
[0012] FIG. 3 illustrates a sectional view of a mirror switch in accordance with another embodiment of the present disclosure;
[0013] FIGS. 4A through 4D illustrate a process for fabricating an optical member of a mirror switch in accordance with one embodiment of the present disclosure;
[0014] FIGS. 5A through 5D illustrate a process for fabricating a support member of a mirror switch in accordance with one embodiment of the present disclosure; and
[0015] FIG. 6 illustrates a process for fabricating a mirror switch including the optical member and the support member, in accordance with one embodiment of the present disclosure.
DETAILED DESCRIPTION
[0016] The following detailed description is of the best currently contemplated modes of carrying out the present disclosure. The description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating the general principles of the present disclosure, because the scope of the present disclosure is defined by the appended claims.
[0017] As used herein, the singular forms “a,” “an,” and “the” include the plural reference unless the context clearly dictates otherwise.
[0018] Except where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and the claims are to be understood as being modified in all instances by the term “about.” Further, any quantity modified by the term “about” or the like should be understood as encompassing a range of ±10% of that quantity.
[0019] For the purposes of describing and defining the present disclosure, it is noted that the term “substantially” is utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The term “substantially” is also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.
[0020] FIG. 1 illustrates a sectional view of an optical mirror switch 100 at an OFF state, in accordance with one embodiment of the present disclosure. Switch 100 may be manufactured from silicon wafers using the MEMS technology. In one embodiment, switch 100 includes a suspended optical member 102 and a support member 104 on which optical member 102 is securely disposed. In one embodiment, optical mirror switch 100 is at an OFF state because no electrical voltage is applied thereon.
[0021] Referring to FIG. 1 , a suspended optical member 102 comprises support frame 14 , a mirror electrode 10 , a silicon cantilever spring 12 , silicon spring stopper 20 , and an upper stopper 18 . In one embodiment, a suspended optical member 102 may be formed from a single crystal silicon wafer by etching silicon. It is appreciated that a silicon cantilever spring 12 is mechanically coupled and suspend a mirror electrode 10 over bottom electrode 104 . In one embodiment, a spring stopper reduces the mechanical impact when the side of a suspended optical member 102 away from a cantilever spring 12 touches either bottom electrode or upper stopper during switching operation. In addition, suspended optical member 102 may optionally comprises a highly reflective layer 16 coated on mirror electrode element 10 . In one embodiment, suspended optical member 102 is a free end cantilever, that is, one end of suspended optical member 102 is supported by silicon cantilever spring 12 which is anchored to support frame 14 , while the other end of suspended optical member 102 is connected to spring stopper 20 which is free to fluctuate.
[0022] Referring again to FIG. 1 , support member 104 comprises a bottom electrode body 24 , a dielectric layer 30 on bottom electrode body 24 , and a spacer step 26 . Support member 104 may comprise a gap 22 formed by etching into bottom electrode body 24 to have a size commensurate with the size of a mirror electrode 10 , so as to provide sufficient space for a mirror electrode 10 to move or fluctuate therein. Further, support member 104 may comprise a plurality of apertures 28 formed by etching through bottom electrode body 24 so as to allow air to escape from gap 22 while a mirror electrode 10 moves in gap 22 . As shown in FIG. 1 , optical member 102 and support member 104 securely are engaged with each other by aligning mirror electrode 10 and silicon spring stopper 20 of optical member 102 with gap 22 of support member 104 . In various embodiments, bottom electrode body 24 is electrically grounded.
[0023] FIG. 2 illustrates a sectional view of a mirror switch 100 at an ON state, in accordance with one embodiment of the present disclosure. Mirror switch 100 in FIG. 2 is substantially the same as mirror switch 100 in FIG. 1 , except that a voltage Vd is applied to mirror electrode 10 and bottom electrode 24 of mirror switch 100 in FIG. 2 , while no voltage is applied to mirror switch 100 in FIG. 1 . Voltage Vd applied to mirror switch 110 may induce electrostatic force that attracts mirror electrode 10 to move toward bottom electrode 24 . As a result, MEMS mirror electrode 10 may be actuated and switched to an ON state in response to voltage Vd, as shown in FIG. 2 . When mirror switch 100 is at an ON state, mirror electrode 10 is electrically insulated with bottom electrode 24 due to dielectric layer 30 .
[0024] When voltage Vd is removed, mirror electrode 10 of switch 100 reverts back to the OFF state due to the restoration force of silicon spring 12 , as shown in FIG. 1 . When mirror electrode 10 reverts back to the OFF state, upper stopper 18 of optical member 102 may physically contact stop spring portion 20 of mirror electrode 10 so as to prevent mirror electrode 10 from over overshooting. Further, stop spring 20 may absorb the kinetic energy of the movable portion of optical member 102 and avoid hard contact when snapping down or restoring back to neutral position. As a result, both switching ring effect and mechanical damage are illuminated to enhance the stability and reliability of switch 100 .
[0025] The mirror switch 100 of the present disclosure may be operated in an acceleration mode to achieve faster speed than conventional devices. While not desiring to be bound by theory, one physical explanation is that when the actuation force is much larger than the intrinsic MEMS mechanical spring force, the MEMS structure is at a non-steady state. The rotation rate is very fast, and the higher the applied voltage Vd, the faster the rotation rate. The recovery time and maximum actuation frequency is affected by the primary mechanical resonant frequency of mirror electrode suspension including silicon suspension spring 12 , mirror electrode 10 , and spring stopper 20 . The mechanical resonant frequency depends mainly on the length and stiffness silicon spring 12 . The mechanical resonant frequency f of suspended mirror structure (including reference numerals 10 , 12 , 16 , and 20 ) may be related to the rotational spring constant K and rational inertia I of suspended mirror structure (including reference numerals 10 , 12 , 16 , and 20 with the following formula:
[0000]
f
=
1
2
π
K
I
,
(
Equation
1
)
[0000] The recovering time constant is
[0000]
τ
=
1
2
π
f
=
I
K
(
Equation
2
)
[0026] By MEMS technology, one may design rotational spring constant K and rational inertia I, such that the rotational frequency f can be as high as 16 kHz, which may correspond to a recovering time constant τ of about 10 μSec. In one instance, the mechanical resonant frequency ranges from about 1 kHz to about 100 kHz. By confining displacement of the mirror electrode 10 to a space between the upper stopper 18 and a surface of the 22 , the optical mirror switch 100 is configured to withstand mechanical vibration from 10 to 2000 Hz and impact of to 2000 G.
[0027] In sum, when mirror switch 100 is at the OFF state, mirror 10 is in a neutral position suspended by spring portion 12 , as illustrate in FIG. 1 . When driving voltage Vd is applied, mirror switch 100 changes to the ON state by rotating mirror electrode suspension 10 to snap down to ground plate 24 . The rotation is then stopped by stop spring portion 20 , which lands on dielectric layer 30 on ground plate 24 , as illustrate in FIG. 2 . When a light beam impinges on mirror switch 100 at the OFF state, the light beam is reflected to a first destination. When mirror switch 100 is changed to the ON state, the light beam is then reflected to a second destination different from the first destination. Accordingly, mirror switch 100 of the present disclosure can be used to quickly control the optical path of a light beam.
[0028] As shown in FIGS. 1 and 2 , mirror element 10 is suspended through silicon spring 12 over electrode plate 24 that is grounded. Gap 22 is formed between suspended mirror 10 and grounded electrode plate 24 . Mirror 10 may be made of either N or P type heavily doped single crystal silicon with low resistivity for applying a driving voltage to achieve mirror switch by electrostatic force. By using silicon micro-machining technology, gap 22 may be precisely defined by spacer 26 and can be as small as in the micron range, in which a large electrostatic driving force may be produced to achieve fast switching, even with a low driving voltage. In one embodiment, gap 22 may has a thickness of less than 100 micro meters. In addition, the reflective loss is minimized due to the high quality mirror surface 10 as well as the high reflective coating 16 on mirror surface 10 .
[0029] On electrode plate 24 , arrays of through holes 28 are created to reduce air thin film squeeze damping and to increase switch speed. Stop spring portion 20 is created along the outer mirror edge away from suspended silicon spring 12 to avoid hard contact when mirror 10 switch down to ground plate 24 . When mirror 10 restores back to the neutral position, stop spring portion 24 absorbs the kinetic energy by contacting upper stopper 18 , thereby minimizing the ringing effect of switching.
[0030] Although mirror 10 and ground plate 24 can be in parallel in order to reduce the complexity of assembly, as shown in FIGS. 1 and 2 , mirror 10 and ground plate 24 can be arranged in a wedge form to further reduce driving voltage of the switch. FIG. 3 illustrates a sectional view of a mirror switch 100 in accordance with another embodiment of the present disclosure. Mirror switch 100 in FIG. 3 is substantially the same as mirror switch 100 in FIGS. 1 and 2 , except that optical member 102 and support member 104 of mirror switch 100 in FIG. 3 are not parallel with each other. Rather, optical member 102 is deposed on support member 104 with a wedged angle. In one embodiment, the wedge form of mirror switch 100 may be achieved by selectively over-etching spacer 26 of support member 104 prior to engaging optical member 102 with support member 104 .
[0031] Hereafter, a process for fabricating mirror switch 100 in accordance with on embodiment of the present disclosure is described.
[0032] FIGS. 4A through 4D illustrate a process for fabricating optical member 102 of mirror switch 100 in accordance with one embodiment of the present disclosure. Referring to FIG. 4A , the fabrication process begins from silicon wafer In one embodiment, the top surface of silicon wafer may be the prime polished surface that is ideal for an optical mirror surface.
[0033] Referring to FIG. 4B , silicon is etched from one side to define the bottom boundaries of mirror electrode suspension including silicon suspension spring 12 , mirror electrode 10 , and spring stopper 20 It is noted that mirror electrode 10 , and suspending spring 12 are mechanically and electrically coupled with each other.
[0034] Referring to FIG. 4C , silicon is etched from the other side, to define mirror element 10 and thickness of suspension spring 12 and spring stopper 20 .
[0035] Referring to FIG. 4D , a high reflective (HR) layer 16 , in which reflectivity is more than 99.5%, is coated on an upper surface of mirror element 10 . In one embodiment, HR layer 16 may be formed by coating a HR material to an entire upper surface of optical element 102 and then etching the HR material such that only the portion on mirror element 10 remains. It is appreciated that, in other embodiments, HR layer 16 may be formed after the bonding of optical member 102 and support member 104 . This completes the fabrication of optical element 102 of switch 100 , as shown in FIGS. 1 and 2 .
[0036] FIGS. 5A through 5C illustrate a process for fabricating support member 104 of mirror switch 100 in accordance with one embodiment of the present disclosure. Referring to FIG. 5A , the fabrication process begins from providing silicon wafer.
[0037] Referring to FIG. 5B , silicon is etched to form spacer 26 on electrode plate 24 , thereby defining gap 22 . In one embodiment, gap 22 may have a dimension commensurate to that of mirror electrode suspension including silicon suspension spring 12 , mirror electrode 10 , and spring stopper 20 .
[0038] Referring to FIG. 5C , silicon is etched through to form an array of apertures 28 . In one embodiment, apertures 28 are through holes that permit air to communicate between two sides of the silicon electrode 24 .
[0039] Referring to FIG. 5C , a dielectric layer 30 is deposited on the top of bottom electrical plate 24 . This completes the fabrication of support element 104 of switch 100 , as shown in FIGS. 1 and 2 .
[0040] FIG. 6 illustrates a process for fabricating mirror switch 100 including optical member 102 and support member 104 , in accordance with one embodiment of the present disclosure. Referring to FIG. 6 , optical member 102 as shown in FIG. 4D and support member 104 as shown in FIG. 5D are bonded together by facing and aligning mirror electrode suspension including silicon suspension spring 12 , mirror electrode 10 , and spring stopper 20 with gap 22 of support member 104 . Upper stopper is aligned between the edge of bottom electrode 24 and spring stopper 20 , and bonded to the bottom electrode 24 .
[0041] Referring to FIG. 6 , once optical member 102 and support member 104 are bonded, mirror switches 100 fabricated on a large wafer may be separated into individual chip units. Each individual mirror switch 100 may then be wire bonded with electrical terminals such that a driving voltage may be applied to mirror electrode 10 and that bottom electrode 24 may be grounded. It is appreciated that, in alternative embodiments, a driving voltage may be applied to bottom electrode 24 , while mirror electrode 10 may be grounded.
[0042] In view of the foregoing, it can be seen that the present disclosure provides a MEMS optical mirror switch that is optimized to achieve a significantly increased electrical response speed. It is to be understood that the method and the apparatus of the present disclosure are described for exemplary and illustrative purposes only. Various modifications and changes may be made to the disclosed embodiments by persons skilled in the art without departing from the scope of the present disclosure as defined in the appended claims. | The present disclosure provides a micro-machined switchable optical mirror device with a fast response speed. The mirror device includes a substrate defining a gap space, and a mirror assembly disposed on the substrate and deflectable in the gap space, the mirror assembly including a free end cantilever and a reflector on the cantilever, wherein the cantilever is anchored on the substrate adjacent a side of the gap space through an elastic member. In one aspect, the mirror device further includes a stop spring at an end of the cantilever opposing the elastic member. | 1 |
TECHNICAL FIELD
The present invention relates to a process for producing a fluorinated organic compound, and a fluorinating reagent.
BACKGROUND ART
Fluorine compounds are extremely important as chemical products such as functional materials, compounds for medicines and agrochemicals, and electronic materials, the intermediates of the chemical products, or the like.
Fluoride, hydrogen fluoride, sulfur tetrafluoride, etc., have been used as fluorinating agents to obtain a target fluorine compound by fluorinating a various organic compound as a starting material. These fluorinating agents, however, are difficult to handle due to their toxicity, corrosiveness, explosion risk at the time of reaction, etc., and thus require special devices or techniques.
A reaction for introducing a fluorine atom into an organic compound by utilizing nucleophilic substitution with a fluoride ion has recently been developed, in addition to various fluorinating agents used for the reaction.
For example, iodine pentafluoride (IF 5 ) is known as a powerful fluorinating agent with high oxidizability; however, it is a dangerous liquid fluorinating agent because it reacts with moisture in air and decomposes while generating HF. Non-patent Literature 1 recently reported that IF 5 having such features becomes a stable white solid (IF 5 -pyridine-HF) in air when mixed with pyridine HF, and is effective for fluorination of various sulfur compounds.
CITATION LIST
Non-Patent Literature
NPL 1: S. Hara, M. Monoi, R. Umemura, C. Fuse, Tetrahedron, 2012, 68, 10145-10150
SUMMARY OF INVENTION
Technical Problem
Although IF 5 -pyridine-HF is an excellent fluorinating agent, some fluorinated organic compounds cannot be produced with a sufficient yield by the method for producing a fluorinated organic compound using a fluorinating agent containing IF 5 -pyridine-HF alone. Accordingly, an improved method for producing a fluorinated organic compound and an improved fluorinating agent are desired.
Therefore, an object of the present invention is to provide a method for producing, with a high yield, a fluorinated organic compound, the fluorinated organic compound having not been produced with a sufficient yield by a conventional method for producing a fluorinated organic compound using a fluorinating agent containing IF 5 -pyridine-HF alone. Another object of the present invention is to provide a fluorinating reagent.
Solution to Problem
As a result of extensive research, the inventors found that the above object can be achieved by a method for producing a fluorinated organic compound comprising step A of fluorinating an organic compound by bringing the organic compound into contact with (1) IF 5 -pyridine-HF and (2) at least one additive selected from the group consisting of amine/hydrogen fluoride salt, X a F (wherein X a represents hydrogen, lithium, sodium, or potassium), oxidizers, and reducing agents. The inventors conducted further research to accomplish the present invention.
The present invention includes the following embodiments.
Item 1. A method for producing a fluorinated organic compound comprising step A of fluorinating an organic compound by bringing the organic compound into contact with (1) IF 5 -pyridine-HF and (2) at least one additive selected from the group consisting of amine/hydrogen fluoride salt, X a F (wherein X a represents hydrogen, potassium, sodium, or lithium), oxidizers, and reducing agents. Item 2. The method according to Item 1, wherein the additive is Et 3 N-nHF (wherein n is a real number of 1 to 9). Item 3. A fluorinating reagent comprising (1) IF 5 -pyridine-HF and (2) at least one additive selected from the group consisting of amine/hydrogen fluoride salt, X a F (wherein X a represents hydrogen, potassium, sodium, or lithium), oxidizers, and reducing agents. Item 4. The fluorinating reagent according to Item 3, wherein the additive is Et 3 N-nHF (wherein n is a real number of 1 to 9).
The method for producing a fluorinated organic compound and the fluorinating reagent of the present invention are detailed below.
Method for Producing a Fluorinated Organic Compound
The method for producing a fluorinated organic compound of the present invention comprises step A of fluorinating an organic compound by bringing the organic compound into contact with (1) IF 5 -pyridine-HF and (2) at least one additive selected from the group consisting of amine/hydrogen fluoride salt, X a F (wherein X a represents hydrogen, potassium, sodium, or lithium), oxidizers, and reducing agents.
In the present invention, examples of the organic compound include
(1) compounds having an OH group; (2) ketones (including diketone, β-ketocarboxylic acid, β-ketoester), aldehydes, Schiff base, hydrazone and like imines, or esters; (3) sulfides; (4) epoxies; (5) aromatic compounds (e.g., phenylhydrazine derivatives, phenol derivatives, 2-naphthol derivatives, or aniline derivatives); (6) thiocarbonyl compounds; and (7) unsaturated carbon compounds (e.g., olefin compounds).
The fluorination of organic compounds in the present invention includes replacement of a hydrogen atom with a fluorine atom, and replacement of the following atom or group with a fluorine atom as shown in each set of parenthesis: hydrogen atom (CH→CF), carbonyl group (CO→CF 2 ), hydrazino group (C—NHNH 2 →C—F; C═N—NH 2 →CF 2 ), hydroxyl group (C—OH→C—F), and epoxy group (C—O—→C—F).
Fluorination conducted in the production method of the present invention is exemplified. Fluorinated organic compounds obtained by the production method below of the present invention are also exemplified.
(1) Fluorination of Compounds Having an OH Group
In the fluorination, the following reactions, for example, are conducted.
(In the above formulae, R 1 represents an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an alkenyl group that may have at least one substituent, an acyl group, a cycloalkyl group that may have at least one substituent, or a heterocycloalkyl group that may have at least one substituent. R 1a represents an alkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an alkenyl group that may have at least one substituent, an acyl group, a cycloalkyl group that may have at least one substituent, or a heterocycloalkyl group that may have at least one substituent).
In the present specification, “may have a substituent” includes both cases where a substituent is contained (i.e., substituted) and not contained (unsubstituted). For example, an alkyl group that may have at least one substituent includes alkyl groups (i.e., unsubstituted alkyl groups) and alkyl groups having a substituent (i.e., substituted alkyl groups).
Specific examples of compounds having an OH group include alcohols including aliphatic alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, hexanol, octanol, decanol, palmityl alcohol, stearyl alcohol, and oleyl alcohol; alicyclic alcohols, such as benzyl alcohol, a mono-, di- or trisaccharide having at least one non-protected hydroxyl group, cyclohexyl alcohol, and ascorbic acid; steroid alcohols, such as cholesterol, cholic acid, and cortisone; and carboxylic acids including aliphatic monocarboxylic acids, such as acetic acid, trifluoroacetic acid, propionic acid, acrylic acid, methacrylic acid, crotonic acid, butyric acid, valeric acid, isovaleric acid, pivalic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and cinnamic acid; polycarboxylic acids, such as oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and citric acid; aromatic carboxylic acids, such as benzoic acid, salicylic acid, (o-, m-, p-)phthalic acid, nalidixic acid, and nicotinic acid; vitamins having carboxylic acid groups, such as pantothenic acid and biotin; 20 kinds of natural amino acids, such as glycine, alanine, phenylalanine, cysteine, aspartic acid, glutamic acid, threonine, histidine, lysine, methionine, and proline; and hydroxycarboxylic acids, such as lactic acid, citric acid, malic acid, and tartaric acid.
(2) Fluorination of Ketones (Including Diketone, β-Ketocarboxylic Acid, β-Ketoester), Aldehydes, Imines Such as Schiff Base and Hydrazone, and Esters
In the fluorination, the following reactions, for example, are conducted.
R 2 —CH 2 —C(═X)—R 2a →R 2 —CHF—C(═X)—R 2a →R 2 —CF 2 —C(═X)—R 2a (a-1)
H—CH 2 —C(═X)—R 2a →H—CHF—C(═X)—R 2a →H—CF 2 —C(═X)—R 2a (a-2)
R 2 —CH 2 —C(═X)—H→R 2 —CHF—C(═X)—H→R 2 —CF 2 —C(═X)—H (a-3)
R 2 —C(═X)—CH 2 —C(═X)—R 2a →R 2 —C(═X)—CHF—C(═X)—R 2a →R 2 —C(═X)—CF 2 —C(═X)—R 2a (b-1)
H—C(═X)—CH 2 —C(═X)—R 2a →H—C(═X)—CHF—C(═X)—R 2a →H—C(═X)—CF 2 —C(═X)—R 2a (b-2)
R 2 —C(═X)—R 2a →R 2 —CF 2 —R 2a (R 2 ) 2 CH—COOR 2b →(R 2 ) 2 CF—COOR 2b (c)
R 2 —C(═N—NHR 2c )—R 2a →R 2 —CF(—N═NR 2c )—R 2a →R 2 —CF 2 —R 2a (d-1)
HC(═N—NHR 2 )—R 2a →F 2 C(—N═NR 2 )—R 2a →CF a —R 2a (d-2)
(In the above formulae, X represents O or NR′ (R′ represents a hydrogen atom, an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cycloalkyl group that may have at least one substituent, a heterocycloalkyl group that may have at least one substituent, a heterocyclic group that may have at least one substituent, an alkoxy group that may have at least one substituent, an aryloxy group that may have at least one substituent, an amino group, a monoalkylamino group that may have at least one substituent, a dialkylamino group that may have at least one substituent, an acyl group, or an acylamino group. R 2 , R 2a , and R 2c may be the same or different, and each represents a hydrogen atom, an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cycloalkyl group that may have at least one substituent, a heterocycloalkyl group that may have at least one substituent, a heterocyclic group that may have at least one substituent, an alkoxy group that may have at least one substituent, an aryloxy group that may have at least one substituent, a monoalkylamino group that may have at least one substituent, a dialkylamino group that may have at least one substituent, an acyl group, or an acylamino group. R 2 and R 2a may bond to each other to form a ring structure).
R 2b represents an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, or an aryl group that may have at least one substituent).
Examples of substances having a ring structure include 4 to 7-membered rings of an aliphatic group that may have at least one substituent.
Examples of ketones include acetone, methyl ethyl ketone, acetylacetone, acetoacetic acid, acetoacetate, cyclohexanone, acetophenone, benzophenone, propiophenone, 4-piperidone, 1-oxo-1,2-dihydronaphthalene, benzylideneacetophenone(chalcone), deoxybenzoin, and ketals thereof, etc.
Examples of aldehydes include acetoaldehyde, propionaldehyde, butylaldehyde, isobutylaldehyde, valeraldehyde, isovaleraldehyde, acrylaldehyde, benzaldehyde, cinnamaldehyde, anisaldehyde, nicotinealdehyde, and acetals thereof, etc.
Examples of imines of Schiff base, hydrazone, and the like include condensates of ketone or aldehyde with an appropriate primary amine.
Examples of esters include methyl isobutyrate, ethyl isobutylate, etc.
(3) Fluorination of Sulfides (Including Dithioacetal and Dithioketal)
In the fluorination, one or two hydrogen atoms of methylene that is located adjacent to a sulfur atom are substituted with fluorine atoms, or a sulfur atom is substituted with fluorine.
R 3 —CH 2 —S—R 3a →R 3 —CFH—S—R 3a →R 3 —CF 2 —S—R 3a (a-1)
R 3 —CHR 3b —S—R 3a →R 3 —CFR 3b —S—R 3a (a-2)
R 3 —CO—CH 2 —S—R 3a →R 3 —CO—CFH—S—R 3a →R 3 —CO—CF 2 —S—R 3a (b-1)
R 3 —CO—CHR 3b —S—R 3a →R 3 —CO—CFR 3b —S—R 3a (b-2)
R 3c R 3d C═C(SR 3a ) 2 →R 3c R 3d CH—CF 2 —SR 3a →R 3c R 3d CH—CF 3 (c)
R 3c R 3d C(SR 3a′ ) (SR 3a″ )→R 3c R 3d CF 2 (d)
R 3 —C(SR 3a ) (SR 3a′ ) (SR 3a″ )→R 3 —CF 3 (e)
R 3 —C(SR 3a ) (SR 3a′ )—S—R 3e —S—(SR 3a′ )—(SR 3a )—R 3 →R 3 —CF 3 (f)
(In the above formulae, R 3a , R 3a′ , and R 3a″ may be the same or different, and each represents an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cycloalkyl group that may have at least one substituent, a heterocycloalkyl group that may have at least one substituent, or a heterocyclic group that may have at least one substituent. Alternately, R 3a and R 3a′ bond to each other may represent 4 to 7-membered rings of an aliphatic group that may have at least one substituent. R 3 and R 3b may be the same or different, and each represents an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cycloalkyl group that may have at least one substituent, a heterocycloalkyl group that may have at least one substituent, a heterocyclic group that may have at least one substituent, an alkoxy group that may have at least one substituent, an aryloxy group that may have at least one substituent, an amino group, a monoalkylamino group that may have at least one substituent, a dialkylamino group that may have at least one substituent, an acyl group, an acylamino group, a cyano group, an alkylsulfinyl group that may have at least one substituent, an aralkylsulfinyl group that may have at least one substituent, an arylsulfinyl group that may have at least one substituent, a cycloalkylsulfinyl group that may have at least one substituent, a heterocycloalkylsulfinyl group that may have at least one substituent, a sulfinyl group bonded by a heterocyclic group that may have at least one substituent, an alkylsulfonyl group that may have at least one substituent, an aralkylsulfonyl group that may have at least one substituent, an arylsulfonyl group that may have at least one substituent, a cycloalkylsulfonyl group that may have at least one substituent, a heterocycloalkylsulfonyl group that may have at least one substituent, or a sulfonyl group bonded by a heterocyclic group that may have at least one substituent. Alternately, R 3 and R 3b may form 4 to 8-membered rings with carbon atoms with or without having a heteroatom in the ring. (The ring may be substituted with at least one substituent selected from the group consisting of a halogen atom, an oxo group, an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cyano group, and an amino group.) R 3c and R 3d may be the same or different, and each represents a hydrogen atom, an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cycloalkyl group that may have at least one substituent, a heterocycloalkyl group that may have at least one substituent, a heterocyclic group that may have at least one substituent, an alkoxy group that may have at least one substituent, an aryloxy group that may have at least one substituent, a monoalkylamino group that may have at least one substituent, a dialkylamino group that may have at least one substituent, an acyl group, or an acylamino group. Alternately, R 3c and R 3d may bind to an adjacent carbon atom to form a saturated or unsaturated 4 to 7-membered rings of an aliphatic group that may have at least one substituent. (The ring may be substituted with at least one member selected from the group consisting of a halogen atom, an oxo group, an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cyano group, and an amino group.))
Examples of sulfide compounds include methyl ethyl sulfide, methyl benzyl sulfide, 2-phenylthioacetate, 2-phenylthioacetophenone, 2-(methylthio)acetophenone, bis(methylthio)methylbenzene, 2-octyl-1,3-dithiane, 2-phenyl-2-trifluoromethyl-1,3-dithiolane, tris(ethylthio)hexane, 4-tris(methylthio)toluene, etc.
(4) Fluorination of Olefin Compounds or Epoxy Compounds
In the fluorination, the following fluorine addition reaction, for example, is conducted.
(In the above formula, R 4 , R 4a , R 4b , and R 4c may be the same or different, and each represents a hydrogen atom, an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cycloalkyl group that may have at least one substituent, a heterocycloalkyl group that may have at least one substituent, or a heterocyclic group that may have at least one substituent).
Examples of olefines include tetrafluoroethylene, methyl acrylate, methyl methacrylate, etc.
Examples of epoxy compounds include oxirane, 1,2-epoxyethylbenzene, 1-chloro-2,3-epoxypropane, α,α′-epoxybibenzyl, etc.
(5) Fluorination of Aromatic Compounds
In the fluorination, a fluorine substituent is introduced in an aromatic ring by, for example, the following reaction. Fluorination of an aromatic ring in a phenol derivative or aniline derivative can be carried out by fluorinating it, then reducing it by zinc powder or like reducing agents, to obtain the targeted fluorine compound.
(5-1) Fluorination of Phenylhydrazine Derivatives
A phenylhydrazine residue that may have at least one substituent can be substituted with a fluorine atom.
(In the above formula, R 5a , R 5b , R 5c , R 5d , and R 5e may be the same or different, and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an alkanoyl group, an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoylamino group, an arylcarbonyl amino group, or an alkylthio group).
(5-2) Fluorination of Phenol Derivatives
A phenol derivative forms the difluorinated quinonoid structure as shown below by reacting with IF 5 . Thereafter, by reducing the resultant compound, a phenol derivative having fluorine introduced in the ortho- or para-position is produced.
(In the above formulae, R 5a , R 5b , R 5c , and R 5d may be the same or different, and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an alkanoyl group, an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoylamino group, an arylcarbonyl amino group, or an alkylthio group).
In a starting material in which all atoms or groups in the ortho- and para-positions are substituted, fluorine atoms are introduced into the ortho- or para-position, forming compounds having a fluorine quinonoid structure.
In the above example, phenol that may have at least one substituent is used as a phenol derivative; however, it is also possible to introduce fluorine atoms into benzene-based aromatic compounds or condensed polycyclic hydrocarbons that may be substituted and have electron-releasing groups such as a hydroxyl group or an alkoxy group.
(5-3) Fluorination of 2-Naphthol Derivatives
A carbon atom in the 1-position of naphthol can be subjected to mono- or difluorination.
(In the above formulae, R 5a , R 5b , R 5c , R 5d , R 5e , R 5f , and R 5g may be the same or different, and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an alkanoyl group, an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoylamino group, an arylcarbonyl amino group, or an alkylthio group).
(5-4) Fluorination of Aniline Derivatives
Similar to a phenol derivative, an aniline derivative forms the difluorinated quinonoid structure as shown below by reacting with IF 5 . Then, by reducing the resultant compound, an aniline derivative having fluorine introduced in the ortho- or para-position is produced.
(In the above formulae, R 5a , R 5b , R 5c , and R 5d may be the same or different, and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an alkanoyl group, an arylcarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, an alkanoylamino group, an arylcarbonyl amino group, or an alkylthio group).
Using aniline that may have at least one substituent or naphthylamine that may have at least one substituent as an aniline derivative also allows a fluorine atom to be introduced into an aromatic ring.
(6) Fluorination of Thiocarbonyl Compounds (Including Thioketone, Thioester, Thiocarbonic Ester, Thioamide, Dithiocarboxylate, and Dithiocarbamate)
The following reactions are conducted.
R 6 —C(═S)—R 6a →R 6 —CF 2 —R 6a (a)
R 6 —C(═S)—SR 6b →R 6 —CF 2 —SR 6b →R 6 —CF 3 (b)
(In the above formulae, R 6 and R 6a may be the same or different, and each represents a hydrogen atom, an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cycloalkyl group that may have at least one substituent, a heterocycloalkyl group that may have at least one substituent, a heterocyclic group that may have at least one substituent, an alkoxy group that may have at least one substituent, an aryloxy group that may have at least one substituent, a monoalkylamino group that may have at least one substituent, a dialkylamino group that may have at least one substituent, an acyl group, or an acylamino group. R 6 and R 6a may bond to each other to form a ring structure. R 6b represents an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cycloalkyl group that may have at least one substituent, a heterocycloalkyl group that may have at least one substituent, or a heterocyclic group that may have at least one substituent).
Examples of thiocarbonyl compounds include O-(4-isopropylphenyl)S-methyl dithiocarbonate, O-(4-bromophenyl)S-methyl dithiocarbonate, ethyl 4-(((methylthio)carbonothioyl)oxy)benzoate, O-decyl S-methyl dithiocarbonate, O-(3-phenylpropyl)S-methyl dithiocarbonate, O-methyl cyclohexanecarbothioate, O-propyl1-piperidinecarbothioate, methyl dithiobenzoate, thiobenzophenone, O-phenyl thiobenzoate, N,N-dimethylphenylthioamide, ethyl 3-quinolinedithiocarboxylate, trifluoromethane carbothioyl naphthalene, N-methyl-N-phenyl trifluoromethanethioamide, N-benzyl-N-phenylheptafluoropropane thioamide, O-(4′-pentyl-[1,1′-bi(cyclohexane)]-4-yl)S-methyl dithiocarbonate,
etc.
(7) Polyfluorination of Ethyl Portion of —COOR Group-Containing Ethylsulfides
In the fluorination, an ethyl portion located adjacent to an S atom is polyfluorinated.
R 7 —S—CH(COOR 7a )—CH 3 →R 7 —S—CHF—CF 2 —COOR 7a
(In the above formula, R 7 represents an aryl group that may have at least one substituent or an aromatic heterocyclic group that may have at least one substituent. R 7a represents a hydrogen atom, an alkyl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an alkenyl group that may have at least one substituent, a cycloalkyl group that may have at least one substituent, a heterocycloalkyl group that may have at least one substituent, a heterocyclic group that may have at least one substituent, an alkoxy group that may have at least one substituent, an aryloxy group that may have at least one substituent, an amino group, a monoalkylamino group that may have at least one substituent, a dialkylamino group that may have at least one substituent, an acyl group, an acylamino group, a cyano group, an alkylsulfinyl group that may have at least one substituent, an aralkylsulfinyl group that may have at least one substituent, an arylsulfinyl group that may have at least one substituent, a cycloalkylsulfinyl group that may have at least one substituent, a heterocycloalkylsulfinyl group that may have at least one substituent, a sulfinyl group bonded by a heterocyclic group that may have at least one substituent, an alkylsulfonyl group that may have at least one substituent, an aralkylsulfonyl group that may have at least one substituent, an arylsulfonyl group that may have at least one substituent, a cycloalkylsulfonyl group that may have at least one substituent, a heterocycloalkylsulfonyl group that may have at least one substituent, or a sulfonyl group bonded to a heterocyclic group that may have at least one substituent).
Examples of —COOR group-containing ethylsulfides include 2-((4-chlorophenyl)thio)ethyl propanate.
(8) Fluorination of Unsaturated Carbon Compound.
In the fluorination, fluorine or iodine is added to a carbon-carbon double bond or carbon-carbon triple bond.
(In the above formulae, R 8a , R 8a′ , R 8b , and R 8b′ may be the same or different, and each represents a hydrogen atom, an alkyl group that may have at least one substituent, an aryl group that may have at least one substituent, an aralkyl group that may have at least one substituent, an alkenyl group that may have at least one substituent, an acyl group, a cycloalkyl group that may have at least one substituent, a heterocycloalkyl group that may have at least one substituent, an ester group, or a halogen atom. At least two of the R 8a , R 8a′ , R 8b , and R 8b′ may be bonded from one another to form a cyclic structure.)
Examples of the cyclic structure include 4 to 12-membered rings of an aliphatic group that may have at least one substituent.
Examples of the unsaturated carbon compound include C 2 - 20 unsaturated carbon compounds such as decene, cyclodecene, dodecyne, phenylacetylene, 4-octyne, 10-undecen-1-yl acetate, 10-undecynoic acid isopropyl ester, and 3-cyclohexylpropine.
Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and like straight or branched C 1 -C 18 alkyl groups. Preferable examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and like straight or branched C 1 -C 6 alkyl groups.
Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy and like straight or branched C 1 -C 6 alkoxy groups.
Examples of alkenyl groups include a vinyl group, an allyl group, a 3-butenyl group and like C 2 - 6 alkenyl groups, etc.
Examples of halogens include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
Examples of aryl groups include a phenyl group, a naphthyl group, etc.
Examples of aryloxy groups include a phenoxy group, a naphthyloxy group, etc.
Examples of aralkyl groups include 2-phenylethyl, benzyl, 1-phenylethy, 3-phenylpropyl, 4-phenylbutyl and like C 7 - 10 aralkyl groups, etc.
Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and like C 3 -C 8 cycloalkyl groups, etc. Preferable are C 3 -C 7 cycloalkyl groups.
Examples of heterocycloalkyl groups include substances in which one or more ring-constituting carbon atoms of cycloalkyl groups are replaced by atoms of nitrogen, oxygen, sulfur, etc.
Examples of monoalkylamino groups include amino groups monosubstituted with the above-described C 1 -C 6 alkyl groups.
Examples of dialkylamino groups include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, dibutylamino, dipentylamino, dihexylamino and like amino groups di-substituted with the above-described C 1 -C 6 alkyl groups.
Examples of acylamino groups include formylamino, benzoylamino, acetylamino, propionylamino, n-butyrylamino and like C 1 -C 8 acylamino groups (e.g., formylamino, alkanoylamino, and arylcarbonylamino).
Examples of alkylthio groups include —S—(C 1 -C 6 alkyl groups), etc. (C 1 -C 6 alkyl groups are the same as described above.)
Examples of heterocyclic groups include piperidyl, furyl, thienyl, imidazolyl, oxazolyl, triazolyl, pyrrolyl, pyrrolidinyl, triazolyl, benzothiazolyl, benzoimidazolyl, oxadiazolyl, thiadiazolyl, indolyl, pyrazolyl, pyridazinyl, cinnolinyl, quinolyl, isoquinolyl, quinoxalinyl, pyradinyl, pyridyl, benzofuryl, benzothienyl, tetrazolyl and like 5 to 10-membered monocyclic or bicyclic heterocyclic groups having at least one hetero atom selected from nitrogen, oxygen, and sulfur as a ring constituting atom.
Of the heterocyclic groups, examples of aromatic heterocyclic groups include furyl, thienyl, imidazolyl, oxazolyl, thiazolyl, pyrrolyl, triazolyl, benzothiazolyl, benzoimidazolyl, oxadiazolyl, thiadiazolyl, indolyl, pyrazolyl, pyridazinyl, cinnolinyl, quinolinyl, isoquinolinyl, quinoxalinyl, pyradinyl, pyridyl, benzofuryl, benzothienyl, tetrazolyl and like 5 to 10-membered monocyclic or bicyclic heteroaryl groups having at least one hetero atom selected from nitrogen, oxygen, and sulfur as a ring constituting atom.
Examples of acyl groups include formyl group; acetyl, propionyl, n-butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl and like straight or branched C 2 - 6 alkanoyl groups; and benzoyl and like C 7 -C 15 arylcarbonyl groups.
Specific examples of an alkyl group, an aralkyl group, an aryl group, a cycloalkyl group, a heterocycloalkyl group, and a heterocyclic group in an alkylsulfinyl group, an aralkylsulfinyl group, an arylsulfinyl group, a cycloalkylsulfinyl group, a heterocycloalkylsulfinyl group, and a sulfinyl group having a heterocyclic group bonded thereto are as described above.
Specific examples of an alkyl group, an aralkyl group, an aryl group, a cycloalkyl group, a heterocycloalkyl group, and a heterocyclic group in an alkylsulfonyl group, an aralkylsulfonyl group, an arylsulfonyl group, a cycloalkylsulfonyl group, a heterocycloalkylsulfonyl group, and a sulfonyl group having a heterocyclic group bonded thereto are as described above.
Examples of esters include an acyl-O-group and an alkoxy-CO-group. Herein, the above-mentioned “acyl groups” and “alkoxy groups” can be used as “acyl” and “alkoxy.”
The number of substituents in an alkyl group having at least one substituent, an alkoxy group having at least one substituent, or an alkenyl group having at least one substituent is 1 to 5, and preferably 1 to 3. Examples of the substituent include halogen, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, cyano, nitro, an amino group, a hydroxyl group, a C 1 -C 6 alkyl-carbonyloxy group (e.g., acetoxy), a C 1 -C 6 alkoxy-carbonyl group (e.g., isopropyloxycarbonyl), a C 3 -C 6 cycloalkyl group (e.g., cyclohexyl), and the like. Examples of an alkyl group having a halogen include an alkyl group in which a part or all of the hydrogen atoms are substituted with fluorine.
The number of substituents in an aralkyl group having at least one substituent, an aryl group having at least one substituent, an aryloxy group having at least one substituent, a cycloalkyl group having at least one substituent, a heterocycloalkyl group having at least one substituent, a heterocyclic group having at least one substituent, a monoalkylamino group having at least one substituent, a dialkylamino group having at least one substituent, an acylamino group, an alkylsulfinyl group having at least one substituent, an aralkylsulfinyl group having at least one substituent, an arylsulfinyl group having at least one substituent, a cycloalkylsulfinyl group having at least one substituent, a heterocycloalkylsulfinyl group having at least one substituent, a sulfinyl group to which a heterocyclic group having at least one substituent is bonded, an alkylsulfonyl group having at least one substituent, an aralkylsulfonyl group having at least one substituent, an arylsulfonyl group having at least one substituent, a cycloalkylsulfonyl group having at least one substituent, a heterocycloalkylsulfonyl group having at least one substituent, or a sulfonyl group to which a heterocyclic group having at least one substituent is bonded is 1 to 5, and preferably 1 to 3. Examples of the substituent include C 1 -C 6 alkyl groups, a halogen atom, C 1 -C 6 alkoxy groups, C 1 -C 6 alkylthio, cyano, nitro, an amino group, a hydroxyl group, and the like.
The number of substituents in 4 to 7-membered rings of an aliphatic group having at least one substituent is 1 to 5, and preferably 1 to 3. Examples of substituents include C 1 -C 6 alkyl groups, a halogen atom, C 1 -C 6 alkoxy groups, C 1 -C 6 alkylthio, cyano, nitro, an amino group, a hydroxyl group, carboxy ester, and the like. In addition,
is also included in a 4 to 7-membered ring of an aliphatic group having at least one substituent.
Examples of acyl groups include chloroacetyl group, bromoacetyl group, dichloroacetyl group, trifluoroacetyl group and like substituted acetyl groups; methoxyacetyl group, ethoxyacetyl group and like alkoxy-substituted acetyl groups; methylthioacetyl group and like alkylthio-substituted acetyl groups; phenoxyacetyl group, phenylthioacetyl group, 2-chlorobenzoyl group, 3-chlorobenzoyl group, 4-chlorobenzoyl group, 4-methylbenzoyl group, 4-t-butylbenzoyl group, 4-methoxybenzoyl group, 4-cyanobenzoyl group, 4-nitrobenzoyl group and like substituted benzoyl groups, etc.
IF 5 -pyridine-HF used in the production method of the present invention is a known substance disclosed in Non-patent Literature 1.
IF 5 -pyridine-HF is a complex constituted by (1) IF 5 , (2) 1 mol of pyridine per mol of IF 5 , and (3) 1 mol of HF per mol of IF 5 .
IF 5 -pyridine-HF can be produced according to the method disclosed in Non-patent Literature 1.
Specifically, IF 5 -pyridine-HF can be obtained by mixing IF 5 with pyridine-HF (pyridine 50 mol %, HF 50 mol %). Pyridine HF (pyridine 50 mol %, HF 50 mol %) can be obtained by adding pyridine to an equivalent mol of anhydrous HF.
As long as the effect of the present invention is not significantly impaired, the reaction system used in the production method of the present invention may contain IF 5 , pyridine, HF, or a combination thereof, which do not constitute the IF 5 -pyridine-HF.
In the production method of the present invention, at least one additive selected from the group consisting of amine/hydrogen fluoride salt, X a F (wherein X a represents hydrogen, potassium, sodium, or lithium), oxidizers, and reducing agents is used together with IF 5 -pyridine-HF.
The additive presumably functions as a reaction accelerator in the production method of the present invention; however, the present invention is not limited thereto.
Of the additives, the mechanism in which a reducing agent functions as a reaction accelerator is presumably based on the addition of IF generated from IF 5 in the IF 5 -pyridine-HF in the reaction system to an organic compound, which is a substrate; however, the present invention is not limited thereto.
The additive is preferably an amine/hydrogen fluoride salt or a reducing agent. In a preferable embodiment of the production method of the present invention, the additive is a reducing agent.
Examples of amine/hydrogen fluoride salt include primary amine/hydrogen fluoride salt, secondary amine/hydrogen fluoride salt, and tertiary amine/hydrogen fluoride salt.
Preferable examples of amine/hydrogen fluoride salt include aliphatic primary amine/hydrogen fluoride salt, aliphatic secondary amine/hydrogen fluoride salt, and aliphatic tertiary amine/hydrogen fluoride.
Specific examples of aliphatic primary amines in the aliphatic amine/hydrogen fluoride salt include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, etc.
Specific examples of aliphatic secondary amines in the aliphatic amine/hydrogen fluoride salt include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, etc.
Specific examples of aliphatic tertiary amines in aliphatic tertiary amine/hydrogen fluoride salt include trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N,N′,N′-tetramethylethylenediamine, etc.
Preferable examples of aliphatic groups of the aliphatic primary amine/hydrogen fluoride salt, aliphatic secondary amine/hydrogen fluoride salt, and aliphatic tertiary amine/hydrogen fluoride salt include methyl, ethyl, and butyl. More preferable examples include ethyl and butyl.
Amine/hydrogen fluoride salt are preferably tertiary amine/hydrogen fluoride salt, and more preferably aliphatic tertiary amine/hydrogen fluoride salt, and particularly preferably triethylamine/hydrogen fluoride salt.
Examples of triethylamine/hydrogen fluoride salt include Et 3 N-nHF (n is a real number of 1 to 9).
Examples of oxidizers include iodine, bromine, chlorine, etc.
Examples of reducing agents include hydrazine, formic acid, amines (e.g., primary amines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, and ethylenediamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, and dicyclohexylamine; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N,N′,N′-tetramethylethylene diamine, triphenylamine, diphenyl methylamine), potassium iodide, sodium iodide, lithium iodine, catechols that may have a substituent (e.g., catechols that may have at least one C 1 -C 3 alkyl group such as catechol and methylcatechol), hydroquinones that may have a substituent (e.g., hydroquinones that may have at least one C 1 -C 3 alkyl group such as hydroquinone and methyl hydroquinone), pyrogallols (e.g., pyrogallol that may have at least one C 1 -C 3 alkyl group such as pyrogallol and methyl pyrogallol), palladium carbon (Pd/C), tin (Sn), triphenyl phosphine (PPh 3 ), magnesium (Mg), aluminum (Al), etc. Preferable examples thereof include potassium iodide, catechols that may have a substituent (catechols that may have at least one C 1 to C 3 alkyl group such as catechol and methylcatechol), hydroquinones that may have a substituent (e.g., hydroquinones that may have at least one C 1 -C 3 alkyl group such as hydroquinone and methyl hydroquinone), Pd/C, Sn (turnings), triphenyl phosphine (PPh 3 ), magnesium (Mg), and aluminum (Al). More preferable examples thereof include potassium iodide (KI), catechols that may have a substituent (e.g., catechols that may have at least one C 1 to C 3 alkyl group such as catechol and methylcatechol) and hydroquinones that may have a substituent (e.g., hydroquinones that may have at least one C 1 -C 3 alkyl group such as hydroquinone and methyl hydroquinone).
The additive used in the production method of the present invention is preferably Et 3 N-nHF (wherein n is a real number of 1 to 9).
The amount of the IF 5 -pyridine-HF used in Step A is preferably in the range of 1 to 10 mol, more preferably 1 to 5 mol, and even more preferably 1.5 to 3 mol per mol of the organic compound, which is a starting material compound.
The amount of the additive used in Step A is preferably in the range of 0.01 to 10 mol, more preferably in the range of 0.1 to 5 mol, and even more preferably in the range of 0.1 to 2 mol per mol of the IF 5 -pyridine-HF.
Step A in the production method of the present invention can be preferably performed in air. The air may be an ordinal air that has not been dried. Accordingly, the production method of the present invention can be performed at low cost, and is industrially advantageous.
The reaction temperature of Step A in the production method of the present invention is generally in the range of −20 to 140° C., preferably in the range of 0 to 120° C., and more preferably in the range of 20 to 100° C.
The reaction time of Step A in the production method of the present invention is generally in the range of 0.5 to 48 hours, preferably in the range of 1 to 24 hours, and more preferably in the range of 2 to 24 hours.
The production method of the present invention is preferably performed in the presence of a reaction solvent.
Examples of the reaction solvent include methylene chloride, tetrachloroethane, chloroform, carbon tetrachloride, cyclohexane, and mixed solvents of two or more of these.
The amount of the reaction solvent used in Step A is in the range of 5 to 50 parts by weight, and more preferably in the range of 10 to 30 parts by weight per part by weight of the organic compound which is a starting compound.
The production method of the present invention can be carried out in air by adding, to a reaction solvent and IF 5 -pyridine-HF that have been placed in a reactor, an organic compound having at least one hydrogen atom.
The fluorinated organic compound produced by the method of the present invention can be generated by a known method, such as extraction.
Fluorinating Reagent
The fluorinating reagent of the present invention contains at least one additive selected from the group consisting of (1) IF 5 -pyridine-HF, and (2) amine/hydrogen fluoride salt, X a F (wherein X a is a hydrogen atom, sodium, potassium, or lithium), oxidizers, and reducing agents.
In a preferable embodiment of the fluorinating reagent of the present invention, the additive is a reducing agent.
IF 5 -pyridine-HF and the additive contained in the fluorinating reagent of the present invention are those explained in the production method of the present invention.
The form of the fluorinating reagent of the present invention is not limited as long as the fluorinating reagent contains IF 5 -pyridine-HF and the additive. For example, the fluorinating reagent may be a mixture of IF 5 -pyridine-HF and the additive, or a kit in which IF 5 -pyridine-HF and the additive are separated from each other.
The additive contained in the fluorinating reagent of the present invention is preferably Et 3 N-nHF (wherein n is a real number of 1 to 9).
The amount of the additive contained in the fluorinating reagent of the present invention is preferably in the range of 0.01 to 10 mol, more preferably in the range of 0.1 to 5 mol, and even more preferably in the range of 0.1 to 2 mol per mol of the IF 5 -pyridine-HF.
Advantageous Effects of Invention
The production method or fluorinating reagent of the present invention can provide, with a high yield, a fluorinated organic compound that has not been produced with a sufficient yield by a conventional method using a fluorinating agent containing IF 5 -pyridine-HF alone.
Examples of the fluorinated organic compound that have not been produced with a sufficient yield by a conventional method include compounds with a larger fluorine amount. Specific examples of the compounds include
trifluoromethyl 4-isopropyl phenyl ether,
1-bromo-4-(trifluoromethoxy)benzene,
ethyl 4-(trifluoromethoxy)benzoate,
1-(trifluoromethoxy)decane,
(3-(trifluoromethoxy)propyl)benzene,
ethyl 3-((4-chlorophenyl)thio)-2,2,3-trifluoropropanate,
4-pentyl-4′-(trifluoromethoxy)-1,1′-bi(cyclohexane),
1-fluoro-2-iodocyclododecane,
5-fluoro-6-iododecane, and
(Z)-2-fluoro-1-iodododecan-1-ene.
DESCRIPTION OF EMBODIMENTS
The present invention is detailed below with reference to the Examples; however, it is not limited to the Examples.
Example 1-1
In air, IF 5 -pyridine-HF (370 mg, 1.15 mmol) and Et 3 N-6HF (1.15 mmol) were added to methylene chloride (2 mL) in a Teflon (trade name) container, and compound 1a (O-(4-isopropyl phenyl)S-methyl dithiocarbonate) (0.5 mmol) was added thereto at room temperature, followed by stirring at 60° C. for six hours. The reaction mixture was added to water (20 mL), and extraction was performed using methylene chloride three times (20 mL×3). The organic layer was washed with a saturated sodium bicarbonate aqueous solution (20 mL) and a saturated sodium thiosulfate aqueous solution (20 mL), and then dried with magnesium sulfate. After condensation, product 2a (trifluoromethyl 4-isopropyl phenyl ether) was obtained by silica gel column chromatography (hexane ether) with a yield of 70%.
Example 1-2
In air, IF 5 -pyridine-HF (321 mg, 1.00 mmol) and Et 3 N-6HF (553 mg, 2.50 mmol) were added to methylene chloride (1 mL) in a Teflon (trade name) container, and compound 1a (O-(4-isopropyl phenyl)S-methyl dithiocarbonate) (0.5 mmol) was added thereto at room temperature, followed by stirring at 60° C. for nine hours. The reaction mixture was added to water (30 mL), and extraction was performed using methylene chloride three times (20 mL×3). The organic layer was washed with a saturated sodium bicarbonate aqueous solution (20 mL) and a saturated sodium thiosulfate aqueous solution (20 mL), and then dried with magnesium sulfate. After condensation, product 2a (trifluoromethyl 4-isopropyl phenyl ether) was obtained by silica gel column chromatography (hexane ether) with a yield of 74%.
Comparative Example 1
In air, IF 5 -pyridine-HF (321 mg, 1.00 mmol) was added to methylene chloride (1 mL) in a Teflon (trade name) container, and compound 1 (0.5 mmol) was added thereto at room temperature, followed by stirring at 60° C. for nine hours. The reaction mixture was added to water (30 mL), and extraction was performed using methylene chloride three times (20 mL×3). The organic layer was washed with a saturated sodium bicarbonate aqueous solution (20 mL) and a saturated sodium thiosulfate aqueous solution (20 mL), and then dried with magnesium sulfate. After condensation, product 2 was obtained by silica gel column chromatography (hexane ether) with a yield of 4%.
It is obvious from the comparison of Example 1-1 and Comparative Example 1 that the use of additive Et 3 N-6HF remarkably increased the yield of product 2 in Example 1-1.
Comparative Example 2
In air, IF 5 (1.00 mmol), pyridine-HF (pyridine 1.00 mmol, HF 7.00 mmol), and Et 3 N (1.00 mmol) were added to methylene chloride (1 mL) in a Teflon (trade name) container, and compound (0.5 mmol) was added thereto at room temperature, followed by stirring at 60° C. for nine hours. The reaction mixture was added to water (20 mL), and extraction was performed using methylene chloride three times (20 mL×3). The organic layer was washed with a saturated sodium bicarbonate aqueous solution (20 mL) and a saturated sodium thiosulfate aqueous solution (20 mL), and then dried with magnesium sulfate. After condensation, product 2 was obtained by silica gel column chromatography (hexane ether) with a yield of 41%.
It is obvious from the comparison of Example 1-1 and Comparative Example 2 that although IF 5 , pyridine, HF, and triethylamine were used in Comparative Example 2 in the same molar ratio as in Example 1-1, and the same reaction temperature, reaction time, and purification method were employed, product 2 was not obtained with a sufficient yield. This indicates that product 2 was not obtained with a high yield merely by adding Et 3 N as an additive to the reaction system.
TABLE 1
Fluorinating reagent
Example 1-1
(IF 5 -Py-HF) +
Yield 70%
(Et 3 N—6HF)
Comparative
(IF 5 -Py-HF)
Yield 4%
Example 1
Comparative
IF 5 + Py +
Yield 41%
Example 2
7HF + Et 3 N
Example 2
Products were synthesized in the same manner as in Example 1, except that the substrate (compound 1a), reaction temperature, time, and solvent used in Example 1-1 were changed to those shown in Table 2.
Regarding the “yield/%” in Table 2, the 19 F-NMR yield is based on the substrate. The value in parenthesis is an isolation yield.
TABLE 2
Temperature/
Time/
Yield/
Substrate
° C.
h
Solvent
Product
%
60
24
(CH 2 Cl) 2
70
60
24
(CH 2 Cl) 2
65(55)
r.t.
2
CH 2 Cl 2
93(91)
r.t.
3
CH 2 Cl 2
100(67)
0
24
CH 2 Cl 2
(70)
Example 3s
Polyfluorination Reaction of Alkyl Sulfide
IF 5 -pyridine-HF (321 mg, 1 mmol) and dichloroethane (2.0 mL) were added to a Teflon (trade name) reaction vessel with a lid. Three drops of Et 3 N-7HF (54 mg, 0.22 mmol) were added thereto at room temperature. Subsequently, substrate 3 (122 mg, 0.5 mmol) was added thereto, followed by reaction at 80° C. for 14 hours. The reaction mixture was poured into water (30 mL) in a polycontainer, and neutralized with saturated NaHCO 3 water, followed by ether extraction. After dehydration with magnesium sulfate, the solvent was removed under reduced pressure. An internal standard (monofluorobenzene) was added to the residue, and the product was quantified by 19 F-NMR. The results indicate that trifluoro body 4 was produced with a yield of 63%.
Example 4
Addition to Alkene (1)
A substrate (alkene 5a, 0.5 mmol), methylene chloride (3 mL), and IF 5 -pyridine-HF (161 mg, 0.5 mmol) were added to a Teflon (trade name) container, and KI (83 mg, 0.5 mmol) was added thereto while stirring the mixture at 0° C. The mixture was then stirred at 0° C. for 30 minutes, and at room temperature for 17 hours. After the reaction, product 6a was extracted with methylene chloride, and purified by silica gel column chromatography (ethyl acetate-hexane) to obtain product 6a with a yield of 78%.
Example 5
Addition to Alkene (2)
A substrate (alkene 5b, 0.5 mmol), methylene chloride (3 mL), and IF 5 -pyridine-HF (161 mg, 0.5 mmol) were added to a Teflon (trade name) container, and KI (83 mg, 0.5 mmol) was added thereto while stirring the mixture at 0° C. The mixture was then stirred at 0° C. for 30 minutes, and at room temperature for 17 hours. After the reaction, product 6b was extracted with methylene chloride, and purified by silica gel column chromatography (ethyl acetate-hexane) to obtain product 6b with a yield of 60%. The 19 F-NMR yield was 90%.
Example 6
Addition to Alkyne
Alkyne 7 (0.5 mmol), IF 5 -pyridine-HF (1.0 mmol, 320 mg), and dichloroethane (5 mL) were added to a Teflon (trade name) container, and the mixture was stirred at 0° C. for 20 minutes. An additive shown in Table 3 (hydroquinone (1.0 mmol, 110 mg) or catechol (1.0 mmol, 110 mg) was added thereto, and the mixture was further stirred at 0° C. for 30 minutes, and at room temperature for 12 hours. After extraction with dichloroethane, isolation and purification was performed by silica gel column chromatography (ethyl acetate-hexane). Table 3 shows the yield of product 8.
In Table 3, regarding the “yield/%,” the 19 F-NMR yield was based on the substrate. The value in parenthesis is the isolation yield.
TABLE 3
8
Additive
Yield/%
Hydroquinone
82 (63)
Catechol
75
Example 7
Products were synthesized in the same manner as in Example 6, except that the substrate (compound 7), amount of IF 5 -pyridine-HF, additive, time, and reaction solvent used in Example 6 were changed to those shown in Table 4.
Regarding the “yield/%” in Table 4, the 19 F-NMR yield is based on the substrate. The value in parenthesis is an isolation yield.
TABLE 4
Time/
Yield/
Substrate
IF 5 -pyridine-HF
Additive
h
Solvent
Product
%
Ph—≡—H 7b
1.5 eq.
Hydroquinone 1.5 eq.
9
CH 2 Cl 2
56
Ph—≡—Ph 7c
2.0 eq.
Hydroquinone 2.0 eq.
15
CH 2 Cl 2
90(72)
Pr—≡—Pr 7d
2.0 eq.
Hydroquinone 2.0 eq.
15
CH 2 Cl 2
87
2.0 eq.
Hydroquinone 2.0 eq.
19
CH 2 Cl 2
73
2.0 eq.
Hydroquinone 2.0 eq.
20
CH 2 Cl 2
72
2.0 eq.
Hydroquinone 2.0 eq.
20
CH 2 Cl 2
67 | Object: An object of the present invention is to provide a method for producing, with a high yield, a fluorinated organic compound, the fluorinated organic compound having not been produced with a sufficient yield by a conventional method for producing a fluorinated organic compound using a fluorinating agent containing IF 5 -pyridine-HF alone. Another object of the present invention is to provide a fluorinating reagent.
Means for achieving the object: A method for producing a fluorinated organic compound comprising step A of fluorinating an organic compound by bringing the organic compound into contact with (1) IF 5 -pyridine-HF and (2) at least one additive selected from the group consisting of amine hydrogen fluorides, X a F (wherein X a represents hydrogen, potassium, sodium, or lithium), oxidizers, and reducing agents. | 2 |
FIELD OF THE INVENTION
The present invention relates to automotive vehicle components and heat shields, and more particularly, to an automotive vehicle component having an integral heat shield.
BACKGROUND OF THE INVENTION
Various automotive vehicle components include temperature sensitive regions. These same components are often used in high temperature applications. Therefore, a heat shield is used to protect the heat sensitive region. One type of heat shield includes a strap-type heat shield. A strap-type heat shield attaches to the component in a manner similar to that of a belt. The strap is fed through at least one loop or flange portion on the automotive component and the ends are buckled or attached together. The strap-type heat shield has a primary shielding area, which is disposed over the heat sensitive region of the component. Problems associated with using a strap-type heat shield includes the additional cost of purchasing the heat shield, additional cost and complexity associated with manufacturing loops or flanges on the automotive component, and the extreme difficulty of assembly in mass production. As stated above, the strap-type heat shield is typically fed through at least one loop or flange formed on the automotive component. The loop or flange sometimes has less than 5 mm of clearance through curved, sharp and tacky rubber bonded surfaces. Therefore, manipulating the strap through these areas can be frustrating and time consuming.
SUMMARY OF THE INVENTION
The present invention provides an integrated automotive vehicle component and heat shield apparatus. The apparatus includes a body having a heat sensitive region and a heat shield integrally molded thereon. The heat shield includes a first edge and a second edge. The first edge is bonded, via the molding process, to a first area of the body. The second edge is attached to a second area of the body. The second area is opposite the heat sensitive region from the first area. Thus, the heat shield covers the heat sensitive region of the body.
Another aspect of the present invention includes a method of providing an integrated automotive vehicle component and heat shield apparatus. The method first includes selecting a component body. Next, a first edge of the heat shield is molded onto a first area of the component body. The heat shield is then folded about the first edge such that a second edge becomes juxtaposed with a second area of the component body. Finally, the second edge is attached to the second area of the component body.
Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
FIG. 1 is an isometric view of an exemplary integrated automotive vehicle component and heat shield apparatus in accordance with the principles of the present invention;
FIG. 2 is a front view of the integrated automotive vehicle component and heat shield apparatus of FIG. 1 as removed from the mold;
FIG. 3 is a front view of the integrated automotive vehicle component and heat shield apparatus of FIGS. 1 and 2 with the second edge of the heat shield attached to the component body;
FIG. 4 is a front view of an exemplary mold assembly used to fashion the integrated automotive vehicle component and heat shield apparatus of FIGS. 1–3 ; and
FIG. 5 is a flowchart of a method of providing an integrated automotive vehicle component and heat shield apparatus in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
With reference to FIGS. 1 and 2 , an integrated automotive vehicle component and heat shield apparatus 10 is described. The apparatus 10 includes an automotive component body 12 having a body cap 14 , a pedestal 16 , a base plate 18 , and a heat shield 20 . In the embodiment illustrated, the automotive component is a powertrain mount. It should be appreciated, however, that any mechanical component requiring a heat shield is intended to be within the scope of the present invention. The base plate 18 supports the pedestal 16 , which supports the base cap 14 . The heat shield 20 includes a first edge 22 and a second edge 24 . The first-edge 22 is integrally bonded to a first area 26 of the base plate 18 such that the heat shield 20 naturally appends from the base plate 28 . The pedestal 16 includes a heat sensitive region 25 . The body cap 14 and base plate 18 are molded of steel and the pedestal 16 and heat shield 20 are molded of rubber.
Referring to FIG. 3 , the second edge 24 of the heat shield 20 is attached to a second area 28 of the body cap 14 . In the embodiment illustrated, the second edge 24 is attached to the second area 28 with an adhesive. In an alternative exemplary embodiment, the second edge 24 is attached to the second area 28 with an interference fit. It is envisioned that the interference fit may include a tongue formed on the heat shield 20 and received in an aperture formed in the second area 28 of the body cap 14 . It is further envisioned that the interference fit may include a tongue formed on the second area 28 of the body cap 14 and received in an aperture molded into the second edge 24 of the heat shield 20 . It is also envisioned that the engagement between the second edge 24 and the second area 28 is more robust than the bonding between the first edge 22 and the first area 26 of the base plate 18 . This ensures that the heat shield 20 will continue to cover the heat sensitive region 25 of the pedestal 16 even in the event that the first edge 22 becomes debonded from the first area 26 .
With further reference to FIGS. 2 and 3 , the heat shield 20 has a dimension D 1 that is greater than a dimension D 2 between the first area 26 of the body 12 and the second area 28 of the body 12 . This provides for a heat shield 20 having an arch-shaped front elevation upon attachment of the second edge 24 . Such arch-shaped front elevation reduces tension at the interfaces between the first and second edges 22 , 24 and the first and second areas 26 , 28 , respectively.
With reference to FIG. 4 , a mold assembly 30 for integrally forming a heat shield 20 onto an automotive vehicle component in accordance with the present invention is described. The mold assembly 30 includes a top mold member 32 , a bottom mold member 34 , a first intermediate mold member 36 , and a second intermediate mold member 38 . The top mold member 32 includes a body cap cavity 40 adapted to receive the preformed body cap 14 of the body 12 . The bottom mold member 34 includes a base plate cavity 42 , a heat shield cavity 44 , and a first feed bore 45 . The base plate cavity 42 is adapted to receive the preformed base plate 18 of the body 12 . The heat shield cavity 44 is adapted to define the geometry of the integrated heat shield 20 upon injection with a liquid rubber. The first and second intermediate mold members 36 , 38 include cooperative first and second pedestal cavities 46 , 48 for defining the pedestal 16 of the body 12 upon injection with a molten rubber. The first intermediate mold member 36 further includes a second feed bore 49 . This configuration of split mold members enables the heat shield 20 to be integrally molded onto the body 12 of the automotive component in accordance with the present invention. It should be appreciated, however, that the above-described mold assembly 30 is merely exemplary, and that other mold assemblies capable of producing the same result are intended to be within the scope of the present invention.
FIG. 5 is a flowchart illustrating a method of providing an integrated automotive vehicle component and heat shield apparatus 10 in accordance with the present invention. Initially, a component body 12 is selected 50 , which, in an exemplary embodiment includes a powertrain mount having a body cap 14 and a base plate 18 . Next, adhesive is applied 52 to the first area 26 and a pedestal support area (not shown) of the base plate 18 . Further, adhesive is applied 54 to an underside area (not shown) of the body cap 14 . The base plate 18 is then deposited 56 into the base plate cavity 42 in the bottom member 34 and the body cap 14 is deposited 58 into the body cap cavity 40 in the top member 32 . The top, bottom and intermediate members 32 , 34 , 36 , and 38 of the mold assembly 30 are then assembled 60 into the configuration illustrated in FIG. 4 . Molten rubber is injected 62 through the first and second feed bores 45 , 49 to fill the heat shield and cooperating pedestal cavities 44 and 46 , 48 . This creates the pedestal 16 having the heat sensitive region 25 . In an exemplary embodiment, the steps of filling the pedestal cavities 46 , 48 and the heat shield cavity 44 occur substantially contemporaneously.
Subsequent to the pedestal 16 and heat shield 20 curing, the mold members 32 , 34 , 36 , and 38 are disassembled 64 and the integrated automotive vehicle component and heat shield apparatus 10 is removed 66 . The second edge 24 of the heat shield 20 is then folded 68 about the first edge 22 of the heat shield 20 and attached 70 to the second area 28 of the body cap 14 . In an exemplary embodiment, the second edge 24 is attached by applying an adhesive to either the second edge 24 , the second area 28 , or both. In an alternative exemplary embodiment, the second edge 24 is attached by inserting a tongue formed on the second edge 24 into an aperture formed in the second area 28 . In yet another alternative exemplary embodiment, the second edge 24 is attached by inserting a tongue formed on the second area 28 into an aperture formed on or near the second edge 24 of the heat shield 20 . It should be appreciated that while a number of attaching means have been described herein, any means of attaching the second edge 24 to the second area 28 is intended to be within the scope of the present invention.
The description of the invention is merely exemplary in nature and, thus, variations that do not depart from the gist of the invention are intended to be within the scope of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention. | An integrated automotive vehicle component and heat shield apparatus is provided. The apparatus includes a body having a heat sensitive region and a heat shield integrally molded thereon. The heat shield includes a first edge and a second edge. The first edge is bonded, via the molding process, to a first area of the body. The second edge is attached to a second area of the body. The second area is opposite the heat sensitive region from the first area. Thus, the heat shield covers the heat sensitive region of the body. | 5 |
BACKGROUND OF THE INVENTION
A plasma spray apparatus is employed for spraying powdered material to provide a permanent coating on all or part of a workpiece. This is done to modify the surface characteristics of the workpiece, for example, to change the dimensions of the workpiece, to make the workpiece more adaptable to temperature variations, to vary the coefficient of friction of the workpiece surface, to alter the ability of the workpiece to withstand exposure to abrasive chemicals and environment, etc.
A plasma spray apparatus utilizes powdered materials such as metals, ceramics, intermetallics or plastics. The powdered materials are carried to the plasma flame or stream by a powder feed system that utilizes a metering device and a feed tube. The powdered material is carried through the feed tube and toward the plasma flame by a pressurized gas. The powdered particles then pass through the plasma flame, where temperatures are typically in the range of 12,000 F. to 20,000 F., and are carried to and deposited on the workpiece.
Prior art plasma spray or powder feed systems require several seconds, typically eight or nine seconds, from the time the entire system is activated until a uniform flow of powdered material passing through the system is obtained. During this transition period, the rate of flow of powder will gradually increase from zero up to the desired rate for application on the workpiece. Similarly, when a prior art system is deactivated, several seconds elapse before the flow of powder stops completely. This elapsed or transition time is caused in part by the distance from the reservoir or hopper where the powder is stored to the workpiece. Additionally, the pressurized gas and the powder must overcome inertia to be accelerated during activation of the system, and decelerated during deactivation of the system.
This inertial phenomena of a variable flow rate during the transition period immediately following activation or deactivation of the prior art systems causes operating problems and inefficiencies. Specifically, workpiece specifications typically require the application of a uniform thickness of plasma spray powder. However, as mentioned above, the rate of flow of powder varies during the transition period following activation or deactivation of the plasma spray system. Therefore, to insure a uniform application of the powdered material on the workpiece, a prior art system must be activated and sprayed for several seconds before directing the plasma spray on the area to be coated. Similarly, the time required for deactivation of the prior art feed system cannot be commenced until after the plasma spray powder has been applied to the entire area for which the coating is required. As a result, the powder expended during the activation and deactivation periods is wasted causing a substantial inefficiency in the operation of the prior art plasma spray system. Furthermore, since the powdered materials used with plasma spray systems is extremely expensive, inefficiencies caused by the activation and deactivation periods adds significantly and unnecessarily to the cost of operating the system.
The magnitude of the loss caused by the elapsed or transition time in activating and deactivating a prior art feed system varies according to the workpiece. In certain applications, for example, it is desirable to apply a uniform thickness of plasma spray coating to one area of the workpiece without applying it to adjacent areas. To overcome the problem of variable flow rates during the transition period immediately after activation or deactivation of the system, a prior art plasma spray applicator would be directed at areas of the workpiece for which no coating is desired until the maximum flow is achieved. The spray then would be directed at the area to be coated, but then would be directed to another area for which no coating is desired during the deactivation period. A separate machining step would then have to be carried out to remove the plasma spray coating that was applied during the activation and deactivation of the prior art plasma spray system. As an alternative to machining the unwanted plasma spray coating of the workpiece, the workpiece could be initially masked adjacent to the area for which the coating is intended. Thus, the plasma spray would be directed at the masked area during the transition periods of powder feed. These machining and masking operations are time-consuming and add significantly to the manufacturing cost. Furthermore, as mentioned above, there is a substantial amount of costly powder wasted during the activation and deactivation, i.e., transition, periods when utilizing prior art feed systems in a plasma spray apparatus.
The magnitude of the inefficiencies described above is even greater in applications where a single workpiece includes several areas for which a uniform coating of plasma spray material is desired. Because of the time required to activate and deactivate the system, it becomes virtually impossible to shut the system down while moving the plasma spray applicator from one area of desired application to the next. As a result, the plasma spray system is operated at its peak application rate even in areas between the areas of desired application. Thus, the plasma spray material is applied at its full thickness in these areas and afterwards must be removed by machining or removal of the mask. In applications such as this, the amount of powder wasted may easily exceed the amount of powder applied.
Accordingly, it is an object of the subject invention to provide a plasma spray apparatus on which the flow of powdered materials may be started and stopped abruptly without a transition period of variable flow rate.
It is a further object of the subject invention to provide a plasma spray apparatus that avoids the need to machine or mask the areas adjacent to the parts of the workpiece on which the plasma spray coating is desired.
It is still a further object of the subject invention to provide a plasma spray apparatus that will significantly reduce the cost and time required to properly coat a workpiece.
SUMMARY OF THE INVENTION
The plasma spray apparatus of the subject invention includes a powder feed hopper capable of storing a relatively large volume of powdered material for application on the workpiece. The powder feed hopper includes a means, such as a metering wheel, for feeding powder at a predetermined rate into a powder feed tube. The powder feed tube extends from the powder feed hopper to a plasma spray applicator. Typically, the plasma spray applicator is a gun and includes a flame which operates in the range of 12,000 F. to 20,000 F. The flame heats the powder and the workpiece prior to application of the powder on the workpiece. A pressure source is provided to direct a pressurized gas into the powder feed tube at the powder feed hopper. The powdered material is interspersed in the pressurized gas and is carried through the powder feed tube toward the applicator as a gas-powder mixture. A powder accumulator also is provided, and is connected to the powder feed tube by a diversion tube or other similar device. The diversion tube is connected to the powder feed tube at a location on the powder feed tube close to the plasma spray applicator. A valve means is provided at the connection between the powder feed tube and the diversion tube enabling the gas-powder mixture traveling through the powder feed tube to be alternately diverted to either the plasma spray applicator or the powder accumulator. A recirculation tube with a recirculation valve can connect the powder accumulator to the powder feed hopper to enable the powder to be recirculated from the powder accumulator to the powder feed hopper. Gas tubes also may be provided to alternately direct a flow of pressurized gas into either the powder feed hopper or the powder accumulator, and a vent and vent valve may be provided on the powder accumulator to selectively allow the release of gas therefrom.
During periods when it is desired not to coat the workpiece with the plasma spray coating, the gas-powder mixture traveling through the powder feed tube is directed from the plasma spray applicator to the powder accumulator by means of the diversion tube. The close proximity of the diversion tube to the plasma spray applicator enables the powder flowing to the workpiece to be ceased abruptly. Thus, there is no transition period during which the flow of powder onto the workpiece varies. During these periods the vent valve on the vent in the powder accumulator may be opened to enable the gas from the gas-powder mixture to escape from the powder accumulator and to allow the powder to remain therein.
Conversely, during periods when it is desirable to apply the powdered material to the workpiece, the gas-powder mixture is directed toward the plasma spray applicator, the vent in the powder accumulator may be closed, and forced gas may be injected into the powder accumulator to recirculate the powder therein to the powder feed hopper. The gas-powder mixture traveling from the powder accumulator through the recirculation tube into the powder feed hopper functions to facilitate the movement of powdered material in the powder feed hopper from the powder feed tube.
During periods of both application and diversion, the powder is continuously moving through the powder feed tube. Therefore, the inertial problem associated with activation of the system is avoided when the powder is directed back to the plasma spray applicator from the diversion tube.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of the plasma spray system of the subject invention adjusted to enable the application of the powdered material onto the workpiece.
FIG. 2 is a schematic view of the plasma spray system of the subject invention adjusted to divert the powder material to the powder accumulator instead of onto the workpiece.
FIG. 3 is a cross-sectional view of a cylindrical workpiece having annular grooves disposed in a central bore, and having the plasma spray coating applied in the grooves.
FIG. 4 is a cross-sectional view taken perpendicular to the longitudinal axis of the cylindrical workpiece of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, the plasma spray system of the subject invention includes a powder feed hopper 10 with a supply of powder P stored therein. The powder feed hopper 10 is typically a one-to-ten gallon container. Metering wheel 12 is attached to powder feed hopper 10 and feeds stored powder P into powder feed tube 13. Powder feed tube 13 extends from the metering wheel 12 to plasma spray applicator 14. Powder feed gas tube 15 is connected to powder feed tube 13 at metering wheel 12, and directs pressurized gas indicated by arrows G from pressure source 16 into powder feed tube 13. The gas G is mixed with powder P from the powder feed hopper 10 and moves as a gas-powder mixture M through powder feed tube 13 toward powder applicator 14. The powder applicator 14 provides a flame with a maximum temperature in the range of 12,000 F. to 20,000 F. The flame heats the gas-powder mixture M and the workpiece 18. The heated gas-powder mixture M then is applied as plasma stream 17 to workpiece 18.
Diversion tube 19 is connected to powder feed tube 13 at location 20 which is in close proximity to plasma spray applicator 14. Diversion tube 19 extends from powder feed tube 13 at location 20 to powder accumulator 21. Valve 22 is located on powder feed tube 13 between plasma spray applicator 14 and location 20 where diversion tube 19 meets powder feed tube 13. Valve 23 is located on diversion tube 19 near connection 20 of diversion tube 19 to powder feed tube 13. Valves 22 and 23 operate as a pair such that when one is opened, the other is closed. As shown by the arrows in FIG. 1, valve 23 is in the closed position thereby prohibiting the gas-powder mixture M to travel through diversion tube 19 to powder accumulator 21. Valve 22, on the other hand, is opened thereby enabling the gas-powder mixture M to travel through powder feed tube 13 to plasma spray applicator 14 and onto workpiece 18 in the form of plasma stream 17. Although valves 22 and 23 are schematically shown as being separate, a single valve at location 20 could be provided to direct gas-powder mixture M selectively and alternatively to either plasma spray applicator 14 or diversion tube 19.
Gas tube 24 is connected to powder feed gas tube 15 at T-connection 25, and carries gas G from pressure source 16. Although gas tube 24 and powder feed gas tube 15 are depicted as being connected to a single pressure source 16 they could be connected to separate pressure sources. Hopper gas tube 26 extends from gas tube 24 at T-connection 27 to powder feed hopper 10. Accumulator gas tube 28 extends from gas tube 24 at T-connection 27 to powder accumulator 21. Hopper gas tube valve 29 located on hopper gas tube 26 and accumulator gas tube valve 30 located on accumulator gas tube 28 operate as a pair such that when one is opened, the other is closed. In FIG. 1, as shown by the arrows, hopper gas tube valve 29 is closed and accumulator gas tube valve 30 is opened. As a result, there is no gas flowing through hopper gas tube 26. Conversely, gas G from pressure source 16 flows through gas tube 24 and through accumulator gas tube 28 into powder accumulator 21. Hopper gas tube valve 29 and accumulator gas tube valve 30 could be replaced by a single valve located at the T-connection 27.
Recirculation tube 31 extends from powder accumulator 21 to powder feed hopper 10. Recirculation tube valve 32 is located on recirculation tube 31 to selectively permit the gas-powder mixture M to travel through recirculation tube 31 toward powder feed hopper 10.
Vent 33 with vent valve 34 is connected to powder accumulator 21 to selectively permit gas G to escape from powder accumulator 21 as described below.
In operation, gas G travels through powder feed gas tube 15 into powder feed tube 13 at metering wheel 12. Simultaneously, powder P is released from powder feed hopper 10 and dispensed into powder feed tube 13 by metering wheel 12. Gas G and powder P combine in the metering wheel 12 to form gas-powder mixture M which travels through powder feed tube 13. As shown in FIG. 1, diversion tube valve 23 is closed and powder feed tube valve 22 is opened. Therefore, gas-powder mixture M continues through powder feed tube valve 22 to plasma spray applicator 14. Heat is applied to gas-powder mixture M at plasma spray applicator 14 to form plasma stream 17 which is applied to workpiece 18.
Gas G from pressure source 16 also is directed through gas tube 24. Hopper gas tube valve 29 is closed and accumulator gas tube valve 30 is opened. Therefore, gas G from gas tube 24 flows through accumulator gas tube valve 30 and through accumulator gas tube 28 into the powder accumulator 21. Vent valve 34 on vent 33 is closed thereby prohibiting gas G which enters powder accumulator 21 through accumulator gas tube 28, to be released through vent 33. However, recirculation valve 32 is opened. As a result, gas G from accumulator gas tube 28 will flow through powder accumulator 21 and through recirculation tube 31 into powder feed hopper 10, thereby facilitating the powder P in powder feed hopper 10 to be forced into powder feed tube 13 through metering wheel 12. If, as shown in FIG. 1, powder P is accumulated in powder accumulator 21, the gas G traveling through accumulator gas tube 28 will mix with powder P in powder accumulator 21. The resultant gas-powder mixture M will be forced through recirculation tube 31 to powder feed hopper 10. The powder P from the gas-powdered mixture M that enters powder feed hopper 10 through recirculation tube 31 will be stored in powder feed hopper 10 while the gas G from the gas-powder mixture M facilitates the movement of powder P in powder feed hopper 10 into powder feed tube 13.
By this operation, powder P from powder feed hopper 10 is directed through powder feed tube 13 to plasma spray applicator 14 at a constant rate to achieve a uniform coating of plasma spray on workpiece 18.
FIG. 2 shows the plasma spray system of the subject invention adjusted to prohibit the flow of powder P to plasma spray applicator 14. In this arrangement, accumulator gas tube valve 30 is closed and hopper gas tube valve 29 is opened. As a result, gas G is directed through hopper gas tube 26 and into powder feed hopper 10 instead of being directed through accumulator gas tube 28 and into powder accumulator 21 as had been shown in FIG. 1. The gas G that enters powder feed hopper 10 in FIG. 2 facilitates the movement of powder P into metering wheel 12 where it mixes with gas G to form gas-powder mixture M, and travels through gas feed tube 13. FIG. 2 also shows that powder feed tube valve 22 is closed and diversion tube valve 23 is opened. As a result, gas-powder mixture M is directed through diversion tube 19 into powder accumulator 21 instead of continuing through powder feed tube 13 to plasma spray applicator 14 as had been the case in FIG. 1.
FIG. 2 also shows recirculation tube valve 32 in a closed position. As a result, the gas-powder mixture M cannot travel through recirculation tube 31 from powder accumulator 21 to powder feed hopper 10. Vent valve 34 is opened in FIG. 2, thereby enabling gas G from the gas-powder mixture M that enters powder accumulator 21 through diversion tube 19 to be released through vent 33. On the other hand, the powder P from the gas-powder mixture M that enters powder accumulator 21 through diversion tube 19 remains in powder accumulator 21.
All the valves shown in FIGS. 1 and 2 are electronically operated and are connected to one another so that the valves can be changed simultaneously from the open/shut arrangement shown in FIG. 1 to the arrangement shown in FIG. 2, or the reverse. In other words, by a single switch, the system can be changed from the spraying and recirculating arrangement of FIG. 1 to the accumulating arrangement of FIG. 2.
As mentioned above, the plasma spray applicator 14 is in close proximity to connection 20 between diversion tube 19 and powder feed tubes 13. Thus, in switching from the arrangement shown in FIG. 1 to the arrangement shown in FIG. 2, there is an abrupt cessation of the spraying operation with virtually no transition period. Conversely, when a spraying operation is started by switching from the arrangement in FIG. 2 to the arrangement in FIG. 1, the gas-powder mixture M flows into plasma spray applicator 14 immediately with virtually no transition period as had been the case in the prior art. Furthermore, the powder P is continuously moving both in the arrangement of FIG. 1 and the arrangement of FIG. 2. As a result, in switching from the FIG. 2 to the FIG. 1 arrangement, there is no need to overcome the inertia of stationary powder, and the powder flows immediately at its optimum rate.
FIGS. 3 and 4 show a sample cylindrical workpiece 35 with a central bore 36 defined by alternating cylindrical surfaces 37 and 38, and radially aligned surfaces 39 extending between surfaces 37 and 38. By this arrangement, as shown in FIG. 4, bore 36 of cylindrical workpiece 35 has alternating annular grooves 40 and annular ridges 41. Product specifications require a plasma spray coating on surface 38 of the ridges 41, but not on surfaces 37 and 39 of the grooves 40. The prior art system, as explained above, would achieve the required product in one of two ways. First, the entire bore 36 of workpiece 35 could be coated, and then the coating could be machined off surfaces 37 and 39. Second, surfaces 37 and 39 could be masked prior to spraying. Then the entire workpiece could be coated and the masking would be removed afterward.
The subject invention substantially reduces the time, effort and cost to properly coat surface 38 of workpiece 35. To accomplish this coating, the plasma spray applicator 14 is directed radially at surfaces 38 of an annular ridge 41 in bore 36 of workpiece 35 while the plasma spray system is arranged as shown in FIG. 1. Workpiece 35 is rotated about its longitudinal axis to enable complete and even coating of the surface 38. As soon as surface 38 of one annular ridge 41 is coated, the system is switched to the arrangement shown in FIG. 2. The powder P stops flowing immediately, and the plasma spray applicator 14 is moved axially into alignment with the next annular ridge 41 in bore 36, without coating surfaces 37 and 39. Once the plasma spray applicator is directed to surface 38 of the next annular ridge 41 in bore 36, the system is switched back to the arrangement shown in FIG. 1, and the coating operation is commenced at its optimum rate with virtually no transition period.
In summary, a plasma spray system is provided that can quickly and abruptly stop spraying operations and quickly and abruptly start spraying operations thereby avoiding the transition period that follows the activation and deactivation of the prior art plasma spray system. As explained above, there are substantial cost and time savings in this unique plasma spray system.
While the preferred embodiment of the subject invention has been described and illustrated, it would be obvious that various changes and modifications can be made therein without departing from the spirit of the invention which should be limited only by the scope of the appended claims. For example, the system could be provided without the recirculation tube. In that particular embodiment, when the powder accumulator becomes sufficiently filled, it could be manually or mechanically removed for subsequent reuse of the powdered material therein. More specifically, the filled powder accumulator could be emptied and then returned to its position, or removed and replaced by an interchangeable substitute. In such an arrangement, the powder feed hopper and the powder accumulator could be interchangeable. Similarly, the apparatus could be provided without the hopper gas tube or the accumulator gas tube. Gravity could be relied upon to urge the powdered material from the powder feed hopper and, in applications, using a recirculation tube the force of the moving powder could be relied on to urge the powdered material from the powder accumulator. This feed system can be used in any powder metallizing apparatus. | A powder feed system with a recirculator is provided for a plasma spray apparatus so that spraying operations may be started and stopped abruptly. The subject system utilizes a pressurized gas to direct a powdered material from a powder feed hopper to the plasma spray applicator. A diverter valve is located intermediate the powder feed hopper and the plasma spray applicator and in close proximity to the plasma spray applicator for selectively diverting the powdered material toward or away from the plasma spray applicator. Powdered material diverted away from the plasma spray applicator is directed to a powder accumulator for subsequent reuse. The powdered material is kept in continuous motion during both spraying and diverting operations thereby avoiding the need to overcome inertia each time spraying operations are commenced. Furthermore, because of the close proximity of the diverter valve to the plasma spray applicator, spraying operations may be started and stopped abruptly with little or no transition period of variable flow rate. In a preferred embodiment the powder accumulator is in communication with the powder feed hopper thereby facilitating the recirculation and reuse of the diverted powdered material. | 1 |
[0001] This application claims priority to Provisional Application Ser. No. 61/602,783 filed Feb. 24, 2012, the content of which is incorporated by reference.
BACKGROUND
[0002] This application relates to mobile energy storage systems in commercial buildings.
[0003] Electric vehicles (EVs) have attracted much attention in recent years mainly due to economic and environmental concerns. It is expected that 3 million EVs to be on the read in California by 2015. While wide-scale penetration of EVs in electric systems brings new challenges to electric systems that need to be addressed, at the same time, it shows great potentials and new opportunities to improve efficiency of energy and transportation sectors. One can take advantage of the unique characteristics of these relatively new components of energy systems to address some of the existing issues of the grid.
[0004] EVs can be considered as Mobile Energy Storage (MES) that are available only during certain hours of a day. The presence of these MESs in an energy system, e.g., commercial building, offices, schools, colleges, etc., depends on many uncertain parameters such as end-users driving patterns, weather conditions, fuel price, and electricity price. Also, the initial level of energy stored in each MES connected to an energy system is an uncertain parameter. These probabilistic parameters might follow specific patterns that are associated with some probability distribution functions, and can be forecasted with a degree of uncertainty.
[0005] The use of EVs is particularly of importance for commercial buildings, where employees can plug in their EVs to the building energy system to be charged and/or discharged controlled by the Energy Management System (EMS) of the building. This invention investigates the optimal planning, operation, and control of such MESs using stochastic optimization techniques.
[0006] In the context of smart grids, smart distribution systems are envisioned as coupled microgrids (μG) that not only are connected to the grid, but also utilize Distributed Energy Resources (DERs) to generate power. High level of DERs integration in μGs raises concerns about the availability of high quality power supply mainly due to the variable and intermittent nature of power generation by Renewable Energy Resources (RESs). To cope with these issues, energy storage systems have been proposed to be used in μGs with DERs. When added, an energy storage system can immediately improve μGs' availability. Today, pumped hydro, flywheel, compressed air, and different types of batteries are the main energy storage technologies considered in the US electric power grid. In addition to these technologies, EVs can be considered as MES that are available only during certain hours of the day. FIG. 1 shows an exemplary load profile of a large commercial building office during weekdays and weekends for summer and winter. As shown therein, peak energy usage occurs during working hours, and drops off during non-working hours.
SUMMARY
[0007] In one aspect, systems and methods for energy management includes receiving parameters from commercial building management system components; generating a stochastic programming model of electric vehicles (EVs) as mobile energy storage (MES) for optimal planning, operation, and control purposes; and controlling operation of EVs according to the stochastic programming model to lower operating cost and carbon emission.
[0008] In another aspect, systems and methods are disclosed that uses EVs as MESes that are available only during certain hours of the day. For commercial buildings, employees can plug in their EVs to the building energy system to be charged and/or discharged by Energy Management System (EMS) of the building. One embodiment analyzes economic and environmental benefits of the application of EVs as MES in commercial building μGs. The system models energy systems of a commercial building including its grid connection, DERs, Stationary Energy Storage (SES), and demand profile. Based on the developed models, a Mixed Integer Linear Programming (MILP) problem is formulated in one embodiment to optimizes the operation of a commercial building μG. The objective is to minimize μG's daily operational costs and greenhouse gas emissions (GHG). Technical and operational constraints of DERs and Energy Storage (ES) systems such as minimum up time and down time, and charging and discharging power and capacity constraints of ES devices are formulated to appropriately model the operation of a grid connected commercial μG.
[0009] Implementations of the above system can include one or more of the following. Optimal planning, operation, and control of EVs as MESs are formulated as stochastic optimization problems considering different uncertainties in parameters. Mathematical models are used to properly formulate the optimal planning, operation, and control of energy systems with EVs as MESs. This includes mathematical modeling of grid connection, energy pricing schemes, various DERs, Stationary Energy Storage (SES), demand profiles, and MESs as well as uncertain deriving patterns of EV owners. Technical and operational constraints of DERs, SESs, and MESs such as minimum up time and down time, and charging and discharging power and capacity constraints are formulated to appropriately model the operation of an energy system. Based on the developed models, stochastic optimization problems are formulated to optimizes the planning, operation, and control of an energy systems with EVs. Different objective functions such as minimizing total costs, daily operational costs, and greenhouse gas emissions (GHG) are provided. The optimization models are formulated as stochastic linear programming problem considering several random quantities such as initial state of charge of EVs, arrival and departure times (connection and disconnection times) of EVs, electricity price, electricity demand of the energy system, and renewable energy generation.
[0010] Advantages of the preferred embodiments may include one or more of the following. The provided stochastic optimization framework results in more accurate and realistic representation of these energy systems which may lower total costs and emissions of such systems. The system provides economic and environmental benefits of the application of EVs as MES in commercial building μGs. A comprehensive analysis is done where energy systems of a commercial building including its grid connection, DERs, Stationary Energy Storage (SES), and demand profile are modeled. Based on the developed models, a Mixed Integer Linear Programming (MILP) problem is formulated to optimizes the operation of a commercial building μG. The system minimizes μG's daily operational costs and greenhouse gas emissions (GHG). Technical and operational constraints of DERs and Energy Storage (ES) systems such as minimum up time and down time, and charging and discharging power and capacity constraints of ES devices are formulated to appropriately model the operation of a grid connected commercial μG. The ability to use EVs to augment energy supply is particularly of interest for commercial buildings, where employees can plug in their EVs to the building energy system to be charged and/or discharged by Energy Management System (EMS) of the building. Technical and operational constraints of DERs and ES such as minimum up time and down time, load sharing characteristics of diesel generators, and charging and discharging constraints of ES devices are formulated to appropriately model the operation of a grid connected commercial μG. This provides a more accurate model to assess economic and environmental impacts of EVs in commercial buildings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 shows an exemplary load profile of a large commercial building office during weekdays and weekends for summer and winter.
[0012] FIG. 2 shows an exemplary block diagram of a commercial building microgrid generator.
[0013] FIG. 3 shows an exemplary system for optimizing economic and environmental impacts using EVs as mobile energy storage systems.
[0014] FIG. 4 shows an exemplary system for Using EVs as mobile energy storage in commercial buildings.
DESCRIPTION
[0015] In Smart Grids, commercial buildings can be seen as μGs that not only have grid connection, but also utilize various types of DERs to supply their demand. In this context, commercial building EMSs are expected to have the capability of controlling the operation of various components of their energy systems including DERs, ESs, and energy trade with the grid.
[0016] In commercial building μGs, EVs can be considered as MES mediums that are only available during certain hours of the day, and during these hours, the EMS can utilize both the energy stored in these EVs and their connected capacity. In this work, we consider integrated values of all connected EVs to the commercial building as a single MES. This MES is assumed to have a known (forecasted) connection time, available capacity and stored energy. The available capacity and stored energy of the MES might change during the day, reflecting the connection/disconnection of EVs to/from the building. The developed model generates operational schedule for all the components, including MES. The charging/discharging control of the obtained schedule for the MES among the connected EVs can be estimated using suitable processes.
[0017] A block diagram of an exemplary commercial building μG used to carry out simulations is presented in FIG. 2 . The μG consists of DC and AC buses and utilizes PV, FC, ICE, and MT in addition to the grid connection to supply its demand. SES and MES are connected to the DC bus of the system and their energy flow and storage can be controlled by the EMS of the μG. The μG trades energy with the grid and can sell to and/or buy from the grid. The grid charges the μG for its energy consumption and peak demand, and pays for its energy supply and spinning reserve capacity. As shown therein, MTs 1 , FC 2 , and ICE 3 supply energy over AC/DC buses to power AC load 40 , DC/AC converter 30 , and grid 50 . Each vehicle or MES 10 includes a plurality of battery units that are connected to a DC/DC converter 20 that provides energy over a private bus to supply power to a DC load 24 , SES 22 , and DC/AC converter 30 . A photovoltaic panel 26 can power a DC/DC converter 28 that supplies power to the private bus.
[0018] FIG. 3 shows an exemplary system for optimizing economic and environmental impacts using EVs as mobile energy storage systems. Power generation data and energy price forecast are provided ( 300 ). Load forecast data is also input ( 302 ). The system also receives commercial building energy system components and parameters ( 304 ). Weather forecast data ( 306 ) is provided. EV capacity and energy level forecast are also received ( 308 ). With the input data, the system performs one or more optimization models of the system components ( 310 ). Next, the system optimizes for selected objective functions ( 312 ). An optimal generation schedule of system components is generated ( 314 ). The system then analyzes economic and environmental impacts ( 316 ).
[0019] FIG. 4 shows an exemplary system for Using EVs as mobile energy storage in commercial buildings as a stochastic programming modeling of electric vehicles as mobile energy storage in energy systems ( 400 ). In 410 , the system can perform mathematical modeling of components. Such modeling can include EVs Modeling 412 . In 414 , the system can model charge/discharge constraints of EVs. In 416 , the system can model treatment of arrival/departure of EVs (driving patterns) in the model. In 418 , the system can develop a model for available discharge power of EVs. In 420 , the system can develop a model for available energy of connected EVs. In 422 , the system includes modeling degradation costs of EVs.
[0020] In 430 , grid connection is modeled and such model can include a number of details. In 432 , the system can model peak demand charges. In 434 , the system models Spinning Reserve requirements. In 436 , the system can model uncertainty in energy price.
[0021] The system can apply one or more optimization techniques ( 450 ). For example, stochastic optimization can be done ( 452 ) or deterministic approaches can be done ( 490 ). In 454 , the system takes a scenario based modeling approach. In 456 , MILP modeling of the problem can be done. In 458 , a single objective can be done, or alternatively, in 460 , a multi-objective optimization can be done. In 462 , the system can do MINLP modeling.
[0022] The system can also model uncertain parameters in 470 . For example, in 472 , the system can use discretized probability distribution functions. In 480 , the system can select the first and second stage variables.
[0023] In one embodiment, stochastic programming modeling is done for electric vehicles as mobile energy storage for optimal planning, operation, and control purposes is novel in terms of both the mathematical modeling of components and the optimization techniques.
The general form of the developed the two-stage model is as follows:
[0000] min xε n c′x+ [Q ( x ,ξ)]
[0000] s.t. Σ j a ij x j ≦b i (1)
where Q(x, ξ) is the optimal value of the second-stage problem:
[0000] min yε m q′y
[0000] s.t. Σ k V ks x k +Σ k w ks y s ≦h s (2)
here ξ:=(q, h, V, W) are the data of the second-stage problem, and some or all elements of vector ξ are random. [Q(x, ξ)] is the expected operator with respect to the probability distribution of ξ, which has a finite number of realizations (called scenarios) ξ s :=(q s , h s , V s , W s ) with respective probabilities p s :
[0000] [ Q ( x ,ξ)]=Σ s=1 S p s Q ( x,ξ s ) (3)
The whole two-stage problem is equivalent to the following problem:
[0000] min xε n c′x+Σ s=1 S p s q s ′y s
[0000]
s.t. Σ
j
a
ij
x
j
≦b
i
[0000] Σ k V ks x k +Σ k w ks y s ≦h s s= 1 , . . . , S (4)
[0029] Another embodiment performs mathematical modeling of the EVs for optimal planning, operation, and control purposes is new.
Energy balance equation for MES is given as follows:
[0000]
e
mes
,
t
,
s
=
(
1
-
Φ
mes
)
e
mes
,
t
-
1
,
s
+
τ
(
p
mes
,
t
,
s
chg
η
mes
chg
-
p
mes
,
t
,
s
dch
η
mes
dch
)
+
E
mes
,
t
,
s
conn
-
E
mes
,
t
,
s
disc
(
5
)
where E mes,t,s conn and E mes,t,s disc represent stochastic energy level of EVs connected to and disconnected from at time t in scenario s, respectively. These parameters are assumed to be random inputs to this model.
Energy storage levels of EVs are limited by minimum and maximum available capacities of the EVs at each time interval in each scenario, E mes,t,s and Ē mes,t,s respectively, as follows:
[0000] SOC mes,s Ē mes,t,s ≦e mes,t,s ≦ SOC mes,s Ē mes,t,s (6)
where minimum and maximum available capacities of the EVs are calculated using following equations:
[0000] Ē mes,t,s =( Ē mes,t-1,s +Ē mes,t,s conn −Ē mes,t,s disc ) (7)
[0000] E mes,t,s =( Ē mes,t-1,s +Ē mes,t,s conn −Ē mes,t,s disc ) (8)
[0000] One embodiment considers charge/discharge constraints of EVs. The following constraints are considered to ensure that p mes,t chg and p mes,t dch are less than maximum charging and discharging power of the EVs at each time interval:
[0000] 0 ≦p mes,t,s chg ≦u mes,t,s chg P mes,t,s (9)
[0000] 0 ≦p mes,t,s dch ≦u mes,t,s dch P mes,t,s (10)
where P mes,t,s and P mes,t,s are calculated as follows:
[0000] P mes,t,s =( P mes,t-1,s + P mes,t,s conn − P mes,t,s disc ) (11)
[0000] Operational and maintenance costs of EVs includes its degradation costs and considers the effect of charging and discharging cycles on capacity loss of the EVS, is assumed to be proportional to the number of charging and discharging cycles, and is modeled as follows:
[0000]
v
ses
,
t
,
s
chg
≥
u
ses
,
t
,
s
chg
-
u
ses
,
t
,
s
-
1
chg
(
12
)
v
ses
,
t
,
s
dch
≥
u
ses
,
t
,
s
dch
-
u
ses
,
t
-
1
,
s
dch
(
13
)
C
mes
,
t
,
s
=
C
mes
dg
1
2
(
v
mes
,
t
,
s
chg
+
v
mes
,
t
,
s
dch
)
+
C
mes
c
E
_
mes
,
t
,
s
+
p
mes
,
t
,
s
dch
η
mes
dch
C
mes
,
t
,
s
s
-
p
mes
,
t
,
s
chg
η
mes
chg
C
mes
,
t
,
s
d
(
14
)
[0000] where C mes,s dg represents costs of the EVs degradation per cycle to be paid to EV owners to reimburse their battery degradation due to charge and discharge, and C mes,s c denotes capacity costs to be paid to EV owners for the hours connecting their vehicles in each scenario. C mes,t,s s and C mes,t,s d represent the selling and buying energy price of the EV in each scenario, respectively.
[0034] The arrival and departure times of EVs (driving patterns) are treated as a probabilistic quantities. For each time interval a distribution of different trips (driving patterns) is constructed. Using these trip distribution functions, distribution functions are built for the arrival and departure times of EVs. For each time interval, a probability distribution of connectivity is calculated based on the distribution of driving.
[0035] In one embodiment, available charging/discharge power capacity of EVs is formulated as a random variable. Probability distributions of the initial energy level of EVs' batteries are built based on historical data for each time interval. Using this probability distributions and data generated, total connected EVs' charging/discharge power capacity is constructed, which at each time interval has a mean value and variance
[0036] Available charging/discharging energy capacity of EVs is formulated as a random variable. Probability distributions of the initial energy level of EVs' batteries are built based on historical data for each time interval. Using this probability distributions and data generated in prior operation, total connected EVs' charging/discharge energy capacity is constructed, which at each time interval has a mean value and variance.
[0037] Modeling degradation costs of EV batteries can be done. In one embodiment, C mes,s dg represents costs of the EVs degradation per cycle to be paid to EV owners to reimburse their battery degradation due to charge and discharge, and C mes,s c denotes capacity costs to be paid to EV owners for the hours connecting their vehicles in each scenario.
[0038] The system can perform mathematical modeling of the grid connection in the problem formulation. The system can consider peak demand charges for grid connection.
[0039] The system can also modeling contribution of EVs is Spinning Reserve requirements. In one embodiment, Spinning Reserve contributions of EVs are calculated as follows:
[0000]
p
mes
,
t
,
s
sp
=
min
{
(
e
mes
,
t
,
s
-
SOC
_
mes
,
s
E
_
mes
,
t
,
s
)
τ
,
P
_
mes
,
t
,
s
-
p
mes
,
t
,
s
dch
}
(
16
)
These constraints are reformulated as linear constraints in the mode as follows:
[0000]
p
mes
,
t
,
s
sp
≤
(
e
mes
,
t
,
s
-
SOC
_
mes
,
s
E
_
mes
,
t
,
s
)
τ
(
17
)
p
mes
,
t
,
s
sp
≤
P
_
mes
,
t
,
s
-
p
mes
,
t
,
s
dch
(
18
)
[0041] The system can consider uncertainty in energy prices for grid connection. The model can be formulated as a whole two-stage problem. Stochastic optimization techniques can be used to model electric vehicles as mobile energy storage is new. Another embodiment applies stochastic scenario based MILP modeling.
[0042] A Single Objective stochastic scenario based MILP modeling of the problem can be done, and the following objective functions are considered for the single objective MILP model of C1:
1—Maximization of daily profit 2—Minimization of GHG emissions 3—Minimization of total costs
[0046] In another embodiment, a Multi-Objective stochastic scenario based MILP modeling of the problem can be done. Any combination of the following objectives can be used for the multi-objective MILP model:
1—Maximization of daily profit 2—Minimization of GHG emissions 3—Minimization of total costs
[0050] Stochastic scenario based MINLP modeling of the problem can be done, with a non-linear energy balance equation for EVs is given as follows:
[0000]
e
mes
,
t
,
s
=
(
1
-
Φ
mes
)
e
mes
,
t
-
1
,
s
+
τ
(
p
mes
,
t
,
s
chg
η
mes
,
t
,
s
chg
-
p
mes
,
t
,
s
dch
η
mes
,
t
,
s
dch
)
+
E
mes
,
t
,
s
conn
-
E
mes
,
t
,
s
disc
(
19
)
where η mes,t,s chg and η mes,t,s dch are functions of p mes,t,s chg and p mes,t,s dch at each time and scenario, respectively. This makes Problem C1 an MINLP problem, which is a new formulation for this problem.
[0052] A Single Objective stochastic scenario based MINLP modeling of the problem can be used. The following objective functions are considered for the single objective MINLP model of C1:
1—Maximization of daily profit 2—Minimization of GHG emissions 3—Minimization of total costs
[0056] Another embodiment performs Multi-Objective stochastic scenario based MINLP modeling of the problem. Any combination of the following objectives can be used for the multi-objective MINLP model of C1:
1—Maximization of daily profit 2—Minimization of GHG emissions 3—Minimization of total costs
[0060] The modeling of the uncertain parameters in scenario based stochastic programming approach to model electric vehicles as mobile energy storage can be done. The system can calculate discretized probability distribution functions of the uncertain parameters for problem. For each time interval the following approach is used to construct discretized probability distribution functions of the uncertain parameters. The continuous probability distribution curves are constructed from data, then are discretized to quantize different levels. The process of discretization is required for the proposed optimization method. The discrete levels considered are [μ−3σ, μ−2σ, μ−σ, μ, μ+σ, μ+2σ, μ+3σ] with corresponding probabilities obtained from a given probability distribution function. Here μ is the mean value at an interval and σ represents the standard deviation of the data at each time interval.
[0061] Selection of the first and second stage variables in the scenario based stochastic programming approach to model electric vehicles as mobile energy storage can also be done. Variables used for the optimal operation and control of various devices such as EVs, DERs, grid connections, and stationary energy storages at each time interval are selected as second-stage variables. Variables such as total number of EVs, power and energy capacity of total EVs, power and energy capacity of DERs, Grid connection, and stationary storage systems are considered as the first-stage variables.
[0062] The above system determines economic and environmental benefits of the application of EVs as MES in commercial building μGs. Energy systems of a commercial building including its grid connection, DERs, Stationary Energy Storage (SES), and demand profile are modeled. Based on the developed models, a Mixed Integer Linear Programming (MILP) problem is formulated to optimizes the operation of a commercial building μG. The objective is to minimize μG's daily operational costs and greenhouse gas emissions (GHG). Technical and operational constraints of DERs and Energy Storage (ES) systems such as minimum up time and down time, and charging and discharging power and capacity constraints of ES devices are formulated to appropriately model the operation of a grid connected commercial μG. | Systems and methods for energy management includes receiving parameters from commercial building management system components; generating a stochastic programming model of electric vehicles (EVs) as mobile energy storage (MES) for optimal planning, operation, and control purposes; and controlling operation of EVs according to the stochastic programming model to lower operating cost and carbon emission. | 8 |
RELATED APPLICATIONS
This is a divisional of U.S. patent application Ser. No. 10/759,448, filed Jan. 16, 2004, now U.S. Pat. No. 7,316,844 incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is concerned with new protective coatings (primer layer, first protective coating, and optional second protective coating) for use in the manufacture of microelectronic devices such as those used in microelectromechanical systems (MEMS).
2. Description of the Prior Art
Etchants used for deep etching may vary depending upon the etch selectivity requirements for the devices to be fabricated. Basic etchants may contain amines such as ethylene diamine, ethanolamine, and/or water-miscible lower alcohols such as isopropanol to modulate the etching behavior of the solution. Bulk silicon etching is typically performed at temperatures in the range of 40° to 120° C. and most typically at 60° to 90° C. The etching times range from 1 to 24 hours and most typically are in the range of 5 to 15 hours.
Acidic etchants include aqueous solutions of hydrofluoric acid (HF), including concentrated (49% to 50%) HF, aqueous dilutions of the same, and buffered oxide etchants comprising aqueous mixtures of HF and ammonium fluoride. HF etchants are used primarily for etching silicon dioxide. Mixed acid etchants typically comprise mixtures of 70% nitric acid (HNO 3 ), 49% HF, and a diluent acid (e.g., 85% phosphoric acid (H 3 PO 4 ) or 100% acetic acid) and are used primarily for bulk silicon etching. Common component ratios by volume for the mixtures are, for example,
HNO 3 /HF/H 3 PO 4 =7:1:7 or 3:1:4.
Etching times for bulk silicon in these acid mixtures are typically in the range of 5 to 30 minutes and in some cases as long as 120 minutes at room temperature.
It is common in silicon etching processes to utilize a thin (100- to 300-nm) silicon nitride or silicon dioxide coating on the silicon substrate as a mask for patterned etching or as a passivating layer to enclose active circuitry. Therefore, the protective coating system described here is commonly applied onto Si 3 N 4 or SiO 2 , which means good adhesion to these substrates is critical for obtaining acceptable protection.
In the prior art, etch protective coatings or masks for MEMS fabrication processes have been selected primarily by using a trial-and-error method because there are no general-purpose protective coatings on the market. The etch selectivity of the etchants to various materials is often used as a guide for MEMS process engineers. With a much lower etch rate than silicon, films of silicon nitride have been used as a protective layer or hardmask during KOH or TMAH bulk silicon etching. Silicon dioxide has a higher etch rate than silicon nitride. Therefore, it is only used as a protective/mask layer for very short etches. Gold (Au), chromium (Cr), and boron (B) have also been reportedly used in some situations. Non-patterned hard-baked photoresists have been used as masks, but they are readily etched in alkaline solutions. Polymethyl methacrylate was also evaluated as an etch mask for KOH. However, because of saponification of the ester group, the masking time of this polymer was found to decrease sharply from 165 minutes at 60° C. to 15 minutes at 90° C. Black wax (Apiezon® W, available from Scientific Instrument Services, Inc., New Jersey) was also used as a protective coating in a 30% by weight KOH etch process (70° C.). After wet etching, the wax was removed using trichloroethylene.
Organic polymers are ideal candidates for protective coatings. The IC and MEMS industries have been using polymeric coating materials as photoresists, anti-reflective coatings, and planarization layers for many years. These materials are conveniently applied as thin films by the spin-on method and then balked or UV-cured to achieve the final coating form. One important requirement for the polymer is that it be highly soluble at room temperature in an environmentally friendly solvent. Because of the lack of a proper solvent, semicrystalline polyolefins such as polypropylene and polyethylene, as well as semicrystalline fluoropolymers such as Teflon®, which are known to have excellent corrosion resistance to strong acids and strong bases, cannot be formulated into spin-coated compositions for protective coating applications. At the same time, many common thermoplastic polymers such as polystyrene, poly(cyclic olefins), polymethyl methacrylate, polydimethylsiloxanes, polyimides, polysulfones, and various photoresist polymers (e.g., polyhydroxystyrene and novolac resins) fail to survive many common, harsh deep-etching processes because of their susceptibility and permeability to the etchants, poor adhesion to the substrate, tendency to form coating defects, or lack of solubility in solvents accepted in the microelectronics industry.
SUMMARY OF THE INVENTION
The present invention overcomes these problems by providing spin-applied, polymer coating systems which protect device features from corrosion and other forms of attack during deep-etching processes which utilize concentrated aqueous acids and bases. Furthermore, these coating systems can be easily removed at the end of the processes.
In more detail, these systems comprise a first protective layer which is applied to a microelectronic substrate surface. The first protective layer is formed from a composition which comprises a polymer dispersed or dissolved in a solvent system. Preferred polymers are thermoplastic polymers and comprise recurring monomers having the formula
wherein:
each R 1 is individually selected from the group consisting of hydrogen and C 1 -C 8 (and preferably C 1 -C 4 ) alkyls; and each R 2 is individually selected from the group consisting of hydrogen, C 1 -C 8 (and preferably C 1 -C 4 ) alkyls, and C 1 -C 8 (and preferably C 1 -C 4 ) alkoxys.
The polymer preferably comprises at least about 50% by weight of monomer (I), more preferably from about 50-80% by weight of monomer (I), and even more preferably from about 65-78% by weight of monomer (I), based upon the total weight of the polymer taken as 100% by weight. The polymer preferably comprises at least about 15% by weight of monomer (II), more preferably from about 15-40% by weight of monomer (II), and even more preferably from about 20-35% by weight of monomer (II), based upon the total weight of the polymer taken as 100% by weight.
Monomers other than monomers (I) and (II) can also be present in the polymer, if desired. When other monomers are present, the combined weight of monomers (I) and (II) in the polymer is preferably at least about 60% by weight, more preferably from about 60-99% by weight, based upon the total weight of the polymer taken as 100% by weight. Examples of suitable other monomers include those having functional groups which can react with groups in a primer layer (e.g., an organo silane primer layer as discussed herein) are desirable for achieving chemical bonding between the two layers, thereby reducing the likelihood of lifting of the first coating layer during the etching process. The monomers may have, by way of example haloalkyl (e.g. benzyl chloride, 2-chloroethyl methacrylate), ester (methacrylates, acrylates, maleates, fumarates), epoxy, or anhydride functional groups, which react readily with functional groups such as hydroxyl, amino, or oxiranyl groups which can be present in the primer layer. Some exemplary co-monomers are represented by the formulas
where:
each R 5 is individually selected from the group consisting of hydrogen and haloalkyls (preferably C 1 -C 4 ), with at least one R 5 preferably being a haloalkyl; each R 6 is individually selected from the group consisting of hydrogen, C 1 -C 10 alkyls (e.g., methyl, ethyl, butyl, isobornyl), haloalkyls (preferably C 1 -C 4 , e.g., 2-chloroethyl)), and epoxy-containing groups (preferably C 1 -C 4 , e.g., glycidyl groups);
In the instance of functional groups derived from carboxylic acids such as esters or anhydrides, it is important that the corresponding monomer concentration in the thermoplastic copolymer be less than about 20% by weight, and preferably less than about 10% by weight to limit the possibility of hydrolysis and consequent dissolution or swelling of the first coating layer by basic etchants. Alternatively, the copolymer may be alloyed with other compatible polymers (e.g., polymethyl methacrylate, polyethyl methacrylate, poly(6-caprolactone), and polyvinyl chloride) that enhance coating adhesion to the primer layer via chemical or physical bonding, or that reduce permeability and chemical susceptibility to basic etchants.
The polymer should be included in the first protective layer composition at a level of from about 5-30% by weight, preferably from about 10-25% by, weight, and even more preferably from about 15-22% by weight, based upon the total weight of the first protective layer composition taken as 100% by weight.
The solvent system utilized in the first protective layer composition should have a boiling point of from about 100-220° C., and preferably from about 140-180° C. The solvent system should be utilized at a level of from about 70-95% by weight, preferably from about 75-90% by weight, and more preferably from about 72-85% by weight, based upon the total weight of the first protective layer composition taken as 100% by weight. Preferred solvent systems include a solvent selected from the group consisting of methyl isoamyl ketone, di(ethylene glycol) dimethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and mixtures thereof.
While the first protective layer composition can be a cross-linkable composition, it is preferably a non-crosslinkable composition. Furthermore, it is preferred that the first protective layer formed from the first protective layer composition be nonconductive. The final first protective layer should also be non-photosensitive (i.e., a pattern cannot be defined in the layer when it is exposed to about 1 J/cm 2 ) and non-alkaline soluble (i.e., it is substantially—less than 0.5% by weight—insoluble in an aqueous solution having a pH of greater than about 8, and preferably greater than about 10).
There is preferably also a primer layer utilized in the protective systems of the invention. This layer should be included between the substrate and the first protective layer. Preferred primer layers are formed from primer layer compositions including a silane dispersed or dissolved in a solvent system. Aromatic and organo silanes are particularly preferred silanes for use in the primer layers of the invention. The most preferred silanes have the formula
each of i, j, and k is individually selected from the group consisting of 0 and 1, and if one of i and j is 1, then the other of i and j is 0;
each R 3 is individually selected from the group consisting of hydrogen, the halogens, C 1 -C 8 (preferably C 1 -C 4 ) alkyls, C 1 -C 8 (preferably C 1 -C 4 ) alkoxys, C 1 -C 8 (preferably C 1 -C 4 ) haloalkyls, aminos, and C 1 -C 8 (preferably C 1 -C 4 ) alkylaminos;
each R 4 is individually selected from the group consisting of C 1 -C 8 (preferably C 1 -C 4 ) aliphatic groups;
each X is individually selected from the group consisting of halogens, hydroxyls, C 1 -C 4 alkoxys and C 1 -C 4 carboxyls;
Y is selected from the group consisting of oxygen and sulfur;
Z is selected from the group consisting of nitrogen and phosphorus; and
each d is individually selected from the group consisting of 0 and 1.
Particularly preferred silanes include phenylsilanes such as phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriethoxysilane, phenyltriacetoxysilane, and diphenylsilanes such as diphenyldimethoxysilane, diphenyldichlorosilane, and diphenylsilanediol. The most preferred silanes include 2-phenylethyltrialkoxysilane, p/m-chlorophenyltrimethoxysilane, p/m-bromophenyltrimethoxysilane, (p/m-chloromethyl)phenyltrimethoxysilane, 2-(p/m-methoxy)phenylethyltrimethoxysilane, 2-(p/m-chloromethyl)phenylethyltrimethoxysilane, 3,4-dichlorophenyltrichlorosilane, 3-phenoxypropyltrichlorosilane, 3-(N-phenylamino)propyltrimethoxysilane, and 2-(diphenylphosphino)ethyltriethoxysilane.
An effective primer layer composition according to the invention is a mixture of diphenyldialkoxysilane (e.g., diphenyldimethoxysilane) and phenyltrialkoxysilane, (e.g., phenyltrimethoxysilane) or, even more preferably, a mixture of diphenylsilanediol and phenyltrimethoxysilane in a solution of 1-methoxy-2-propanol or 1-propoxy-2-propanol with from about 5-10% by weight water. A particularly effective primer layer composition for first protective layers comprising a poly(styrene-co-acrylonitrile) polymer is an alcohol and water solution containing from about 0.1-1.0% (preferably from about 0.25-0.5%) by weight diphenylsilanediol and from about 0.1-1.0% (preferably from about 0.25-0.5%) by weight of phenyltrimethoxysilane. Upon heating, diphenylsilanediol and phenylsilanetriol (the hydrolysis product of phenyltrimethoxysilane) condense to form siloxane bonds and establish a three-dimensional silicone coating layer on the substrate.
Another preferred silane has the formula
Silanes having this structure are not only compatible with styrene-containing copolymers, but they are also reactive with ester, benzyl chloride, and/or epoxy groups that may be present in the first protective layer, and they are excellent adhesion promoters. One particularly preferred silane within the scope of this formula is
This silane is 3-[N-phenylamino]propyltrimethoxysilane, and it is commercially available from Lancaster Synthesis and Gelest Corporation.
The silane should be included in the primer layer composition at a level of from about 0.01-5% by weight, preferably from about 0.1-1% by weight, and even more preferably from about 0.2-0.8% by weight, based upon the total weight of the primer layer composition taken as 100% by weight.
The solvent system utilized in the primer layer composition should have a boiling point of from about 100-220° C., and preferably from about 140-180° C. The solvent system should be utilized at a level of from about 80-99.9% by weight, and preferably from about 85-99% by weight, based upon the total weight of the primer layer composition taken as 100% by weight. Preferred solvent systems include a solvent selected from the group consisting of methanol, ethanol, isopropanol, butanol, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, and 1-propoxy-2-propanol, and mixtures thereof. In one preferred embodiment, water is included in the solvent system at a level of from about 2-15% by weight, and preferably from about 5-10% by weight, based upon the total weight of the primer layer composition taken as 100% by weight.
The primer layer composition can optionally include low levels (e.g., from about 0.01-0.10% by weight) of a catalyst. Suitable catalysts include any inorganic or organic acid (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid) or an inorganic or organic base (e.g., potassium hydroxide, TMAH, ammonia, amines).
In a preferred embodiment, the protective system of the invention further includes a second protective layer on top of the first protective layer to provide further protection against concentrated aqueous acids such as hydrofluoric acid, nitric acid, phosphoric acid, acetic acid, and mixtures of the foregoing. This embodiment is useful in situations where a acid etching is utilized. Preferred second protective layers are formed from second protective layer compositions comprising a linear, slightly branched, or cyclic halogenated polymer dissolved or dispersed in a solvent system. Furthermore, these halogenated polymers should comprise high levels of halogen atoms (at least about 50% by weight halogen atoms, and preferably at least about 60% by weight halogen atoms). The most preferred halogenated polymers are chlorinated polymers such as those comprising recurring monomers having the formula
Specific examples of preferred halogenated polymers include those selected from the group consisting of poly(vinyl chloride), polyvinylidene chloride, poly(vinylidene dichloride)-co-poly(vinyl chloride), chlorinated ethylene, chlorinated propylene, and mixtures thereof. Halogenated chlorinated rubber is also very effective.
The halogenated polymer should be included in the second protective layer composition at a level of from about 8-30% by weight, and preferably from about 10-20% by weight, based upon the total weight of the second protective layer composition taken as 100% by weight. The solvent system utilized in the second protective layer composition should have a boiling point of from about 100-220° C., and preferably from about 140-180° C. The solvent system should be utilized at a level of from about 70-92% by weight, and preferably from about 80-90% by weight, based upon the total weight of the second protective layer composition taken as 100% by weight.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Examples
The following examples set forth preferred methods in accordance with the invention. It is to be understood, however, that these examples are provided by way of illustration and nothing therein should be taken as a limitation upon the overall scope of the invention.
Typical Application Processes
Prior to applying the primer layer, it is preferable to prepare the substrate by exposing it to brief (from about 15-60 seconds) oxygen plasma etching to clean and/or chemically activate the substrate surface to improve bonding by the primer layer. Plasma bombardment with heavy ions such as argon can also be beneficial for improving bonding. Such processes are especially effective for improving the bonding of the protective coating system to silicon nitride.
Preferred substrates for use in this process include those selected from the group consisting of Si substrates, SiO 2 substrates, Si 3 N 4 substrates, SiO 2 on silicon substrates, Si 3 N 4 on silicon substrates, glass substrates, quartz substrates, ceramic substrates, semiconductor substrates, and metal substrates.
The organosilane solution that makes up the primer layer is spin-applied onto the substrate at about 500-5000 rpm, and preferably from about 1000-2000 rpm, for about 30-90 seconds. It is then baked at greater than about 100° C. for about 60-90 seconds to condense the organosilane molecules into a continuous film that is bonded to surface hydroxyl groups present on many microelectronic substrates. It is preferred that the primer layer have an average thickness (as measured by ail ellipsometer over 5 different points) of less than about 5 nm and more preferably from about 2-8 nm.
For the first protective layer, the thermoplastic polymer is dissolved in a suitable solvent at a concentration of from about 5-25% by weight and spin coated onto the substrate at about 500-5000 rpm, and preferably from about 1000-3000 rpm, for about 30-90 seconds. It is soft-baked at a temperature of from about 80-130° C. for about 60-120 seconds to dry the coating and then is subjected to a final bake at a temperature of from about 130-225° C. for about 60-90 seconds to densify the first protective layer and bond it firmly to the primer layer. The preferred process for baking styrene-acrylonitrile coatings is to bake them at a temperature of about 130° C. for about 120 seconds and then at a temperature of about 200° C. for about 60 seconds. The polymer solids level and spinning conditions are adjusted typically to achieve a final coating thickness of from about 1-5 μm, and preferably from about 2-5 μm, depending upon the degree of coverage required over device topography on the substrate.
The second protective layer is applied from a solvent solution in a manner similar to that described above with respect to the first protective layer. The solvents used to apply the second protective layer should be selected to minimize detrimental interaction with the first protective layer. It is preferred that the second protective layer have an average thickness (as measured by an ellipsometer over 5 different points) of from about 1-5 μm, and more preferably from about 2-5 μn.
It is preferred that the protective layer(s) or coating(s) be removed after the wet etching processes have been completed. A particularly preferred technique is stripping the coating(s) with solvents commonly used in microelectronic processing such as acetone, propylene glycol methyl ether acetate, or ethyl lactate. In this technique, the coated substrate is sprayed with, or immersed in, the solvent until the coating layer has fully dissolved. The substrate is then rinsed with fresh solvent until clean. The protective coating system described here is easily removed by dissolving the thermoplastic layer (the first coating layer) in a solvent such as acetone. The second coating layer, if present, is either dissolved at the same time or is lifted as the first layer dissolves.
Practicing the present invention will result in a protective layer system which suffers little or no lifting during etching processes. That is, the layer systems will exhibit less than about 3 mm, preferably less than about 2 mm, and more preferably less than about 1 mm of lifting when subjected for about 2 hours to etching in an approximately 30-35% by weight aqueous KOH solution having a temperature of about 83-87° C. Lifting is determined by measuring from the outside edge of the substrate to the furthest point on the layer system where the layer system is still attached to the substrate.
Furthermore, the inventive protective layer system will experience very little or no etchant penetration during etching processes. Thus, when subjected for about 2 hours to etching in an approximately 30-35% by weight aqueous KOH solution having a temperature of about 83-87° C., the inventive protective systems will have less than about 0.1 pinholes per cm 2 of substrate, and preferably less than about 0.05 pinholes per cm 2 of substrate, when observed under a microscope at 10× magnification.
Example 1
Preparation of Primers I-IV
Primer I was prepared by dissolving 0.5 g of diphenyldichlorosilane in 99.5 g of xylene followed by filtering with a 0.2/0.45-μm polypropylene filter.
Primer II was prepared by dissolving 0.5 g of diphenyldimethoxysilane in 90 g of isopropanol and 10 g of water followed by filtering with a 0.2/0.45-μm polypropylene filter.
Primer III was prepared by dissolving 0.5 g of diphenylsilanediol and 0.5 g of phenyltrimethoxysilane in 90 g of propylene glycol monomethyl ether (PGME) and 10 g of water. The primer was aged for at least 24 hours so that the silanes were partially hydrolyzed and condensed. The primer was then it was filtered using a 0.2/0.45-μm polypropylene filter.
Primer IV was prepared by dissolving 1.0 g of diphenylsilanediol and 1.0 g of phenyltrimethoxysilane in 88 g of PGME and 10 g of water. The primer was similarly aged and then filtered using a 0.2/0.45-μm polypropylene filter.
Example 2
Preparation of Primer V (Comparative Primer)
In a manner similar to Example 1, Primer V was prepared by adding 1.0 g of 3 aminopropyltriethoxysilane into 95 g of PGME and 5 g of water. The primer was aged for at least 24 hours so that the silane was partially hydrolyzed and condensed. The primer was then filtered using a 0.2/0.45-μm polypropylene filter.
Example 3
Preparation of Primer VI
A diethyl fumarate-modified, amino functional silane was prepared by mixing one mole of N-(3-trimethoxysilyl)-propylethylenediamine with one mole of diethyl fumarate, followed by stirring at room temperature for 48 hours. The mixing process was exothermic, indicating the immediate reaction of the two components.
Primer VI was prepared by dissolving 1 g of the above modified silane into 90 g of PGME and 10 g of water. The mixture was aged for 24 to 48 hours at room temperature and then filtered using a 0.2/0.45-μm polypropylene filter for future use.
Example 4
Preparation of Primer VII
Primer VII is an adhesion promoter based on 3-(N-phenyl)aminopropyltrimethoxysilane, which is very effective for polystyrene-co-acrylonitrile polymers, especially for coatings containing reactive groups such epoxy, ester, or chloromethyl (benzyl chloride) groups. Primer VII was prepared by dissolving 0.5 g of the aromatic amino silane in 90 g of PGME and 10 g of water. The mixture was aged in a manner similar to the previous examples and filtered using a 0.2/0.45-μm polypropylene filter.
Example 5
Preparation of Coating Compositions A and B from a Copolymer of Styrene and Acrylonitrile
Commercially available styrene-acrylonitrile resins were used directly for coating formulations. Composition A was formulated by dissolving 12 g of poly(styrene-co-acrylonitrile) (SAN30: M w =185,000, 30 wt % acrylonitrile, available from Aldrich) in 44 g of methyl isoamyl ketone (MIAK) and 44 g of di(ethylene glycol) dimethyl ether. Composition B was formulated by dissolving 18 g of SAN30 in 41 g of methyl isoamyl ketone (MIAK) and 41 g of di(ethylene glycol) dimethyl ether. Both coating compositions were filtered twice using a 0.2/0.45-μm polypropylene filter. Alternatively, a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate in a weight ratio of 9:1 was also used as the solvent. The change of solvent did not noticeably change the coating quality or adhesion.
Example 6
Preparation of a Terpolymer and Formulation of Coating Composition C from the Terpolymer
In this procedure, a terpolymer of styrene, acrylonitrile, and glycidyl methacrylate was prepared. Styrene and glycidyl methacrylate were purified by passing through an aluminum oxide column. Acrylonitrile was purified by washing sequentially with a 5% by weight H 2 SO 4 solution, a 5% by weight NaOH solution, and water to remove inhibitors and amine impurities that might cause crosslinking of the polymer. It was dried over anhydrous calcium chloride and then 4-Å molecular sieves.
A 500-ml two-neck flask containing a 1-inch magnetic stilling bar was charged with 100 g of cyclohexanone (or PGMEA) and a mixture of purified monomers including 35 g of styrene, 10 g of acrylonitrile, and 5 g of glycidyl methacrylate. Next, 300 mg of 2,2′-azobisisobutylnitrile (AIBN) (or benzoyl peroxide) were added to the mixture as an initiator. The side neck of the flask was capped with a rubber septum, and the main neck of the flask was connected to a water-cooled condenser with the top end of the condenser linked to a bubbler containing mineral oil. After fixing the entire glass assembly to a metal stand, the system was purged with nitrogen to remove oxygen through the side neck of the flask through a needle. The flask was heated using a hotplate at 80° C. for about 8 hours to polymerize the monomer mixture. During the reaction, the reactor was slowly purged with nitrogen to prevent oxygen from entering. The polymer obtained was then precipitated in a mixture of isopropanol or ethanol containing 20% by weight water in a fast-stirring blender. The polymer was recovered by filtration and vacuum-dried to remove any solvent or monomer residues. The yield or conversion of the reaction was 80% to 85%. Gel permeation chromatography (GPC) indicated the weight average molecular weight of the polymer was about 200,000 g/mole (relative to polystyrene standard).
Composition C (12.5% solids) was prepared by dissolving 12.5 g of the recovered dry polymers in 94.5 g of PGMEA and 10.5 g of ethyl lactate. It was filtered twice using 0.2/0.45-μm polypropylene filters.
Example 7
Preparation of a Terpolymer and Formulation of a Coating Composition D from the Terpolymer
A terpolymer of styrene, acrylonitrile, and butyl acrylate was prepared in this example. The styrene and acrylonitrile were purified according to the same method described in Example 6. Butyl acrylate was purified by passing through a column of aluminum oxide.
A mixture of purified monomers including 30 g of styrene, 15 g of acrylonitrile, and 5 g of butyl acrylate was polymerized in PGMEA, and the polymer was recovered using the same method described in Example 3. The conversion or the yield of the polymerization for this system was around 80%. GPC molecular weight (M w ) for this polymer was around 99,600 g/mole (relative to polystyrene standard).
Composition D (15% solids) was prepared by dissolving 15 g of the recovered dry polymer in 76.5 g of PGMEA and 8.5 g of ethyl lactate. It was filtered twice using a 0.2/0.45-μm polypropylene filter.
Example 8
Preparation of a Quaterpolymer and Formulation of a Coating Composition E from the Polymer
In this procedure, a quaterpolymer of styrene, acrylonitrile, butyl acrylate, and glycidyl methacrylate was prepared. To accomplish this, styrene, butyl acrylate, and glycidyl methacrylate were purified by passing through a column of aluminum oxide. Acrylonitrile was purified by washing with 5 wt % H 2 SO 4 , 5 wt % NaOH, and deionized water sequentially followed then dined over anhydrous calcium chloride and 4 Å molecular sieves.
A mixture of purified monomers including 25 g of styrene, 15 g of acrylonitrile, 5 g of butyl acrylate, and 5 g of glycidyl methacrylate was polymerized and recovered according to the methods described in Example 6. The conversion or the yield of the polymerization for this system was around 80%. GPC molecular weight (Mw) for this polymer was around 124,600 g/mole (relative to polystyrene standard).
Composition E (15 wt % solids) was prepared by dissolving 15 g of the recovered dry polymers in 76.5 g of PGMEA and 8.5 g of ethyl lactate. It was filtered twice using a 0.2/0.45-μm polypropylene filter.
Example 9
Preparation of Coating Composition F
Composition F was prepared by combining in solution 13.5 g of a copolymer of styrene and acrylonitrile (M w =165,000, 25% acrylonitrile) and 1.5 g of polymethyl methacrylate (PMMA, M w =120,000). The coating composition was filtered using a 0.2/0.45-μm polypropylene filter.
Example 10
Preparation of Coating Composition G
Composition G was prepared by dissolving 12 g of chlorinated rubber (CLORTEX® 20 from American Tartaric Corporation) in 88 g of PGMEA, followed by filtering with a 0.2/0.45-μm polypropylene filter.
Example 11
Preparation of Coating Composition H
Composition H was prepared by dissolving 10 g of chlorinated PVC (TempRite 674X571 from Noven, Inc.) in 90 g of cyclohexanone, followed by filtering with a 0.2/0.45-μm polypropylene filter.
Example 12
Procedure for Applying Primers I-VII and Coating Compositions A-G
A silicon, silicon nitride, or silicon nitride wafer with aluminum deposited at the central area was mounted on a spin-coater and centered properly. Under conditions of a spin acceleration rate of 20,000 rpm 2 , a spin speed of 2,500 rpm, and a duration of 90 seconds, the wafer was first washed with acetone for about 20 seconds to remove any possible contaminants, and then an aliquot of 5 to 10 ml of the primer was dispensed onto the wafer. After spinning for about another 40 to 60 seconds, a uniform primer layer was obtained on top of the wafer. Subsequently, the primed wafer was baked on a hotplate at 100-130° C. for 1 minute to promote chemical bonding between the substrate and the primer as well as partial vulcanization of the primer. After the primed wafer cooled to room temperature, a layer of the particular coating composition (e.g., Composition A) was spin-applied and then baked on a hotplate sequentially at 100° C. for 2 minutes, 130° C. for 1 minute, and 205° C. for 1 minute.
Example 13
KOH Deep-Etch Tests for Various Coating/Primer Combinations
The test equipment included a glass etchant tanker containing about 4000 ml of a 30% to 35% by weight aqueous KOH solution in which a TEFLON® wafer boat holding the test substrates in a horizontal orientation was fully immersed. The etchant solution was heated using an internal heating unit or outer heating unit such as a hotplate, and the temperature of the etchant was controlled to 85° C.±1.5° C. In general, 4-inch wafers of silicon, silicon nitride, or silicon nitride with aluminum deposited at the central circular area (approximately 2 inches in diameter) were used for the test. For silicon wafers, the test was only conducted for 2 to 4 hours because of the high etch rate of silicon in KOH. For silicon nitride wafers, the test was extended to at least 8 hours. During the etch test, the solution was bubbled vigorously with nitrogen to provide agitation. After the etching period, wafer samples were removed, rinsed, dried, and then inspected for pinholes and edge lift or detachment of the coating layer(s).
Because aluminum is very reactive toward KOH solution, any penetration of the coating (either by pinholes or poor KOH resistance of the coating) was indicated by disappearance of aluminum at the area. The distance from the edge of the wafer to the front line of coating detachment in the radial direction was used as a measure of the adhesion quality of the primer/coating combination. Results are shown in Table 1.
TABLE 1
KOH deep-etch test results for various coating/primer combinations.
O 2
Coating
Protective Coating
Results MM of
Exp #
Substrate
Plasma Etch
Primer
Composition
Bake Process
Lifting
Comments
1
Nitride
None
None
A
100° C./120 sec
4–30 mm
Control
130° C./120 sec
205° C./60 sec
2
Nitride + Al pad
None
None
A
100° C./120 sec
4–25 mm
Control
130° C./120 sec
205° C./60 sec
3
Silicon
None
None
A
100° C./120 sec
Completely lifted
Control
130° C./120 sec
205° C./60 sec
4
Nitride
Yes
III
A
100° C./120 sec
2–3 mm
130° C./120 sec
205° C./60 sec
5
Nitride + Al pad
Yes
III
A
100° C./120 sec
1–3 mm
130° C./120 sec
205° C./60 sec
6
Silicon
None
III
A
100° C./120 sec
5–30 mm
Edge lift not
130° C./120 sec
uniform
205° C./60 sec
7
Nitride
Yes
III
B
100° C./120 sec
1–3 mm
130° C./120 sec
205° C./60 sec
8
Nitride + Al pad
Yes
III
B
100° C./120 sec
1–3 mm
130° C./120 sec
205° C./60 sec
9
Silicon
None
III
B
100° C./120 sec
3–25 mm
Edge lift not
130° C./120 sec
uniform
205° C./60 sec
10
Nitride
Yes
IV
B
100° C./120 sec
1–2 mm
130° C./120 sec
205° C./60 sec
11
Nitride + Al pad
Yes
IV
B
100° C./120 sec
1–3 mm
130° C./120 sec
205° C./60 sec
12
Silicon
None
IV
B
100° C./120 sec
10–40 mm
Edge lift not
130° C./120 sec
uniform
205° C./60 sec
13
Nitride
Yes
IV
B
100° C./120 sec
1–3 mm
130° C./120 sec
205° C./60 sec
14
Nitride + Al pad
Yes
IV
B
100° C./120 sec
2–3 mm
130° C./120 sec
205° C./60 sec
15
Silicon
None
IV
B
100° C./120 sec
8–26 mm
Edge lift not
130° C./120 sec
uniform
205° C./60 sec
16
Nitride
Yes
V
A
100° C./120 sec
1–5 mm
Edge lift not
130° C./120 sec
uniform
250° C./60 sec
17
Nitride
Yes
V
A
100° C./120 sec
3–7 mm
Edge lift not
130° C./120 sec
uniform
250° C./60 sec
18
Nitride
None
VII
B
100° C./60 sec
0
205° C./60 sec
19
Nitride + Al pad
None
VII
B
100° C./60 sec
2–4 mm
205° C./60 sec
20
Silicon
None
VII
B
100° C./60 sec
0
205° C./60 sec
21
Nitride
None
VI
C
100° C./60 sec
4–6 mm
205° C./60 sec
22
Nitride
None
VI
C
100° C./60 sec
3–4 mm
205° C./60 sec
23
Nitride
None
VII
C
100° C./60 sec
0
205° C./60 sec
24
Nitride + Al pad
None
VII
C
100° C./60 sec
0
205° C./60 sec
25
Silicon
None
VII
C
100° C./60 sec
0
205° C./60 sec
26
Nitride
None
VII
D
100° C./60 sec
1–2 mm
205° C./60 sec
27
Nitride + Al pad
None
VII
D
100° C./60 sec
1–2 mm
205° C./60 sec
28
Silicon
None
VII
D
100° C./60 sec
0
205° C./60 sec
29
Nitride
None
VII
E
100° C./60 sec
0
205° C./60 sec
30
Nitride + Al pad
None
VII
E
100° C./60 sec
1 mm
205° C./60 sec
31
Silicon
None
VII
E
100° C./60 sec
0
205° C./60 sec
32
Nitride
None
VII
F
100° C./60 sec
1–3 mm
205° C./60 sec
33
Nitride + Al pad
None
VII
F
100° C./60 sec
1–2 mm
205° C./60 sec
34
Silicon
None
VII
F
100° C./60 sec
1–2 mm
205° C./60 sec
Example 14
Resistance of Coating Combinations to Concentrated Hydrofluoric Acid
The test described in this example provided a means for rating the resistance of coating combinations to hydrofluoric acid and the time for the hydrofluoric acid to penetrate the 1.5-micron thick coating layers.
At room temperature, a drop (approximately 0.2 ml) of 49% HF was placed in the center of a silicon wafer coated centrally with aluminum and another drop (approximately 0.2 ml) was placed on the area outside of the aluminum deposit. The wafers were then carefully observed for penetration of hydrofluoric acid through the coating, as indicated by the formation of hydrogen bubbles resulting from the aluminum reacting with hydrofluoric acid. When a silicon nitride-coated wafer was used as the test substrate, penetration of the coating by hydrofluoric acid was observed as etching of the gold-colored silicon nitride layer, which then exposed the gray-colored silicon substrate. The results are shown in Table 2.
TABLE 2
Resistance of coating or coating combination to concentrated hydrofluoric acid.
Protective
Bake Process
Protective
Bake Process
Exp #
Substrate
Primer
Coating 1
Coating 1
Coating 2
Coating 2
Results
1
Silicon
None
A
130° C./60 sec
None
N/A
Coating dissolved or destroyed
Nitride
205° C./5 min
2
Silicon
None
A
130° C./60 sec
G
130° C./60 sec
No penetration observed after 30 minutes,
Nitride
205° C./5 min
205° C./5 min
substrate darkened
3
Silicon
V
G
130° C./60 sec
None
N/A
No penetration observed after 30 minutes,
Nitride
205° C./5 min
substrate darkened
4
Silicon
I
G
130° C./60 sec
None
N/A
No penetration observed after 30 minutes,
Nitride
205° C./5 min
substrate darkened
5
Silicon
II
G
130° C./60 sec
None
N/A
No penetration observed after 30 minutes,
Nitride
205° C./5 min
substrate darkened
6
Silicon
VI
H
100° C./120 sec
None
N/A
No penetration observed after 30 minutes.
Nitride + Al
130° C./120 sec
Pad
205° C./60 sec
Example 15
A Simulated Test for Resistance of Coating Combination to Mixed Acid
This test was conducted in a mechanical batch etching system using a mixture of nitric acid (70% by weight), hydrofluoric acid (49% by weight), and phosphoric acid (85% by weight) (HNO 3 :HF:H 3 PO 4 =3:1:4) as an etchant. The silicon wafers were contained in a wafer carrier boat, which was then placed in the tool for exposure to the etchant. The wafers were tumbled during the entire length of the etching process (approximately 30 minutes). Once removed, the wafers were rinsed and evaluated for coating performance. The test was conducted at room temperature, with a constant fresh supply of etching solution applied to the substrates. Results are shown in Table 3.
TABLE 3
Resistance of primer/coating combination to mixed acid etchants.
Protective
Bake Process
Protective
Bake Process
Exp #
Substrate
Primer
Coating 1
Coating 1
Coating 2
Coating 2
Results
1
Silicon
V
G
130° C./60 sec
None
N/A
Materials lifted off substrate
205° C./5 min
2
Silicon
V
A
130° C./60 sec
None
N/A
Completely dissolved after 10
205° C./5 min
minutes exposure
3
Silicon
None
A
130° C./60 sec
None
N/A
Completely dissolved after 10
205° C./5 min
minutes exposure
4
Silicon
V
A
130° C./60 sec
G
130° C./60 sec
Material lifted off of substrate
205° C./5 min
205° C./5 min
5
Silicon
None
A
130° C./60 sec
G
130° C./60 sec
No observable lifting or
205° C./5 min
205° C./5 min
penetration
6
Silicon Dioxide
V
G
130° C./60 sec
None
N/A
Material lifted off of substrate
205° C./5 min
7
Silicon Dioxide
None
A
130° C./60 sec
G
130° C./60 sec
Material lifted off of substrate
205° C./5 min
205° C./5 min
8
Silicon
None
A
130° C./60 sec
G
130° C./60 sec
Minimal amount of lifting from
250° C./5 min
250° C./5 min
the edge of the wafer observed
after 10 minutes
9
Silicon
V
G
130° C./60 sec
None
N/A
Random penetration of film
250° C./5 min
causing a bubble effect.
10
Silicon
II
G
130° C./60 sec
None
N/A
Film completely lifted after 30
250° C./5 min
minutes of exposure
11
Silicon
I
G
130° C./60 sec
None
N/A
100% of film lifted after 5
250° C./5 min
minutes exposure
12
Silicon
II
A
130° C./60 sec
G
130° C./60 sec
Excellent coating, no lifting
250° C./5 min
250° C./5 min
observed even after 30 minutes
of exposure
13
Silicon
I
A
130° C./60 sec
G
130° C./60 sec
Excellent coating, no lifting
250° C./5 min
250° C./5 min
observed even after 30 minutes
of exposure | New protective coating layers for use in wet etch processes during the production of semiconductor and MEMS devices are provided. The layers include a primer layer, a first protective layer, and an optional second protective layer. The primer layer preferably comprises an organo silane compound in a solvent system. The first protective layer includes thermoplastic copolymers prepared from styrene, acrylonitrile, and optionally other addition-polymerizable monomers such as (meth)acrylate monomers, vinylbenzyl chloride, and diesters of maleic acid or fumaric acid. The second protective layer comprises a highly halogenated polymer such as a chlorinated polymer which may or may not be crosslinked upon heating. | 8 |
TECHNICAL FIELD
[0001] The present invention is generally related to real-time tracking systems and specifically related to systems and methods for physical location self-awareness in network connected devices.
BACKGROUND OF THE INVENTION
[0002] Problematically in computer data centers, where hundreds or thousands of different machines are housed, specific devices are difficult to locate. Therefore, when technicians are dispatched from the various companies housing machines in the data center, the technicians waste time and effort locating the equipment they have been dispatched to service. These data centers are typically multi-thousand square foot facilities with equipment housed in racks that all generally look alike. Additionally, this equipment may not be labeled very clearly or not labeled at all.
[0003] Existing real-time tracking systems typically use electronic or infrared tracking tags, physically placed on equipment. One such existing real-time tracking system is a Real-time Location System (RTLS) from Ameritrac Wireless Corporation (see http://www. ameritracwireless.com/index.html). Such existing tracking systems constantly monitor location of the equipment tags, via triangulation, using antennas dispersed throughout the data center. Global Positioning Satellite (GPS) based systems are also available. However, location information provided by these existing systems is typically maintained in a central database, useful only to those with access to the database. In the case of a data center, there are typically hundreds of customers with equipment located on-site. Problematically, each customer may not have access to the location database.
[0004] Whereas, existing tagging systems typically employ a central server and the central server keeps track of where all the tagged items are located, the tagged items themselves contain no information on their location unless it has been manually entered. Therefore, under existing tracking systems one would not be able to access this information if the central server was down or otherwise unavailable.
[0005] Existing canonical systems for equipment tracking employ manual entry of equipment locations into a central database. An enhancement to existing canonical systems employs Simple Network Management Protocol (SNMP). The canonical location information may be stored in one of the SNMP Management Information Base (MIB) variables such as Syslnfo on the system being tracked as a place holder for device location. However, this data is typically manually entered by the operator of the equipment. If the equipment gets moved it is not necessarily updated, unless the operator is aware of the move and manually performs the update. Thus, use of SNMP MIB in this manner is fraught with update problems. Typically, once the data is set up, it does not remain current.
BRIEF SUMMARY OF THE INVENTION
[0006] The present invention is directed to systems and methods by which a piece of equipment connected to a network may be populated automatically with near real-time information detailing the equipment's own physical location. Applications of the present systems and methods may include use in computer data centers where hundreds or thousands of computers are centrally located in a multi-thousand square foot facility, or for enterprise or government IT inventory systems. While each customer of such a facility may not have access to the location database for the facility, they typically have network access to their own equipment. Implementation of the present systems and methods will allow customers to track the physical location of their own equipment, by making queries to that equipment, without a need to access a central database. The present systems and methods also provide a backup to the central database system. If one wishes to know the location of their equipment at a time when the database is down, they may still query their equipment to get its last known location.
[0007] As used herein, “self awareness” or “awareness” is information integrated into the device on which a location system tag is placed, such that the object can report back its own location when it is queried, thereby portraying that the device is “aware” of its location.
[0008] The present systems and methods may make use of a current real-time tracking system such as the aforementioned RTLS technology from Ameritrac Wireless. The present systems and methods employ or create a location server. The present invention and its location server may operate as an extension of an existing RTLS service, as a separate system, or both. In accordance with embodiments of the present invention, tagged items query the location server on startup and internally store their own location information. This information may be accessed via a shell account from the managed system. Alternatively, if the device is managed via a protocol such as SNMP, the information may be stored on the system being tracked in one of the SNMP MIB variables, such as SysInfo.
[0009] Most existing real-time location systems employ a centralized server on which to store location data, in the aforementioned central database. One advantage of the present invention is that if that server is unavailable, the devices themselves have their last known location information. Therefore, a user that has access to a device can access location information for that device.
[0010] In some embodiments, software on a tagged object periodically seeks out, from the tracking system information repository, the device's location and programs that into the SNMP variables of that object. In other embodiments, the tagged object, as part of its boot procedure, queries the tracking system information repository for its location and stores this location internally. In the case, for example, of a device on which a software agent cannot be running at all times, the device may be able to find its location by running an application at boot, as a part of its boot procedure. Both embodiments may be combined, in that an object can find its location at boot and periodically thereafter update that information, or either embodiment can be used separately.
[0011] In various embodiments, software of the present invention directly queries a tracking system server. In other embodiments where no single RTLS system covers a domain, a hierarchical or hybrid server that can query all the RTLS servers in the domain may be employed to perform hierarchical searches and similar functions. For example, a device's previous location may be known, so the hierarchical server may start with the RTLS system associated with that location and then work outwardly through the domain, rather than querying all tracking system servers in the domain. When several real-time location systems are employed throughout, for example, a campus, one system in, for example, each building, would have a server in each domain (building). These domains may be set up in hierarchies, similar to the domain name system of the Internet, for example. A device would initially query its last known local location server, and if that location server was unavailable it would then be redirected to another location server upward in the hierarchy until it found the authoritative location server for itself. Particularly, in accordance with such an embodiment, the hierarchical server will query the next closest server and work outwardly in a circular pattern similar to the Internet's Domain Naming System (DNS) hierarchy.
[0012] An advantage of the present systems and methods is that the location data is automatically updated on the devices, and the device is thus “self aware”. Another advantage of the present systems and methods is that since devices are “aware” of their own location, if they are moved, the system does not need to be manually updated. This system takes advantage of any real-time location system that is already in place and updates the device itself. Also, since the information is stored in the device's MIB, or the like, the device is “aware” of its location even when the location system is temporarily down. Another advantage of the present invention is that when set up in a hierarchy, it is able to function across multiple real-time location system domains.
[0013] Another advantage is that multiple different, possibly even physically incompatible, location systems may use or make concurrent use of the present invention. For example, two companies, which have each set up real-time location systems, may use different location system products. For example, one company may use an infrared system and the other a radio or GPS based system. If the companies merge, or merge some of their resources (equipment), devices start migrating between company campuses. Once the companies install the physical component(s) or tags needed to track the devices, then a dual tagged device can be located across either system yet the software of the present invention does not have to be updated to work with another location system. The software of the present invention uses the same protocol and the local servers integrate the heterogeneous location systems.
[0014] If a channel is provided via which the location server can contact the device directly, a device may be enabled to react to movement of the device, whereas in a manual system or in all the existing location systems, the device would “know” nothing about its movement. Regardless, under the present system and methods, as long as the device is powered back up, it will be aware of its new location. However, a battery powered device such as a laptop computer might be continuously aware of its location. Resultantly, the present invention might also function as a security system or to supplement a security system. For example, a laptop that has been set-up to alert the present system if it leaves the building, or otherwise defined area, as it leaves the building or area it can alert the system of its departure.
[0015] The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims. The novel features which are believed to be characteristic of the invention, both as to its organization and method of operation, together with further objects and advantages will be better understood from the following description when considered in connection with the accompanying figures. It is to be expressly understood, however, that each of the figures is provided for the purpose of illustration and description only and is not intended as a definition of the limits of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] For a more complete understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawing, in which:
[0017] FIG. 1 is a flow chart of operation of an embodiment of the present invention;
[0018] FIG. 2 is a diagrammatic representation of a data center employing an embodiment of the present invention; and
[0019] FIG. 3 is a diagrammatic representation of multiple domains employing a hierarchical embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0020] The present systems and methods provide a mechanism by which equipment connected to a network may be automatically populated with near real-time information detailing its own physical location. Embodiments may be implemented to provide devices with the capability to become aware of their own physical location. Some embodiments might be particularly useful for devices such as personal computers, workstation, or the like, which can be set to run a software agent on startup. Other embodiments implement new code into device firmware, device Basic Input/Output Operating System (BIOS), or the like, to enable the device to probe for a location server on startup. This type of equipment may include routers, switches, or any other networked devices on which a user cannot easily install new code and/or which may not be capable of running a software agent.
[0021] In these embodiments, a location server will preferably be in place, in accordance with the present invention. The location server may be an extension of services provided by an existing, in place, RTLS system. Alternatively, the location server can be a separate system that either contains a duplicate of the RTLS database or that can query the RTLS database as needed. As a further alternative, the present invention may make use of both a location server that is an extension of an existing RTLS system and a separate location server.
[0022] FIG. 1 is a flow chart of operation 100 of embodiments of the present invention. With a location server in place, under some embodiments of the present invention a software agent is installed on the device to be tracked at 101 . This agent preferably instructs the device to send a query at 102 , via network connectivity to the location server in order to discover its location. Once this information is retrieved at 103 , it is either stored in a local variable, or if the machine is managed via SNMP, or the like, placed in a local MIB variable, or the like, at 104 . The agent may poll ( 105 ) the location server at programmable intervals, preferably by repeating step 102 above, to maintain current location information at least internally, preferably by repeating steps 103 and 104 above.
[0023] In other embodiments, the device employs a built-in agent process 106 that immediately searches for a location server at 102 , preferably in a manner similar to the Dynamic Host Configuration Protocol (DHCP), upon power-up. Again, the device would populate either a local variable or a MIB variable to store this information at 104 , once it is retrieved at 103 . In one embodiment the device would also poll for current data at programmable intervals ( 105 ). As with the embodiments previously described, this location information may also be updated on the location server during the periodic location updates.
[0024] Users of the system may either use standard SNMP MIB enabled browsers to retrieve location information directly from the device, or if the device is not managed via SNMP, they may access a shell account, or the like, and view the system variable.
[0025] FIG. 2 is a diagrammatic representation of data center 201 employing embodiment 200 of the present invention. Devices, such as example device 202 , are located in large data center 201 , which may be a single large building that houses thousands of different pieces of network equipment and/or equipment racks 203 with many pieces of equipment in each rack. Such a data center may already be using real-time location system 210 . This real-time location system generally comprises receivers/antennas 212 mounted at various locations in the building and centralized server 220 . Each device that is installed in the data center may be tagged with whatever technology that this particular RTLS uses, tags 215 such as a Radio Frequency (RF) transponders, or the like. In accordance with the present invention each device 202 to be provided location self awareness has software agent functionality or process 225 installed or incorporated into device 202 . Agent 225 is used to gather location information from location server 230 .
[0026] As an example, PC 202 located in a rack in building 201 has tag 215 on it. In this example PC 202 belongs to service provider 217 . Tag 215 is communicating PC 202 's location to an existing RTLS 210 . RTLS system 210 has a collection point typically in the form of a centralized server 220 where the data is kept for all of the devices in the building, including PC 202 . Server 220 may make that data available via the web or via some specific application that may be accessed locally, through a network, or via a dial-up connection or in other manners known in the art. Software agent 225 , installed on PC 202 , will, upon boot of PC 202 , issue a query for location server 230 via network 232 or other connectivity 233 . Location server 230 responds with that device's location, which is concurrently or which has been previously retrieved from RTLS server 220 via connectivity 237 or network 232 .
[0027] Agent 225 queries a location server application, which may be either software located on central RTLS server 220 or a similar application located on separate system 235 . Agent 225 on the device to be located queries location server 230 upon boot up. Location server 230 preferably keeps a database of information related to the locations of the devices. That information is obtained or has previously been obtained from tracking system 210 server 220 . Location server 230 feeds this location information back to device 202 . Device 202 stores that data in an MIB or in a specialized application in accordance with embodiments of the present systems and methods.
[0028] Periodically, at a programmable time and/or interval, agent 225 preferably prompts device 202 to query location server 230 for the latest location information for device 202 . Alternatively, location server 230 may push updates out to devices any time its data changes, via network 232 or other connectivity 233 . In the case of a security application or the like, pushing updates might be advantageous.
[0029] FIG. 3 is a diagrammatic representation of multiple domains employing hierarchical embodiment 300 of the present invention. A large data center installation, or the like, might be spread over multiple areas, such as buildings or data centers 301 , 302 and 303 , which may be configured similar to data center 201 of FIG. 2 . Such areas may be too large for one tracking system to cover. Thus, multiple RTLSs 306 , 307 and 308 , similar to RTLS 210 of FIG. 2 , may be employed in such an installation. The organization of installation devices 311 , 312 , 313 may not match the organization of an RTLS communications infrastructure of the overall installation. Resultantly, devices might not be communicating with the “correct” location server 321 , 322 or 323 . To deal with this issue locations servers 321 , 322 , 323 in an installation may be configured to be aware of each other in an organizational structure, for example in a hierarchy, web, community, or the like, which may employ a network or other connectivity ( 324 ) which in turn may or may not be a part of the installation. In accordance with this embodiment when a location server ( 321 , 322 or 323 ) is queried for information not directly known by that location server, the location server should return an answer obtained from the correct location server as detailed below.
[0030] By way of example, on boot-up or whenever agent 325 , on device 311 , “wants” location data, it contacts the closest network location server. To do so, agent 325 sends a request out onto a network (not shown, for clarity) for a location server. Closest location server 321 , 322 or 323 , in the network sense, not necessarily in the physical sense, responds. Network topologies do not always match the physical topological locations of network devices. Agent 325 queries the responding location server 321 , 322 or 323 for its device's location. The location server queries its associated RTLS system (or its internal database of RTLS data) and the RTLS system presently returns the device's location as described in greater detail above. If the data is not available to the location server, hierarchical location server 350 queries the next RTLS data system upward in the hierarchy, which queries any sub-location servers it has under it, to determine the device's location.
[0031] In the case of a response, the response is sent back to the originating location server and then to the originating agent on the device. If the device's location is not found, the process is repeated one more level up in the hierarchy. The query is preferably sent along all paths. As a preferable optimization, the query is not sent to the server that sends the request.
[0032] For example, on boot, agent 325 on device 311 requests location data by contacting the closest network location server ( 321 ). Agent 325 queries responding location server 321 for device 311 's location. The location server queries its associated RTLS system 306 (or its internal database of RTLS data). If the location data is not available to location server 321 , the location server queries the next RTLS data system upward in the hierarchy via hierarchical location server 350 to determine the device's location. In FIG. 3 the next RTLS server up in the hierarchy might be RTLS 307 and/or RTLS 308 , depending on the hierarchy arrangement of the data center areas 301 , 302 and 303 of the installation. In this example, using FIG. 3 , RTLS 307 or RTLS 308 should return the device's location.
[0033] In a push embodiment, when the location server changes for a device, the location server that previously served a device can be informed of the location server reassignment. This notification can be made by the new location server. Then when the device reboots, since it remembers the last location server, that previous location server may provide the new server with the device's current location. Additionally or alternatively, this location update information may be pushed out to the moved device itself.
[0034] As an example, in FIG. 3 , if device 311 had been moved from area 303 to area 301 , RTLS 308 location server 323 may inform location server 321 that device 311 is now in RTLS server 306 's area ( 301 ). Thus when device 311 boots, if it seeks out its old location server ( 323 ), server 323 may return the device's correction location (and new local server assignment, 306 ). Alternatively, if the update was pushed directly to device 311 it will be “aware” of its new location.
[0035] Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps. | A system for physical location self awareness in network connected devices comprises a location server acquiring locations of the devices from a real-time location system (RTLS) and an agent running on each of the devices, the agent querying the location server for a location of the device and storing location information for the device on that device. The system may comprise a plurality of RTLSs and a hierarchical server for searching for a location of a device starting from a last known location server outward. A method for providing location self awareness in network connected devices comprises establishing a location server for acquiring a location of the device from an RTLS, executing an agent on the device, instructing the device to send a query to the location server for location information for the device, and storing the location information for the device on the device. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a process and apparatus for making optical fibers from core and cladding glass rods and to the fibers made by the process. More particularly, the invention relates to separately melting core and cladding glass rods and combining the melts proximate a fiber drawing orifice so that the core glass is surrounded by the cladding glass and drawing a glass clad optical fiber from the combined melts.
2. Description of the Background Art
Optical fibers, windows and filters find increasing use for many applications, particularly in data transmission. For example, silica based optical fibers are widely used in the telecommunications industry. However, silica fibers transmit only up to about 2 microns and there are many applications in which the wavelengths are longer than 2 microns, such as infrared imaging, detection and analysis of high temperatures and high temperature effects and power delivery from CO and CO 2 lasers. Remote fiber optic chemical sensing systems are useful for the clean up of Department of Defense and Department of Energy facilities, as well as other industrial applications, because practically all molecular species possess characteristic vibrational bands in the infrared region between 3-11 microns. Zirconium fluoride based fibers transmit to about 3.5 microns, but this still isn't sufficient for most infrared systems. Chalcogenide glasses transmit to beyond 10 microns and are therefore used for optical fibers in fiber optic based sensor systems using evanescent, absorption and diffuse reflectance spectroscopies, which require long wavelength infrared transmission capability. Since the efficiency and capability of such systems depends in large measure on the infrared optical properties of the glass, it is important that the glass have low transmission losses. Therefore, there is a need to fabricate low loss chalcogenide glass fibers and especially in long lengths, to enhance the capabilities of many systems. For practical applications the chalcogenide glass fibers need to be glass clad to eliminate unwanted evanescent absorption and bending losses. Core and cladding glass compositions are selected so that the core refractive index is higher than that of the cladding while maintaining similarity in thermal properties. Typical techniques used to fabricate glass clad chalcogenide glass fibers include drawing the clad fiber from a preform fabricated by collapsing a cladding glass tube onto a core glass rod within. However, significant transmission losses can and do occur with the use of glass clad chalcogenide fibers drawn from such preforms due to bubbles in both the core and cladding glass and at the core/cladding glass interface, and also due to soot particles at the core/cladding glass interface caused by fabrication of the preforms and drawing of the clad fibers. These bubbles and soot particles act to scatter the infrared signals being transmitted which results in significant transmission losses. Further, practical size limitations of the preforms limit the process to drawing multimode fibers and the lengths of fiber drawn to typically less than 100 meters. U.S. Pat. No. 4,908,053 discloses drawing a clad fiber from a composite of a glass core rod concentrically disposed within a cladding glass tube in which a space exists between the tube and rod by melting the composite only at the bottom of the crucible in the vicinity of the drawing nozzle. The melting collapses the tube onto the rod only in the melt zone and the composite slowly moves down through the furnace as it is used up. While this process avoids the use of a core/clad preform, it does not prevent bubbles or soot formation at the core/cladding glass interface.
In order to avoid the need for preforms, double crucible processes have been developed in which a core glass crucible is concentrically disposed inside a cladding glass crucible so that the cladding glass melt is in contact with the outside of the core glass crucible. Both crucibles have a hole or orifice concentrically placed in the bottom of the crucible for the glass melts to flow out of, with both orifices coaxial and with the orifice in the bottom of the core glass crucible disposed just above the orifice in the cladding glass crucible. As the core glass melt flows out the orifice through the bottom of the core glass crucible, it contacts and is surrounded by the cladding glass melt and both melts flow out of the orifice in the bottom of the cladding glass crucible and form a clad fiber which is called a core/clad fiber. One such process is disclosed, for example, in U.S. Pat. No. 4,897,100 in which core and cladding glass chunks are melted in two separate, but concentric crucibles, with the core glass crucible disposed inside the cladding glass crucible. Each crucible has an orifice at the bottom for drawing out the molten glass, with the core glass crucible orifice disposed just above the cladding glass crucible orifice. Both orifices are coaxial. As the core glass melt flows out the orifice in the bottom of the core glass crucible, it is surrounded by cladding glass flowing down through the orifice in the bottom of the cladding glass crucible and a core/clad fiber is drawn. In this process, melting the glass chunks in the crucibles introduces gas bubbles at the interfaces and interstices of the chards or chunks as they melt. As a consequence, the glass melts are held at elevated temperatures for long periods of time to drive out some of the gas and to achieve homogeneity of the melt. Unfortunately, this can change the composition of the glass over a period of time as more volatile components of the glass are vaporized. Both glass melts are simultaneously withdrawn from the orifice at the bottom of their respective crucibles, with the core glass melt flowing through the cladding glass melt below, so that the cladding glass flows around the core glass as both glasses flow out the bottom of the cladding glass crucible. This process is difficult to control, uniform concentricity of the core and cladding glasses is extremely difficult to achieve, and it does not eliminate bubbles or soot formation. Another approach to the double crucible process is one in which a core glass disk and a cladding glass disk are core drilled from large slabs of glass. The core glass disk is heated and melted in a crucible having a hole in the bottom from which is drawn a core glass fiber. The cladding glass disk is heated in a separate crucible coaxial with and disposed vertically below the core glass crucible and it also has a hole or orifice in the bottom. The solid glass fiber drawn from the core glass crucible passes through the cladding glass melt which coats the core fiber with cladding glass and a glass clad fiber is drawn out the bottom of the cladding glass crucible. Since the solid core glass fiber must pass through the cladding glass melt, both glasses must have a different viscosity profile and the core glass must have a higher melting temperature. Aside from inherent stress, bubbles and soot are formed at the core and cladding glass interface of the fiber produced from this process. Also, the clad fiber has a low melting temperature and cannot generally be used above 110° C., which means that it cannot be used for high power lasers. Still further, core drilling the core and cladding glass disks from large slabs of glass can introduce contaminants onto the glass. None of these double crucible processes is suitable for use with the relatively volatile and unstable chalcogenide glass compositions as both glass compositions remain in the molten state for a long period of time and the resulting volatilization losses lead to compositional variations in the core and cladding glasses, which itself leads to increased optical losses. Therefore, there is still a need for a method of producing core/clad glass optical fiber without the need for a core/clad preform or the use of glass chunks, with little or no soot formation at the interface between the glasses, and which will also eliminate or at least minimize the size and frequency of bubbles present in the glasses.
SUMMARY OF THE INVENTION
Accordingly, it is an object of this invention to produce a core/clad glass optical fiber without the need for a core/clad preform or the use of glass chunks.
It is another object of the present invention to reduce or eliminate soot formation at the core/clad interface of a core/clad glass optical fiber.
It is a further object of the present invention to reduce or eliminate bubble formation at the core/clad interface of a core/clad glass optical fiber.
These and additional objects of the invention are accomplished by a process in which the core and clad glass are melted in separate crucibles or melting zones. The two melts are then separately passed into and through two respective glass melt flow zones out of contact with each other to a respective orifice or exit means for each flow zone, wherein they exit their respective flow zones and contact each other as melts proximate a fiber drawing orifice or die, with the cladding glass melt surrounding the core glass melt proximate the fiber drawing orifice or die from which a core/clad fiber is drawn. The two crucibles or melting zones are neither concentric nor coaxial as in the prior art double crucible processes, although they may be so disposed if desired. In an embodiment used to demonstrate the efficacy of the process of the invention, the two glass melting zones are laterally or horizontally spaced apart and not vertically disposed with respect to each other as in the prior art double crucible processes. This enables better control of (i) the glass melting operation, (ii) the atmosphere and pressure in each crucible and (iii) minimizes contamination of the glass melt in each crucible as is explained in detail below. It also permits the melting zones and crucibles to be heated to different temperatures, if desired. The process of the invention forms optical fibers directly from a core glass rod and a cladding glass rod without the need for core/clad preforms, cladding glass tubes, without forming melts from chards or chunks of glass with its concomitant gas absorption and entrapment and prolonged heating times, and without being restricted to maintaining both glass melts at the same temperature. In the process of the invention, the two glass melting zones may be at a temperature different from the temperature in the glass melt flow zones and the glass contacting/fiber drawing zone. The use of glass rods permits the use of simple rod geometries, which need not be cylindrical, but can be of any practicable shape and which can be fabricated in sizes both larger and smaller than is presently practicable with processes which use rod and tube combinations or preforms. Another advantage is that the dimensions of the rods need not be precise, as is the case when using core rod and cladding tube assemblies and fabricating preforms. Still another advantage of forming a glass melt directly from a rod is that the rod can be formed under sealed conditions in a suitable ampoule or other means and the so-formed rod directly melted without undergoing further processing into chards, preforms, tubes and the like, all of which introduce gas bubbles, soot and other contaminants into the glass. If desired by the practitioner, the glass "rods" employed as the source of core and cladding glass in the process of the invention can be disk-shaped and can also be in the form of hollow tubes, if desired. However, to the extent that these disk and hollow-tube shapes can and do result in soot formation and/or gas bubbles and other contaminants in the optical fiber, it is preferred that the rods be solid bodies of glass and still more preferably that the length of the glass body be at least equal to the average cross-sectional dimension or equivalent diameter in the event that a shape other than cylindrical is used. In the process of the invention, the glass melting zones (crucibles) and melt flow zones, as well as the core and cladding glass rods, can be outgassed prior to forming the melts and then replaced with an inert gas atmosphere during melting and drawing. The core and cladding glass rods are each melted either as a single mass or slowly melted proximate their bottom portion only during the process, to further minimize heat exposure of the glass compositions and concomitant volatilization and compositional variation defects during the melting. By melting it is meant that the glass is soft enough to flow and this must be determined empirically for each composition, as it is a function of the melting temperature, the pressure on the glass melt and the viscosity of the glass. In a broad sense, by melt is meant a softened glass at a temperature above its glass transition temperature and having a viscosity within the broad range of from about 10 0 -10 9 poise, and more specifically within the range of from about 10 3 -10 6 poise for chalcogenide glass.
While the process of the invention has been demonstrated with chalcogenide core and cladding glass compositions, it is useful with all glass compositions and not limited for use with chalcogenide glass. Illustrative, but nonlimiting examples of other types of glass which can be formed into glass clad glass fibers include silicates, fluoride glasses, phosphates, borates and germanates. As those skilled in the art know, chalcogenide glasses comprise at least one of the chalcogenide elements S, Se and Te and typically further include at least one of Ge, As, Sb, Tl, Pb, Si, P, Ga, In, La, Cl, Br and I. Such glasses can also contain one or more rare earth elements. Chalcogenide glass typically contains at least about 25 mole % and more generally at least 50 mole % of one or more of the three chalcogenide elements. The presence of tellurium in the glass composition has been found to increase the transmission in the infrared region. Thus, while sulphide fibers such as As 2 S 3 transmit from about 1-6 microns, the transmission window is increased to beyond 10 microns by including the heavier chalcogenide element tellurium. Glasses containing high levels of tellurium typically transmit in the 3-12 microns region.
In demonstrating the invention, a cylindrical core glass rod was placed in a tubular shaped quartz crucible or melting zone and a cylindrical cladding glass rod was placed in a separate quartz crucible or melting zone laterally spaced apart from the core glass crucible, so that the longitudinal axes of both crucibles were not coincident and both crucibles were laterally spaced apart from each other at about the same horizontal level. Each crucible had an orifice at the bottom which is opened into a respective melt flow zone. Each rod was heated in its respective crucible or melting zone to soften the glass so that it flowed down into a respective glass melt flow zone (also fabricated from quartz) without contacting the other glass melt, with the cladding glass melt flow zone surrounding the core glass melt flow zone. The bottom of the cladding glass flow zone contained an orifice which functioned as the fiber drawing orifice and the core glass flow zone had an exit orifice positioned proximate the drawing orifice, but slightly above and coaxial with it, so that the core glass melt was surrounded by the cladding glass melt proximate the drawing orifice to produce a core/clad optical fiber as both melts flowed down and out of the drawing orifice. In this embodiment the core glass melt was surrounded by and contacted the cladding glass melt before the two melts exited the apparatus via the cladding glass orifice which functioned as the fiber drawing orifice. However, in another embodiment the cladding glass melt will flow out of its orifice in the form of a cone-shaped annulus which contacts the core glass melt, which is in the form of a string or fiber of glass, just below the cladding glass melt orifice which is also the fiber drawing orifice or die. In still another embodiment the core glass melt contacts the surrounding cladding glass melt within the cladding glass orifice or fiber drawing orifice or die. By "proximate the fiber drawing orifice" it is meant to include all three embodiments as will be appreciated by those skilled in the art. Both melt flow zones were heated to the same temperature to melt the respective glasses. Both crucibles were heated to the same melt temperature to melt the respective glasses. Thus, in this embodiment the process of the invention comprises the steps of (a) melting a core glass rod and a cladding glass rod in respective crucibles which are neither concentric nor coaxial and are laterally spaced apart from each other, (b) flowing each glass melt through a respective melt flow zone so that the melts are not in contact with each other, (c) passing the melts from the flow zones to a contacting zone in which the glass melts come into contact, with the cladding glass melt surrounding the core glass and drawing a core/clad fiber ( a glass core/glass clad fiber) from the contacting zone. Further embodiments include outgassing the melting zone, the flow and contacting zones and also the core and cladding glass rods in their respective crucibles prior to melting the glasses. Yet another embodiment includes applying an inert gas atmosphere to the respective melts in the respective crucibles and also to applying a pressure to the glass melts by means of the gas to assist the glass melts to flow at a lower temperature than that at which flow would occur without the use of pressure. Further embodiments include (i) maintaining the melt and flow zones at different temperatures and (ii) maintaining the two melting zones or crucibles at different temperatures. Core/clad chalcogenide glass fiber produced by the process of the invention has been made with a concentricity of 100%. Also, while the above illustrations have been directed to multimode optical fiber production, the method of the invention is also useful for producing single mode optical fibers. Finally, those skilled in the art will appreciate that the addition of a third glass melting zone and another melt flow zone at least partially surrounding the first melt flow zone, etc., will enable the production of a double glass clad-glass core optical fiber.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete appreciation of the invention will be readily obtained by reference to the following Description of the Preferred Embodiments and the accompanying drawings in which like numerals in different figures represent the same structures or elements, wherein:
FIG. 1 schematically illustrates a across-section of an apparatus useful for the process of the invention.
FIG. 2(a), FIG. 2(b) and FIG. 2(c) each schematically illustrate, in cross-section, the apparatus of FIG. 1 and the core and cladding glass rods and melts during the process of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, a cross-section of an apparatus 10 useful for the practice of the process of the invention is schematically shown as comprising hollow, tubular crucibles 12 and 14 each having a tapered ground glass (quartz glass) top 16 and 18 covered by respective hollow covers or stoppers 20 and 22 which possess respective gas fittings 24 and 26. Crucibles 12 and 14 contain respective glass melt zones as cavities 30 and 32 within. Gas fittings 24 and 26 enable a vacuum to be applied to the interior of the apparatus for outgassing both the interior surfaces of the apparatus and the exterior surface of a glass core rod (not shown) and a glass cladding rod (not shown). They also enable inert or reactive gas to be applied to the interior 30 and 32 of the crucibles over the glass cladding and core rods and the glass melts during the process of melting, flowing and drawing. The inert gas serves to prevent the surfaces from being contaminated during the process and assists in the melt flow and drawing by applying pressure above the glass melts (not shown). In this embodiment, support 28 aids in maintaining the crucibles in their proper positions and makes the apparatus stronger and less prone to breaking. The apparatus shown is fabricated from quartz which is sometimes referred to as fused silica or quartz glass. Those skilled in the art will appreciate that if a higher melting glass and not chalcogenide glass rods are used, the apparatus will be made of a suitable higher melting material such as platinum, platinum alloy and the like. In this embodiment the ground glass surfaces enable a seal to be made by the hollow quartz stoppers 20 and 22. Support 28 is a quartz rod. The wall 34 of crucible 12 continues down to form a tubular cylinder defined by wall 36 which forms a cylindrical cavity 38 having an annular or washer-shaped cross-section. The bottom of crucible 12 contains an orifice or opening 39 which extends down into cavity 42 in tube 40. Crucible 14 also has an orifice 37 at the bottom which extends down into cavity or bore 43 of tubular conduit 41 and then into cavity 38. Conduit 41 is joined to cavity 38 defined by walls 34 and 36. Bore 43 and cavity 38 are contiguous and serve as the melt flow zone for the cladding glass melt which flows down therethrough as a result of melting the cladding glass rod in cladding glass crucible 14. Similarly, bore 42 serves as the melt flow zone for the core glass melt which is formed by melting the core glass rod (not shown) in core glass crucible 12. Capillary tube 35 extends out from wall 36 and up to near the top of the apparatus and contains a bore 33 opens into cavity 38 at its lower end and at the other end is open to the atmosphere and serves as a gas conduit, so that any gas present in 38 flows into 33 and out through the upper end of the capillary as the cladding glass melt flows out of its crucible or melting zone and fills up cavity 38. The bore 33 is too small for the glass to flow through. Inert gas applied to the top of the melts via hollow stoppers 20 and 22 serves to push the glass melts down through the melt flow zones which are cavities 38, 42 and 43. As can be appreciated by reference to FIG. 1 and as shown in detail in FIGS. 2(a), 2(b), and 2(c), the liquid core glass exits its melt zone (cavity 42) via tubular orifice 44 which extends down and provides an outlet for the cladding glass melt at a point just above orifice 48 where it is surrounded and contacted by the liquid cladding glass flowing out of cavity 38 and gaps 46, 47 through 48 which serves as the fiber drawing orifice. The melts contact each other in contact zone 48 defined by the brief space between the bottom of cladding glass melt flow orifice 44 and fiber drawing orifice 48. A core/clad glass optical fiber (not shown) is drawn down out of orifice 48. A loose fitting quartz plug 62 is placed in the bottom openings 44 and 48 until the fiber is ready to be drawn. Not shown in FIG. 1 is the furnace which comprises the means for heating crucibles 12 and 14 and the melt flow zones. This is illustrated in FIG. 2 and is explained in detail below.
Turning now to FIGS. 2(a), 2(b) and 2(c) which illustrate the process of the invention and an apparatus 50 useful for the process of the invention is shown as comprising an apparatus 10 substantially that illustrated in FIG. 1, but lacking some of the details for the sake of brevity. Apparatus 10 is shown surrounded with a furnace which comprises a glass (Pyrex or quartz) shroud 52 around the outside of which are heating means 58 and 60 which are resistance wire, tape or any other suitable means as is known to those skilled in the art. In the embodiment used in the examples, the heating means were heating tape, with the glass shroud and heating tape wrapped with Fiberfax™ thermal insulation; a type of fiberglass insulation known to those skilled in the art. The glass shroud is sized so as to conform as close as possible to the shape of the exterior of the apparatus so as to achieve uniform heating. With specific reference first to FIG. 2(a), a glass core rod 54 and a glass cladding rod 56 are shown in respective crucibles 12 and 14, with a loose fitting quartz plug 62 placed in the bottom opening. In this embodiment heating means 58 and 60 comprise two separate heating tapes wrapped around the outside of the glass container so that the glass softening or melting zones (crucibles 12 and 14) can be heated to a different temperature than the melt flow and drawing zones below, if desired. The glass core and cladding rods are placed in their respective crucibles as shown and the entire apparatus is heated up to about 100° C. while a vacuum is applied to the interior of the apparatus and to the exterior surface of the glass rods through gas fittings 24 and 26 to vacuum outgas the interior of the apparatus and also the glass rods. The rods and the interior of the apparatus are then purged with dry nitrogen through fittings 24 and 26 and the melting zones or crucibles are then heated to a temperature above the glass transition temperature of the glass by heating tapes 58, while the lower melt flow and fiber drawing zone is heated to the same or different temperature by heating tapes 60. The heating causes the glass rods to soften and the glass to flow into respective core and cladding glass conduits 42 and 43 as shown in FIG. 2(b) and the pressure applied to the glass melts through 24 and 26 is increased. The plug 62 is removed and the core/clad glass fiber drawn from the bottom as illustrated in FIG. 2(c). The process of the invention enables good concentricity of the core and cladding glass to be achieved in the fiber. Concentricity is determined by measuring the cross-section of the core/clad fiber produced at a number of different points along the length of the fiber, measuring the maximum and minimum cladding thickness at each point, and then dividing the minimum value by the maximum value times one hundred to obtain the concentricity as a percentage value. Core/clad chalcogenide glass fiber produced by the process of the invention has been made with a concentricity of 100%.
Having described the invention, the following examples are given to illustrate specific applications of the invention including the best mode now known to perform the invention. These specific examples are not intended to limit the scope of the invention described in this application.
EXAMPLES
In the Examples below, chalcogenide core glass rods having a composition As 40 S 58 Se 2 (atomic %) were fabricated from elemental starting materials of reagent grade purity which had been further purified. For each rod, the arsenic, sulfur and selenium were weighed out, dry mixed and placed in a quartz glass ampoule made from fused silica in a dry box, with the ampoules then evacuated and sealed with an oxygen-methane torch. The chalcogenide cladding glass rod had a composition As 40 S 60 and was fabricated using the same procedure. Melting of the glass batches was done at 850° C. for 8 hours in a rocking furnace to facilitate mixing. The melts were then quenched with the ampoules in a vertical position and annealed from about the glass transition temperature (˜200° C.) to produce rods approximately 10 cm in length and 10 mm in diameter. The difference in thermal expansion and contraction between the chalcogenide glass and the quartz glass results in the diameter of the chalcogenide glass rods being slightly less than that of the quartz, so that the rods are merely removed from the ampoules after the top has been broken off. The chalcogenide glasses do not react with quartz at the temperatures used in the process of the invention as set forth in the examples below.
Example 1
In this example the apparatus schematically illustrated and described in FIGS. 1 and 2 was used. The apparatus as shown in FIG. 1 was fabricated of quartz and then placed within a snug fitting glass container having heating tapes wrapped around the outside as shown in FIG. 2 to form two independent heating zones. The dimensions of the core and cladding glass rod crucible tubes 12 and 14 were both 12×18 mm. The distance from the intersection of the bottom of the cladding glass conduit 41 with quartz glass wall 36 to the bottom of the melt flow and drawing zone was 3 inches. Conduit 41 was 6×10 mm and the core rod glass flow conduit 40 was 5×8 mm with a 1 mm gap between the bottom of the core glass flow orifice 44 and the bottom of the inside of the outer wall 36 which served as the glass melt contact zone in which the core glass flowed down and out of the orifice in the bottom of its flow conduit and contacted the cladding glass melt which surrounded it prior to the glasses exiting out the bottom of the apparatus as a core/clad glass optical fiber. The draw orifice had a diameter of 7 mm and the orifice at the bottom of the core glass flow conduit was 3 mm. Both orifices were ground and slightly tapered outwardly for ease of plugging. As explained above, one heating zone was the upper zone which heated the two crucibles or glass melting zones and the other heating zone was the lower zone which comprised the glass melt flow zone and the fiber drawing zone. The hollow stoppers (20 and 22) were removed from the ground glass joints and the core and cladding glass rods placed in their respective crucibles, with the core glass rod in the central tube 12 and the cladding glass rod in the outer tube 14 as shown in the Figures. The hollow stoppers were then re-positioned in the ground glass joints at the top and connected to a nitrogen gas supply and a loose fitting quartz plug (62) was placed in the bottom opening. The glass rods and apparatus were then purged with dry nitrogen gas and heated up to a set temperature of approximately 395° C. in the upper zone and to a temperature of 375° C. in the lower zone, both temperatures being above the glass transition temperature of approximately 200° C. The zonal temperature differences were arbitrary. Under these conditions, the core and cladding glass rods softened and flowed into their respective melt flow conduits under a nitrogen pressure of approximately one inch of water, thereby plugging up the openings at the bottom of each crucible tube as illustrated in FIG. 2(b). As a result, the pressure above each glass started to increase and the pressure was controlled using a pressure controller and a pressure relief valve. Initially the set temperatures in the upper and lower zones were reduced to 370° C. and 358° C., respectively, and the pressure above the core and cladding glass rods was increased to 1.5 inches (P1) and 2 inches of water (P2), respectively. Subsequently, the quartz plug was removed and the core/clad fiber emerged from the bottom of the quartz glassware as shown in FIG. 2(c). The fiber was drawn with core and cladding diameters of 175 μm and 235 μm. The fiber exhibited a concentricity of 100%. A thicker fiber with core and cladding glass diameters of 190 μm and 250 μm was obtained by decreasing the set temperature of the upper and lower zones to 362° and 348° C., respectively and increasing the pressure above the core and cladding glass rods to 0.2 and 0.5 psi, respectively. Over fifty meters of this fiber was collected on a winding drum and had a concentricity of 100%.
Example 2
In this experiment the lower portion of the quartz glassware was significantly shorter, being only about 3/4 inches long as compared to the 3 inches of the apparatus used in Example 1. Also, the core and cladding glass openings in the bottom were increased to 4 and 8 mm, respectively, from the 3 mm and 7 mm used in Example 1. Increasing the exit dimensions enables a thicker fiber to be drawn. In this experiment a 400 μm diameter core/clad glass fiber was drawn when the top and bottom zone temperatures were 371° C. and 363° C., respectively, and the core and cladding pressures were 0.5 psi and 0.2 psi, respectively. Further, when the top and bottom temperatures were 366° C. and 362° C. and the nitrogen pressure on the core and cladding glass pressures was 0.3 psi and 0.2 psi, respectively, 350 μm diameter core/clad fiber was drawn.
It is understood that various other embodiments and modifications in the practice of the invention will be apparent to, and can be readily made by, those skilled in the art without departing from the scope and spirit of the invention described above. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the exact description set forth above, but rather that the claims be construed as encompassing all of the features of patentable novelty which reside in the present invention, including all the features and embodiments which would be treated as equivalents thereof by those skilled in the art to which the invention pertains. | A core/clad glass optical fiber is made by melting a core glass rod and a adding glass rod in separate crucibles which are not intersecting with respect to each other and the respective core and cladding glass melts passed out of contact with each other to a glass melt contacting zone proximate a fiber drawing orifice in which the cladding glass surrounds the core glass and a core/clad glass fiber is drawn. This process enables the clad glass fiber to be drawn directly from core and cladding glass rods without the need for a preform or forming a melt from glass chards or chunks, thereby reducing the cost of producing the fiber and also producing a glass clad optical fiber of high purity and excellent concentricity. Chalcogenide glass fibers having a concentricity of 100% have been made. | 2 |
FIELD OF THE INVENTION
[0001] This invention is directed to microbial adherence inhibitor, in the form of fowl egg antibodies, for substantially preventing the attachment or adherence of colony-forming immunogens or haptens in the rumen and intestinal tract of host food animals, to the method of producing such adherence inhibitors, and to the methods of using such inhibitors to: (1) promote the growth of food animals by improving feed conversion rates by decreasing the waste of dietary protein caused by the presence of certain colony-forming protein-wasting organisms in food animals, and (2) to substantially reduce or eliminate the incidence of illnesses caused by the presence of certain illness-causing colony-forming immunogens or haptens in meat from food animals, which are not themselves subjected to the targeted illness, and in other food stuffs.
BACKGROUND OF THE INVENTION
[0002] Common bacterial immunogens which cause dramatic decreases in an animal's ability to utilize dietary protein include but are not limited to Peptostreptococcus anaerobius, Clostridium aminophilum , and Clostridium sticklandii . According to Russell (USDA-ARS, May 1993) these organisms, and others disclosed therein, have been collectively responsible for wasting up to 25 percent of the protein in cattle diets. This is a loss of as much as $25 billion annually to cattle producers and is especially apparent in “grazing animals which are often deficient in protein, even though their protein intake appears to be adequate.” As the host consumes protein in the diet, these deleterious organisms wastefully degrade the protein to ammonia which is converted to urea by the liver and kidneys and thus lost to the host when excreted as urine. These deleterious organisms also compete with beneficial organisms which the host needs for the efficient utilization of ammonia. In addition, they need other beneficial organisms in the rumen for greater ammonia utilization.
[0003] The principal objective of the present invention is to substantially prevent the colonization of deleterious organisms such as P. anaerobius, C. sticklandii and C. aminophilum as well as the growth of such organisms in the rumen and the intestinal tracts of food animals resulting in their substantial elimination from the animal by the administration of the fowl egg antibody to the specific organisms.
[0004] Common bacterial immunogens which cause food borne illness in humans include E. coli , Listeria, Salmonella and Campylobacter, all of which produce flu-like symptoms such as nausea, vomiting, diarrhea and/or fever, and in some cases causes kidney damage or death. In recent years foodstuffs contaminated with these bacteria have caused gastrointestinal distress in tens or hundreds of thousands of people and the recall and destruction of millions of pounds of food. The resulting economic loss has been staggering. Especially daunting as a public health threat has been E. coli 0157:H7, a pathogenic strain of the common gut bacterium, first identified in 1982. The bacteria are carried in the intestinal tracts of food animals and expelled in their feces. From there, the bacteria enter the food supply, not only in the meat of those animals, but foods such as milk, fruit juices, lettuce, alfalfa sprouts, radishes and others.
[0005] Haptens are partial or incomplete immunogens such as certain toxins, which cannot by themselves cause antibody formation but are capable of combining with specific antibodies. Such haptens may include bacterial toxin, yeast mold toxin, viruses, parasite toxins, algae toxins, etc.
[0006] Other colony-forming organisms include Actinomycetes, Streptococcus, Bacteriodes such as B. ruminicola , Crytococcus and yeast molds.
[0007] Another principal object of the present invention is to substantially prevent the adherence of immunogens, such as E. coli 0157:H7, or haptens, and the colonization and growth of such immunogens or haptens in the rumen or intestinal tracts of food animals, and substantial elimination of the immunogen or hapten from the feces of the animals, by the administration to the animals of fowl egg antibody to the specific immunogen or hapten.
PRIOR ART
[0008] The production of avian egg antibody for the diagnosis or treatment of specific conditions has been known. The production of avian egg antibody for the inhibition of organisms, specifically the colonization of non-illness-causing protein-wasting organisms, and the adherence and colonization of illness-causing immunogens is not suggested.
[0009] Representative prior art patents include the following:
[0010] Polson, U.S. Pat. No. 4,550,019
[0011] Stolle et al, U.S. Pat. No. 4,748,018
[0012] Tokoro, U.S. Pat. No. 5,080,895
[0013] Carroll, U.S. Pat. No. 5,196,193
[0014] Lee, U.S. Pat. No. 5,367,054
[0015] Coleman, U.S. Pat. No. 5,585,098
[0016] Stolle et al, U.S. Pat. No. 5,753,268
[0017] Raun, U.S. Pat. No. 3,794,732, discusses the uses of polyester antibiotics in ruminant rations to improve the utilization of feed in ruminant animals. This specifically addresses the use of antibiotics in ruminant animals as growth promotants.
[0018] Raun, U.S. Pat. No. 3,947,836, discusses the use of specific antibiotic compounds for ruminant feed utilization improvement when give orally to the animal. Specifically, the animal develops rumen function where more propionates in relation to acetates are produced thus improving feed utilization.
[0019] Ivy et al, U.S. Pat. No. 4,933,364, discusses an alternative process for promoting growth and feed efficiency of food producing mammals. They propose the use of zinc antibiotic that can be added in insoluble form to create a zinc antibiotic complex which enhances feed efficiency of food producing mammals. They reference two U.S. Pat. Nos. 3,501,568 and 3,794,732, that cover monensin in great detail.
[0020] Other references on the use of additives such as monensin have mentioned the need for wise application of these materials because they can be toxic to some animals, such as horses. These antibiotics, which are not approved for use in dairy cows, must be administered carefully. In addition, feed intake is initially reduced as monensin cannot be added to molasses based supplements which are classic additives to cattle fees. (Pate, F., “Ionophores Do Not Appear To Work In Molasses Supplements”, ONA Reports, November, 1966, 2 pages, Florida Cattleman and Livestock Journal; Lona, R. P. et al, J. Anim. Sci. 75(1):2571-2579, 1979.)
[0021] Polson, U.S. Pat. No. 4,550,019, is directed to the manufacture and use of fowl egg yolk antibodies for making immunological preparations for the passive immunizations of animals, including humans, as immuno reagents for immunosorbitive processes and in particular for quantitative analytical tests, especially micro assays for diagnostic, pathological, forensic and pharmacokinectic investigations.
[0022] Stolle et al, U.S. Pat. No. 4,748,018, is directed to a method of passive immunization of mammals using avian egg yolk antibody against any of a variety of antigens using various methods of administration under various conditions and using various compositions incorporating the antibody, after first developing in the mammal a tolerance for the antibody.
[0023] Tokoro, U.S. Pat. No. 5,080,895, is directed to a specific antibody containing substance from eggs and method of production and use thereof for the treatment of infectious or other diseases, and as additives in food for livestock and poultry, cosmetics, and medicines, and in the field of serodiagnosis. Although not explicitly stated, it is apparent that the use of the egg antibody in feeds is to provide an easy means of oral administration of the antibody for the treatment of intestinal infections in livestock or poultry.
[0024] Carroll, U.S. Pat. No. 5,196,193, and divisional U.S. Pat. No. 5,443,976, are directed to anti-venom compositions containing horse antibody or avian egg yolk antibody for neutralizing snake, spider, scorpion or jelly fish venom.
[0025] U.S. Pat. No. 5,367,054, is directed to methods for large scale purification of egg immunoglobulin for the treatment of infections.
[0026] Coleman, U.S. Pat. No. 5,585,098, is directed to a method of oral administration of chicken yolk immunoglobulins to lower somatic cell count in the milk of lactating ruminants.
[0027] Stolle et al, U.S. Pat. No. 5,753,268, is directed to an anti-cholesterolemic egg vaccine and method for production and use as a dietary supplement for the treatment of vascular disorders in humans and other animals.
SUMMARY OF THE INVENTION
[0028] Broadly stated this invention is directed to a method for the production of a microbial adherence inhibitor for administration to host food animals to substantially prevent the adherence of colony-forming immunogens or haptens in the rumen and/or intestinal tracts of the food animals by first inoculating female birds, in or about to reach their egg laying age, with the particular target immunogen. Then, after a period of time sufficient to permit the production in the bird of antibody to the targeted immunogen, the eggs laid by the birds are harvested. The total antibody-containing contents of the eggs are separated from the shells and dried. The egg contents may be dried on a feed extender or carrier material. The dried separated egg antibody adherence inhibiting material may be stored or shipped for use when needed.
[0029] The target immunogen with which the bird is inoculated depends upon the anticipated use of the inhibitor, a non-disease-causing protein-wasting organism where boosting of feed efficiency is the objective, and a targeted disease-causing organism where the objective is the substantial reduction or elimination of illnesses.
[0030] The dried egg contents incorporating the antibody specific to the targeted immunogen is administered to the food animals by distributing the antibody material substantially uniformly throughout an animal feed and then supplying the resulting antibody-containing animal feed to the food animals. When improved feed utilization is the objective, the antibody-containing animal feed is supplied to food animals during the normal finishing schedule prior to slaughter. The substantial prevention of colonization of the targeted organism in the rumen or intestinal tract of the animal will ultimately permit elimination of the organism from the animal. This repression of colonization and elimination of the subject organisms will permit a significant decrease in the wasteful degradation of the dietary protein fed to food production animals. In addition, the resulting decrease in competition to the non-ammonia producing organisms will further enhance the most efficient utilization of feed by the host. (Russell, USDA-ARS, May 1993.) When the objective is the elimination of disease-causing organisms from the meat of food animals, the antibody-containing feed is supplied sufficiently before slaughter to substantially prevent adherence of the target immunogen or hapten in the intestinal tract of the animal, and permit elimination of the immunogen or hapten from the animal.
[0031] The invention is directed particularly to the production of an adherence inhibitor specific to E. coli 0157:H7 and to the substantial reduction or elimination of gastric illnesses caused by this bacterium. The invention is described with particular reference to elimination of illnesses caused by E. coli 0157.H7, but it is understood that the invention is not so limited, but is equally applicable to elimination of illnesses caused by the other colony-forming immunogens and haptens.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0032] The present invention is based on the concept of specifically inhibiting the ability of colony-forming protein-wasting organisms, such as P. anaerobius, C. sticklandii and C. aminophilum , and colony forming disease-causing organisms, such as E. coli 0157:-H7, Listeria, Salmonella and Campylobacter, to adhere in the rumen or intestinal tracts of food animals and thus reduce their ability to multiply, grow and colonize. Dietary modifications may be designed to make the rumen and intestinal tract less receptive to the organisms over the lifetime of the animal. While the microbial inhibitor of the present invention may be administered at will by the producer, it is preferred for efficient animal feed utilization that a carefully determined and managed course of administration during the finishing period at the feedlot level be scheduled and followed. Such a predetermined period which takes advantage of the low dose, longer cumulative effect of the inhibitor and which is also easily integrated into current production practices will provide the most economically attractive rate of return through improved animal performance.
[0033] For the elimination of disease-causing organisms the inhibitor may be administered either immediately pre-slaughter or over some substantial period of the lifetime of the animal. It is preferred that a carefully determined and managed mid-term period course of administration at the feedlot level be followed. As described, a set pre-slaughter period takes advantage of the low dose, longer cumulative effect, is easily integratable into current production practices and is the most economical. It also allows the microorganism to naturally disappear from the mud and manure on the outside of the animal, a significant source of potential contamination at slaughter. Under the current feeding system, food animal feed efficiency is enhanced through the use of ionophores such as monesin, a feed additive marketed under the trade name Rumensin. These are a class of polyester antibiotics approved for feed given to beef cattle and dairy heifers but not approved for use with lactating diary cows. Most gram-positive organisms are non-specifically vulnerable to the ionophores, antibiotics which can also be quite toxic to the host animal if used improperly. As these antibiotics are not specific, many of the ruminal organisms required to digest the cellulose of ingested plant material may also be affected. The problem with carry over and the development of drug resistant strains of organisms are also major concerns to the industry. The use of broad spectrum antibiotics has further drawbacks including vulnerability to human error, additional cost, consumer resistance and the like. In addition, the monensin type additive cannot be administered with commonly used molasses based supplements.
[0034] Any organism that colonizes the rumen or alimentary tract of its host must possess the capability of sticking or adhering to that surface in order to multiply and grow. The specific organisms addressed by this invention are no exception to the rule. As other factors such as the need of beneficial organisms for specific enzymes must also be considered, specific reagents are required to reduce the number of targeted organisms in the rumen or intestinal tract while not interfering with other normal flora. The organism inhibitor of this invention strongly interferes with adherence in a highly specific manner and, on a cumulative basis, thereby prevents the targeted organisms from multiplying, growing and colonizing. Through the vehicle of a simple daily feed supplement, the product essentially supplies the host with an antibody preparation designed not to cure any disease in the animal but to specifically dislodge any resident bacteria in the rumen or alimentary tract and to prevent attachment of any newly introduced numbers of that same bacteria. The microbial inhibitor has no direct effect whatsoever on the ultimate food products and leaves absolutely no undesirable residue in the animal or in the ultimate food products. In addition, since the deleterious organisms are prevented from multiplying, they will over time, for example the 120-day finishing period in the feedlot, disappear through natural degradation from the feedlot environment helping to eliminate that significant potential source of recontamination. The inhibitor product itself can be classified as a natural material of animal origin and as such can be used in almost any kind of feeding program. As the active ingredients are completely natural, they will work well with most feeds and feed additives including molasses based supplements.
[0035] All mammals and birds provide similar types of protection which allow for an immediate immune response in their very young offspring until they too acquire the ability to make the antibodies for themselves. More specifically called passive antibody protection, this defense mechanism is passed to the young of mammals through the placenta, the mother's milk or through both. The young of birds, however, receive their passive antibody protection through the store of antibodies placed in the eggs in which they develop from the embryonic stage. Birds, in particular, have the ability to “load up” their eggs as they are formed, with a very large supply of antibodies concentrated many fold over that which is present in the serum of the mother. In addition, avian antibodies are much more stable and resistant to inactivation through digestion than mammalian antibodies, especially under adverse conditions. Once immunized the hen layers the unique IgY types immunoglobulins in the yolk while depositing the common chicken IgM and IgA immunoglobulins in the albumin. The albumin helps resistance to the whole egg preparations and helps protect the avian antibodies. Furthermore, the large quantities of antibodies which are placed in eggs are much more exclusively those specific for the antigens to which the mother has most recently been exposed to and challenged by. This all results in the eggs of birds being a most ideal source for large quantities of economically produced, highly specific and stable antibodies. While the invention is illustrated by the use of chickens to produce avian antibody, other fowl including turkeys, ducks, geese, etc. may be used.
[0036] Specifically, groups are obtained of young hen chickens typically Rhode Island Reds, White Leghorns, sex-linked hybrid crosses or other breeds suited to large egg size, high volume egg production and ease of handling which are about to reach laying age, about 19 weeks for chickens, on a schedule predetermined by the amount and timing of final product desired resulting in a steady continuous production stream. After a suitable period of isolation and acclimatization of about 2 to 4 weeks, each group will enter into an inoculation program using rehydrated proprietary preparations of specific antigens to which an antibody is desired. The antigens may be obtained from commercial sources such as the American Type Culture Collection (ATCC). The antigen may be injected intramuscularly, but preferably injected sub-cutaneously. In approximately four to five weeks, the average egg collected will contain copious amounts of the desired specific antibody in a readily usable and stable form. The chickens may be reinoculated with the targeted antigen throughout the egg laying period to maintain the high antibody level.
[0037] Batches of eggs from predetermined groups of chickens are cracked, the contents are separated from the shells and mixed and preferably pasteurized (to eliminate potential pathogenic microorganism from the chicken and thus reduce potential contamination of feed). The total egg content is dried using standard commercial methods, such as spray drying using ambient or hot air up to 50° C. and tested to determine overall titer or antibody level. The egg contents may be dried alone or on innocuous feed extenders such as dry soy or rice husks or the like. Standard test procedures are used, such as ELISA, or agglutination, or the like. The typical batch is then blended with batches from groups of chickens at other average production levels resulting in a lot of standardized active ingredient. The dried egg antibody microbial inhibitor material may be stored and shipped on carrier materials such as soy bean hulls, boluses and/or tablets. Dependent on the needs and specifications of the feed formulator and the final customer, the final antibody product may include some type of innocuous additive, such as dried whey or dried soy protein powder, dried soy or rice husks or the like for formulation with feed ration. One egg produced and processed by the above procedures will yield a product sufficiently active and stable to provide at least as many as 350 to 700 daily doses of managed protection against specific microbial colonization. This method provides for the first time, an economical, safe and effective means for controlling feed efficiency organisms in beef cattle and dairy herds, and an economical, safe and effective means for controlling E. coli 0157:H7 and other illness-causing organisms in cattle herds.
[0038] The present invention specifically addresses feed efficiency as it relates to beef cattle, and by extension dairy cattle and dairy herds, and to the problem of eliminating illness-causing organisms from cattle. However, the concept of preventing microbial adherence has great economic potential for a number of diverse food safety and production applications. One such field of application is in feed and water targeting specific undesirable microorganisms. An example of this application would include products to actively inhibit pathogenic or even spoilage microorganisms in animal feed formulated for chickens and other poultry. Another such field of application is as rinse aid ingredients targeted to specific undesirable microorganisms. Examples of this application include products to actively dislodge pathogenic or even spoilage microorganisms for use in solutions for spot cleaning and rinsing beef carcasses or for chilling poultry after they have been dressed.
[0039] The most successful colonizing microorganisms, bacteria, viruses and parasite, etc., have evolved a number of different types of molecules, referred to as “adherins,” on their surfaces which can very tightly stick to one or more types of specific molecules that are part of the host's various surfaces. The adhesion inhibitor is an avian antibody of extraordinarily high specific activity which can very tightly bind to, coat, cover and obliterate these adherins which attach themselves to their hosts with a lock and key type of fit to very unique chemical structures. In addition to this direct attack, components of the complement system included in most biological fluids, such as blood, lymph, saliva, tears and to some extent intestinal secretions, recognize an antibody attachment as triggers for their many types of defensive activities. Specific antibody attachment and coating combined with the very likely mobilization of many other cellular defense systems, therefore, quickly culminates in the chemical inactivation and ultimately the destruction of the targeted microorganism.
[0040] The invention is further illustrated by the following examples:
EXAMPLE 1: Selection of Egg Laying Avian Hens
[0041] The strain of egg laying hen may vary with needs and uses. Any egg laying fowl hens may be immunized including chickens, turkeys, ducks, emus or any other fowl. The common strains of egg laying chickens are the preferred and are usually selected for the number of eggs laid per year, size of egg and ease of housing. Rhode Island Red, White Leghorn and Red Sex Linked hybrids are the animals of choice based on egg size (large to ex-large, 50-65 gm) and were used for the immunization schedules. The ease of handling the animals and the size and uniformity of the eggs along with the number of eggs laid per hen per year were observed. Although any avian egg laying hen could be used, for cost and ease of use these chickens proved to work the best. The Red Sex Linked hybrid gave the most uniformity and greater number of eggs per animal. These animals produce a large to extra-large grade of egg (50-65 gm) and up to 300 eggs a year per hen.
EXAMPLE 2: Preparation of Stock Culture
[0042] The American Type Culture Collection E. coli 0157:H7 Stock #43895 was used as the model bacterium. The organism was isolated from raw hamburger and colonizes in cattle. The ATCC Method for rehydration of the stock was followed. The bacterium is rehydrated in 1.0 ml of TSB Broth (Tryptase Soy Broth, Becton Dickinson), transferred to 5 ml of TSB sterile broth and incubated overnight (approximately 18 hours) at 37° C. . Nice turbid growth was observed. This is used as stock as needed. It was streaked on Sorbitol-MacConkey Agar (Difco) for verification of colony production.
EXAMPLE 3: Preparation of H Antigens for Immunogens
[0043] The H antigens were selected for development into an immunogen for immunizing the egg laying hens. Certain conditions are used to maintain the optimum growth of the H antigen during culturing to give added concentrations for the prep. Veal Infusion Agar (VIS) and Veal Infusion Broth (VIB, Becton Dickinson) is preferred for H antigen production. Stock TSB innoculated with VIB is incubated at 22° to 24° C. or room temperature for 18 hours. This stimulates flagella development on the bacteria. Flasks layered with VIA are inoculated with VIB culture. Good growth was seen after 22 hours. The product was harvested after 4 days. Flasks are combined by washing off the agar surface with Dulbecco's PSB solution (pH 7.3-7.4). The products is collected in tubes. Density is checked using spectrophotometer enumeration and McFarland nephelometer standards. Approximately 3×10/12/ml in stock. Motility is checked with motility agar slant (Northeast Laboratory Services). Stock is diluted to concentration of approximately 1×10 9 per ml in PBS and stirred for 1 hour at room temperature. The flagella is removed from the outside of the bacteria. Supernatant is collected using centrifugation. Pellet of whole bacteria is separated from the supernatant. Dry weight approximately 14.7 mg/ml is determined and the material is used as stock immunogen for H antigen. It is diluted to 1 mg/ml in PBS and heated for 30 minutes at 60° to 70° C. . This helps keep contamination down to a minimum. Thiogylcollate broth is inoculated to check for growth and animals are inoculated with immunogen.
EXAMPLE 4: Preparation of 0 Antigen for Immunogens
[0044] Brain Heart Infusion (BFI, acumedia) is used to stimulate the 0 antigens on the bacterium. Stock TSB innoculate BHI Broth is formed and incubated at 37° C. for 18 hours. This stimulates somatic antigen development on the bacteria. Flasks containing BHI Broth are inoculated with BHI Broth culture. While stirring slowly, flasks are incubated at 37° C. Good growth is seen after 22 hours. Flasks are combined and the material is harvested using centrifugation and sterile saline (0.9%) at approximately 3000 rpm for 30 minutes. The harvest is collected in tubes. Density is checked using spectrophotometer enumeration and McFarland nephelometer standards. The material is diluted to approximately 1×10 9 per ml. Four percent (4%) sodium deoxycholate (Difco) solution is added as a 1:1 ratio with culture in 0.9% sterile saline (Herzberg, 1972) and stirred for approximately 18 hours at room temperature (22° to 24° C.). The material is centrifuged to remove whole cells. Supernatant is used as stock for O antigen. Dry weight is determined at approximately 14.9 mg/ml. The product is diluted in sterile PBS, pH 7.4 to 1 mg/ml for O Immunogen.
EXAMPLE 5: Preparation of WC Antigen for Immunogens
[0045] Tryptic Soy Broth (TSB, Northeast Laboratory Services) plus Yeast Extract (BBL) is used for Whole Cell (WC) antigen production. TSB plus Yeast Extract 0.6% Broth is inoculated with TSB Stock and incubated at 37° C. for 18 hours. This stimulates somatic and other surface antigens to development on the bacteria. Flasks are inoculated with TSB with Yeast Extract Broth. While stirring slowly, it is incubated at 37° C. Good growth is seen after 22 hours. The flasks are combined and the product is harvested using centrifugation at approximately 3000 rpm for 30 minutes and collected in tubes. The product is resuspended in sterile PBS, pH 7.4. Density is checked using spectrophotometer enumeration and McFarland nephelometer standards. Dry weight is approximately 19.7 mg/ml. The product is diluted to approximately 2×10 9 per ml or 2 mg/ml dry weight, and 0.6% formaldehyde solution in PBS is added as a 1 :1 ratio with culture and stirred for approximately 18 hours at room temperature (22° to 24° C.) to fix cells. Thiogylcollate broth is inoculated to check for growth and pH of preparation (pH 7-7.4) is checked. The supernatant is used for WC antigen. The stock is diluted in PHS, pH 7.4 to 1 mg/ml for WC immunogen.
EXAMPLE 6: Preparation of A antigen for Immunogen
[0046] The Minca Medium is used for A antigen production. It is a standard medium for stimulating the pilii and related adherin antigens. Stock TSB Minca Medium Broth (Inf. Immun., February 1977, 676-678) is inoculated and incubated at 37° C. for 18 hours. This stimulated adhesion antigen development on the bacteria. Flasks are inoculated with Minca Medium Broth and while stirring slowing is incubated at 37° C. Good growth is seen after 18 hours. The flasks are combined and the product is harvested using centrifugation at approximately 2500 rpm for 30 minutes and collected in tubes. The pellet is resuspended in PBS and stirred with a stir bar for one hour at 22° to 24° C. (room temperature). This removes the flagella. The product is collected in tubes and the pellet is resuspended in PBS and 0.01% Tween 20™, transferred to Waring Blender in cold (4° C.) at low speed for 30 minutes. Density is checked using spectrophotometer enumeration and McFarland nephelometer standards. The product is centrifuged to remove whole cells. The supernatant is used as stock for A antigen. It may be heated at 60° C. for 40 minutes to inactivate if needed. Gentamycin is added at 50 μ/ml as preservative. Thioglycollate broth is inoculated to check for growth. Dry weight is determined at approximately 10.6 mg/ml. The product is diluted with PBS, pH 7.4 to 1 mg/ml for A immunogen.
EXAMPLE 7: Preparation of P Antigen for Immunogen
[0047] The Reinforced Clostridial Medium is used for P antigen production. It is a standard medium for stimulating adherence antigens for Peptostreptococcus anaerobius. These cultures must be grown under strict anaerobic conditions. The stock culture is grown according to ATCC for #49031. As with other organisms, subcultures are grown in small amounts. Thioglycollate Media (Difco) is inoculated with the stock and incubated for 48 hours. Flasks are inoculated with Reinforced Clostridial Medium Broth. The medium is covered with a mixture of anaerobic gas. Flasks are combined and the product is harvested using centrifugation at approximately 2500 rpm for 30 minutes, collected in tubes and run at low speed for 30 minutes. Density is checked. The product is centrifuged to remove whole cells. The supernatant is used as stock for P antigen. It is heated at 60° for 40 minutes to inactivate if needed. Dry weight is determined. Approximately 20.5 mg/ml. The product is diluted with PBS, pH 7.4 to 1 mg/ml for P immunogen.
EXAMPLE 8: Preparation of CS Antigen for Immunogen
[0048] The Reinforced Clostridial Medium is used for CS antigen production. It is a standard medium for stimulating adherence antigens for Clostridium sticklandii. These cultures must be grown under strict anaerobic conditions. The stock culture is grown according to ATCC for #12662. As with other organisms, subcultures are grown in small amounts. Thioglycollate Media (Difco) is inoculated with the stock and incubated for 48 hours. Flasks are inoculated with Reinforced Clostridial Medium Broth. The medium is covered with a mixture of anaerobic gas. Flasks are combined and the product is harvested using centrifugation at approximately 2500 rpm for 30 minutes. The product is collected in tubes and spun at low speed for 30 minutes. Density is checked using spectrophotometer enumeration and McFarland nephelometer standards. The product is centrifuged to remove whole cells. The supernatant is used as stock for CS antigen. It is heated at 60° C. for 40 minutes to inactivate if needed. Dry weight is determined at approximately 22 mg/ml. The product is diluted with PBS, pH 7.4 to 1 mg/ml for CS immunogen.
EXAMPLE 9: Preparation for CA Antigen for Immunogen
[0049] The Reinforced Clostridial Medium is used for CA antigen production. It is a standard medium for stimulating adherence antigens for Clostridium aminophilius . These cultures must be grown under strict anaerobic conditions. The stock culture is grown according to ATCC for #49906. As with other organisms, subcultures are grown in small amounts. Thioglycollate Media (Difco) is inoculated with the stock and incubated for 48 hours. Flasks are inoculated with Reinforced Clostridial Medium Broth. The medium is covered with a mixture of anaerobic gas. Flasks are combined and the product is harvested using centrifugation at approximately 2500 rpm for 30 minutes. The product is collected in tubes and spun at low speed for 30 minutes. Density is checked using spectrophotometer enumeration and McFarland nephelometer standards. The product is centrifuged to remove whole cells. The supernatant is used as stock for CA antigen. It is heated at 60° C. for 40 minutes to inactivate if needed. Dry weight is determined at approximately 20.5 mg/ml. The product is diluted with PBS, pH 7.4 to 1 mg/ml for CA immunogen.
EXAMPLE 10: Preparation of ELISA Plates Using H, O, WC and A Antigens for Monitoring Antibodies in Eggs, Chickens and Feed
[0050] H, O, WC and A ELISA: Ninety-six well assay plate (flat bottom Costar®) were coated using 100 μl/ml with various concentration of antigens (H, A, O, or WC or combination: 10 μg-200 μg/ml) in carbonate buffer, ph 9.6. Plates were incubated between 22° to 37° C. for up to 18 hours. The wells were aspirated to prevent cross-contamination. The plates were blocked with 390 μl/well of 0.5% BSA and incubated at 37° C. for 1 hour. Plates were coated using alternative rows of positive or negative for controls. Plates were rinsed one time with wash buffer containing Tween™ 20. One hundred microliters per well of diluted sample are added to wells in duplicate wells, and incubated at 37° C. for one hour. Goat anti-Chicken IgG conjugate with Horseradish peroxidase (Kirkegard and Perry Laboratories; 1:1000 to 1:3000) was added. After one hour incubation, the substrate (TMB, KPL) was added according to manufacturer's instructions and the reaction is stopped after 10 minutes with 0.1 M phosphoric acid. Optical densities of the wells were determined in Dynatech ELISA Reader at 450 nm and the information was recorded for further data analysis.
EXAMPLE 11: Analysis of Individual Eggs and Serum Over Time
[0051] Eggs were selected at various periods in the immunization period for monitoring antibody responses to the specific antigens. Selected chickens were monitored at day 0 and continued on a monthly basis after the fourth month. The whole egg was collected from the shell and then a 1 ml sample was taken. This sample was then extracted with buffer to analyze the antibody content. The standard ELISAs for the H, O, WC and A immunogens were used for analysis. The negative readings were subtracted form the OD readings. Serum samples were collected from each animal two weeks after the fourth immunogen injection.
[0052] The data given in the table below are examples of the results obtained over the first four months.
Egg Sample Date H Chicken O Chicken WC Chicken A Chicken 1 day: After first 0.03 OD Neg 0.05 OD Neg injection 1 month 0.60 OD Neg 0.05 OD Neg 5 weeks 0.74 ND ND ND 2 months 1.22 OD 1.11 OD 0.88 OD 0.79 OD 3 months 1.00 OD 1.4 OD 0.99 OD 1.4 OD 4 months 1.16 OD 1.4 OD 0.94 OD 1.22 OD Serum: 1 month 1.4 OD 0.91 OD 1.17 OD 0.97 OD
EXAMPLE 12: Preparation of ELISA Plates Using P, CS and CA Antigens for Monitoring Antibodies in Eggs, Chickens and Feed
[0053] P, CS and CA ELISA: Ninety-six well assay plate (flat bottom Costar®) were coated using 100 μl/ml with various concentrations of antigens (P, CS, CA or combination: 10 μl-200 μg/ml) in carbonate buffer, pH 9.6. Plates were incubated between 22° to 37° C. for up to 18 hours. The wells were aspirated to prevent cross-contamination. The plates were blocked with 390 μl/well of 0.5% BSA and incubated at 37° C. for one hour. Plates were coated using alternative rows of positive or negative for controls. Plates are rinsed one time with wash buffer containing Tween™ 20. One hundred microliters per well of diluted sample are added to wells in duplicate wells, and incubated at 37° C. for one hour. Goat anti-Chicken IgG conjugate with Horseradish peroxidase (Kirkegard and Perry Laboratories: 1:1000 to 1:3000) was added. After one hour incubation, the substrate (TMB, KPL) was added according to manufacturer's instructions and the reaction is stopped after 10 minutes with 0.1 M phosphoric acid. Optical densities of the wells were determined in Dynatech ELISA Reader at 450 nm and the information was recorded for further data analysis.
EXAMPLE 13: Immunization of Chicken with H Immunogen
[0054] Six selected egg laying hens, three White Leghorns and three Rhode Island Reds approximately 19 weeks old were injected with the stock H immunogen. Four injections (500 μg, 100 μg, 200 μg and 250 μg) were given one week apart. A serum sample was collected two weeks after the last initial injection. If boosters were needed, 100 jug was given in each booster (every six months). Within four weeks, four out of six hens produced excellent antibodies in the eggs. ELISA H readings averaged 1.00 OD for 1:10,000 dilution and 0.265 OD for 1:50,000. Leghorn hens did not do as well but all three Rhode Island Reds did well. After six weeks the average ELISA H reading was 1.40 OD for 1:20,000 dilution with all chickens responding.
EXAMPLE 14: Immunization of Chicken with O Immunogen
[0055] Six selected egg laying hens, six White Leghorns, approximately 19 weeks old were injected with the stock 0 Immunogen. Four injections (500 μg, 100 μg, 200 μg and 250 μg) were given one week apart. A serum sample was collected two weeks after the last initial injection. If boosters were needed, 100 μg was given in each booster (every six months). Within four weeks, five out of the six hens produced excellent antibodies in the eggs. ELISA 0 readings averaged 1.42 OD for 1:10,000 dilution and 0.68 OD for 1:50,000. After six weeks the average ELISA 0 reading was 1.15 OD for 1:20,000 dilution with still five chickens responding.
EXAMPLE 15: Immunization of Chicken with WC Immunogen
[0056] Six selected egg laying hens, six Rhode Island Reds, approximately 19 weeks old were injected with the stock WC immunogen. Four injections (500 μg, 100 μg, 200 μg and 250 μg) were given one week apart. A serum sample was collected two weeks after the last initial injection. If boosters were needed, 100 μg was given in each booster (every six months). Within four weeks, four out of the six hens produced excellent antibodies in the eggs. ELISA WC readings averaged 0.95 OD for 1:10,000 dilution and 0.250 OD for 1:50,000. After six weeks the average ELISA WC reading was 0.95 OD for 1:20,000 dilution with still five chickens responding.
EXAMPLE 16: Immunization of Chicken with A Immunogen
[0057] Six selected egg laying hens, six White Leghorns, approximately 19 weeks old were injected with the stock A immunogen. Four injections (500 μg, 100 μg, 200 μg and 250 μg) were given one week apart. A serum sample was collected two weeks after the last initial injection. If boosters were needed, 100 μg were given in each booster (every six months). Within four weeks, five out of the six hens produced excellent antibodies in the eggs. ELISA A readings averaged 1.40 OD for 1:10,000 dilution and 0.576 OD for 1:50,000. After six weeks the average ELISA A reading was 1.15 OD for 1:20,000 dilution with still all chickens responding.
EXAMPLE 17: Immunization of Chicken with P Immunogen
[0058] Six selected egg laying hens, White Leghorns, approximately 19 weeks old were injected with the stock P immunogen. Four injections (500 μg, 100 μg, 200 μg and 250 μg) were given one week apart. A serum sample was collected two weeks after the last initial injection. If boosters were needed, 100 μg were given in each booster (every six months). Within four weeks, five out of the six hens produced excellent antibodies in the eggs.
EXAMPLE 18: Immunization of Chicken with CS Immunogen
[0059] Six selected egg laying hens, White Leghorns, approximately 19 weeks old were injected with the stock CS Immunogen. Four injections (500 μg, 100 μg, 200 μg and 250 μg) were given one week apart. A serum sample was collected two weeks after the last initial injection. If boosters were needed, 100 μg was given in each booster (every six months). Within four weeks, all five out of six hens produced excellent antibodies in the eggs.
EXAMPLE 19: Immunization of Chicken with CA Immunogen
[0060] Six selected egg lay hens, Red Sex-Linked Hybrids, approximately 19 weeks old were injected with the stock CA Immunogen. Four injections (500 μg, 100 μg, 200 μg and 250 μg) were given one week apart. A serum sample was collected two weeks after the last initial injection. If boosters were needed, 100 μg was given in each booster (every six months). Within four weeks, all six hens produced excellent antibodies in the eggs.
EXAMPLE 20: Preparation of Stock Production Whole Egg Reagents
[0061] Selected hens were combined from all four immunogen groups for E. coli 0157:H7 or three immunogen groups for anaerobes, to be used to produce production batches of whole egg reagents. Sterling (U.S. Pat. No. 5,753,228) presents an excellent review of uses for the selection of eggs and storage of the same. The eggs were randomized and shell removed. The whole egg is mixed well and pasteurized using standard conditions (60° C. (140° F.) for 3.5 minutes) Charley, H. and C. Weaver, 3rd Edition, Foods: a scientific approach, Merrill-Prentice Hall, p. 350, 1998). Once pasteurized, samples were tested for activity and store at 4° C. until dried or sprayed onto carriers. Samples of 250 μl were analyzed.
[0062] Examples of results for ELISAs are given:
[0063] Pasteurized Whole Egg: E. coli 0157:H7
Immunogen Dilution O.D. WO 500 0.532 WC 2500 0.113 H 500 0.466 H 2500 0.115 O 500 0.338 O 2500 0.128 A 500 0.588 A 2500 0.155
[0064] Pasteurized Whole Egg: Anaerobes
Immunogen Dilution Batch #1 Batch #2 Batch #3 CA 100 0.339 0.275 0.627 CA 500 0.104 0.296 0.201 P 100 0.724 0.882 0.576 P 500 0.248 0.594 0.651 CS 100 0.457 0.268 0.650 CS 500 0.304 0.143 0.476
EXAMPLE 21: Coating of Feed Additive Carriers
[0065] Although whole egg can be dispensed in water supplies, or in a dried format as whole powdered egg, use of a carrier helps distribute the material in a uniform method. This makes it easier for mixing with standards feeds. A number of carriers can be used to provide a vehicle as a feed additive as needed. Soy hulls in crude, refined and pelted format, rice hulls, corn, cottonseed hulls, distilled dried grains, beet pulp or any other. The production pasteurized whole egg prep is coated onto the carrier and either fed directly to the animals or dried to 10-15% moisture. Approximately 1000 ml of whole, pasteurized egg is sprayed on 50 lbs of pelleted soybean hulls. The preferred carrier for cattle is pelleted soybean hulls while for young swine the fines from pelleted soybean hulls. The feed additive is mixed with the standard animal feed. The preferred level is 10-15 lbs of feed additive to 2000 lbs of animal feed.
EXAMPLE 22: Analysis of Feed Additive Samples After Coating with Reagents
[0066] Samples were collected from batches of feed additive after they were coated on to the carriers. The samples were analyzed and the results are as follows:
Product Name Moisture % Protein % Fat % Fiber, crude % Crude Soybean 11.59 26.76 9.10 18.63 Hulls, uncoated CAMAS EYE 12.35 25.67 8.26 19.46 0157 Crude soybean Hulls CAMAS EYE * 12.06 24.89 9.92 20.38 Control Crude Soybean hulls Soybean Pellets 11.65 9.89 2.43 33.47 uncoated CAMAS EYE 12.37 10.19 2.57 33.12 Efficiency Pellets
EXAMPLE 23: Analysis of Production Eggs Over Time— E. coli 0157:H7
[0067] Samples of the whole egg preparations were analyzed using the ELISA systems for H, O, WC and A immunogens to monitor activity over time after the initial immunization schedule was completed. Selected animals from each group were placed into the production group. The average ELISA OD readings (negative subtracted) for the fourth through the sixth months are given in the table below. The eggs were sampled using 250 μl of the whole eggs and diluted 1:500 and 1:2,500 in PBS buffer and then run in the appropriate ELISA to determine the average OD reading at each dilution. The negative control readings are subtracted from each reading. The immunogens showed different responses in animals along with good specificity. The A immunogen gave the best responses in these tests. Data for these immunogens over time is given below:
Immuogen Fourth Month Fifth Month Six Month H: 1:500 0.388 0.848 0.718 1:2500 0.085 0.237 0.195 O: 1:500 0.593 0.792 0.704 1:2500 0.147 0.294 0.184 WC: 1:500 0.398 0.730 0.578 1:2500 0.062 0.273 0.130 A: 1:500 0.700 1.014 0.909 1:2500 0.102 0.305 0.224
EXAMPLE 24: Analysis of Production Eggs Over Time—Feed Efficiency
[0068] Samples of whole egg preparations were analyzed using the ELISA systems for P, CS and CA immunogens to monitor activity over time after the initial immunization schedule was completed. Selected animals from each group were placed into the production group. The average ELISA OD readings for the fourth through the sixth months are given in the table below. The eggs were sampled using 250 μl of the whole eggs and diluted 1:500 and 1:2,500 in PBS buffer and then run in appropriate ELISA to determine the average OD reading at each dilution. The negative control readings are subtracted from each reading. The immunogens showed different responses in the animals along with good specificity.
Immuogen Fourth Month Fifth Month Six Month P: 1:500 1.182 OD 1.128 OD 0.942 OD 1:2500 0.785 OD 0.489 OD 0.343 OD CS: 1:500 0.843 OD 0.989 OD 0.582 OD 1:2500 0.318 OD 0.356 OD 0.187 OD CA: 1:500 1.156 OD 1.087 OD 0.998 OD 1:2500 0.409 OD 0.282 OD 0.507 OD
EXAMPLE 25: Analysis of Feed Additives for Antibody Activity— E. coli 0157:H7
[0069] Samples of the coated hulls were analyzed using the ELISA systems for H, O, WC and A immunogens to monitor activity after pasteurizing, spraying, drying and storage. Good antibody response was recorded after the processing of the production whole egg batches and drying on crude soybean hulls. Data for two batches is given below:
Batch: Coated WC H O A immu- Hulls Immunogen Immunogen Immunogen nogen Batch #1 1:10 0.673 OD 1.103 OD 1.105 OD 1.299 OD 1:100 0.106 OD 0.236 OD 0.229 OD 0.302 OD Batch #2 1:10 1.174 OD 1.291 OD 1.180 OD 1.224 OD 1:100 0.177 OD 0.396 OD 0.327 OD 0.458 OD
EXAMPLE 26: Analysis of Feed Additives for Antibody Activity—Feed Efficiency
[0070] Samples of the coated hulls were analyzed using the ELISA systems for P, CS and CA immunogens to monitor activity after pasteurizing, spraying, drying and storage. Good antibody response was recorded after the processing of the production whole egg batches and drying on crude soybean hulls. One gram samples of the 15 lbs of coated hulls were extracted and analyzed. Data for three batches is given in the table below:
Batch: Coated Hulls P Immunogen CS Immunogen CA Immunogen Batch #1 1:100 0.067 OD 0.289 OD 0.051 OD 1:500 0.057 OD 0.131 OD 0.037 OD Batch #2 1:100 0.028 OD 0.039 OD 0.095 OD 1:500 0.049 OD 0.015 OD 0.021 OD Batch #3 1:100 0.046 OD 0.115 OD 0.136 OD 1:500 0.012 OD 0.055 OD 0.012 OD
EXAMPLE 27: Recovery of Active Antibody and Egg Protein After Feed Mix
[0071] Bags of coated soybean refined hulls were coated with the production whole egg reagent containing anti- E. coli 0157:H7 adherence inhibitors. One bag of feed additive (15 lbs) was added to 2000 lbs of standard cattle feed. Control feed additive was produced with whole eggs from free ranging chickens. Soybean hulls were coated with this preparation and mixed as the test feed additive containing the specific antibodies. Samples of the mixed feed were collected and analyzed for active antibody to the ELISA WC immunogen as well as commercial ELISA for detecting egg protein in food (Vertatox® Quantitative Egg Allergen Test, Neogen). The data is given in the chart below for two batches of feed ration.
Mixed Feed First Batch Second Batch Test Feed-Additive: 0.172 OD 0.112 OD 1:6000 0.009 OD 0.036 1:12000 Control Feed-No 0.049 Neg. Additive 0.005 Neg. 1:6000 1:12000 Test Feed-Additive: 0.958 OD 17 ppm 1.268 OD > 20 ppm Egg Protein Control Feed-No 0.800 OD 15 ppm 1.050 OD 20 ppm Additive: Egg Protein
EXAMPLE 28: Feeding of Cattle
[0072] Two groups of cattle were fed either the E. coli 0157:H7 feed additive (coated onto refined soybean hulls) or control feed additive (coated with control eggs and no specific adherence inhibitors). The animals were fed at a rate of 15 lbs of feed additive per 2000 lbs of feed. They averaged 10 lbs per animal per day. Animals weighed approximately 1000 lbs when they started and over 1400 lbs when sent to market. All animals looked very healthy with the test animals eating more feed during the 87 days. Five of the test animals were positive during the start of the experiment for E. coli 0157:H7 and only one of the control animals. Within 30 days on feed additive all test animals were negative for E. coli 0157:H7 and stayed negative for three consecutive samples over a 30-day period. Standard protocols were followed for sampling. All animals were ear-tagged and placed in separate pens. Animals were sampled on a weekly basis for the first month and then bi-weekly after that until shipped to market. Grab samples were taken from the rectum and placed into sterile labeled bags. All samples were held on ice until processed in the lab. All samples were processed within four hours of collection each day. The fecal samples were diluted with TSB with 0.6% yeast extract. Dilutions of the mixture were streaked into Sorbitol-MacConkey's agar with or without cefixime-tellurite supplement (Dynal®). Colorless colonies are picked for further testing. A latex agglutination test was used to identify E. coli serogroup 0157 (Oxoid dry Spot™ E. coli 0157). If positive, then individual colonies were selected for further isolation on SMC agar streak plates. Isolated colonies were run on the commercial EIA for EH E. coli 0157 (Binax, NOW® EH E. coli 0157). Biochemical confirmation can be done with API-20E (Analytab Products). (Appl. Environ. Microbiol., 62(7) 2567-2570, 1966; J. Clin. Micro. 36(10): 3112, 1998.)
[0073] One of the most startling and distressing characteristics of E. coli 0157.H7 is the small number of microorganisms necessary to produce cases of human illness. By way of example, at least 10,000 of the more virulent Salmonella serotypes but as few as ten E. coli 0157:H7 are required to cause a person to become symptomatic. Therefore, one animal hosting or externally contaminated with the microorganism can, when slaughtered, affect as much as 16 tons of ground beef to the extent that a single helping of the product could result in illness if improperly prepared. Although the probability of any one animal hosting the microorganism at any one time is low, the probability of its presence in any one particular feedlot is high.
[0074] There are presently three different methods for protecting the consumer from the E. coli 0157:H7 threat which have been officially recognized. The three methods are (1) thorough cooking, (2) steam pasteurization and (3) irradiation, all of which have specific drawbacks, including human and mechanical error, cost, consumer resistance, and the like.
[0075] Any microorganism which colonizes the alimentary tract of its host must possess the capability of sticking or adhering to that surface in order to multiply. E. coli 0157:H7 is no exception to this rule. The adherence inhibitor of this invention strongly interferes with adherence and, on a cumulative basis, thereby prevents the specific targeted microorganism from colonizing and multiplying. Through the vehicle of a simple daily feed additive, the product essentially supplies the host with a specific antibody preparation designed not to cure any disease in the animal (cattle are essentially unaffected by E. coli 0157.H7 being only transitory hosts) but merely to dislodge any resident bacteria and to prevent the attachment of any newly introduced bacteria in the alimentary tract. The adherence inhibitor has no direct effect on the host itself, leaves absolutely no undesirable residue in the animals and thus has no effect whatsoever on the ultimate food products. In addition, since the microorganism is prevented from multiplying, it will over time (for example the 120 day finishing period in the feedlot) disappear through natural degradation from the mud and manure coating the animal, eliminating this significant potential source of contamination at slaughter. Properly managed, the risk of cross contaminating other food sources through feedlot runoff or by the application of manure as fertilizer is also essentially eliminated.
[0076] It is apparent that many modifications and variations of this invention as hereinbefore set forth may be made without departing from the spirit and scope thereof. The specific embodiments described are given by way of example only and the invention is limited only by the terms of the appended claims. | A microbial adherence inhibitor in the form of fowl egg antibodies is disclosed, along with the method of making it and methods of using it. The inhibitor functions by substantially preventing the attachment or adherence of colony-forming immunogens in the rumen and intestinal tracts of host food animals. The inhibitor is made by inoculating female birds with the immunogen, harvesting the eggs which contain antibodies to the immunogen, harvesting the eggs which contain antibodies to the immunogen, drying the egg contents and adding to the feed or water for the host animals. Dependent upon the particular immunogen with which the female bird is inoculated, the egg antibody is used to promote the growth of food animals by improving feed conversion rates by decreasing the waste of dietary protein caused by the presence of certain colony-forming organisms in the animals, and to substantially reduce or eliminate the incidence of illnesses caused by the presence of certain illness-causing colony-forming immunogens, such as E. coli 0157:H7, in meat from food animals, and in other food stuffs. | 2 |
CROSS-REFERENCE TO RELATE APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional applications: No. 62/115,684, filed Feb. 13, 2015; No. 62/240,323, filed Oct. 12, 2015; and No. 62/262,814, filed Dec. 3, 2015. This invention relates to a device for dispensing either spray drops or foam.
BACKGROUND OF THE INVENTION
[0002] The prior art contains many dispensers that dispense liquid drops or foams or both. For many uses, liquid drop sprayers can be useful. Drop spray technology can handle a wide variety of materials including liquid solutions, colloids, suspensions, and emulsions. Solutions can have water or oils of varying grades as the solvent. This makes drop sprayers very versatile.
[0003] Different spray nozzles can emit drops that form well-defined patterns. Those patterns can include, for example, a solid stream, fan-shape, cone, hollow cone, multiple plume. Conventional spray nozzles can come in different spray angles, typically ranging from 15 to 150 degrees of “theoretical coverage.” Drop sizes can also be controlled fairly well, at least at the point where they exit the nozzle. Sizes can range from extremely fine (less than 60 microns) to ultra coarse (greater than 650 microns). Air can be introduced into the nozzle with air induction to change the nature of the drops.
[0004] For dispensing, conventional sprayers can have disadvantages. One big disadvantage of a spray is that much of the dispensed fluid may not reach the target. This may happen for a number of reasons. Many conventional systems operate under high pressure. High pressure can create more fine drops. The finest drops of some liquids may vaporize during dispensing. Vapors will not likely reach a target because the operator of the sprayer cannot control their path. Vapors can move hundreds of meters off-site under certain conditions outdoors. This can lead to harm to beneficial plants and pose risks to humans and animals. Indoors, vapors can remain suspended for long periods of time. This can cause problems such as health concerns for humans and animals.
[0005] Even slightly larger fine drops can move meters in a relatively light wind or current outdoors. Drops dispensed indoors from conventional sprayers may be less susceptible to airborne movement. However, because of the confined space, people, animals, and plants in the vicinity may risk greater exposure from off-target movement. This exposure may have negative effects.
[0006] If spray drops do reach the target, not all of them will be effective. The smaller drops on a surface can dry quickly, especially in open sun or on warm surfaces. One example is cleaners sprayed on a non-absorbent surface such as a window, a smooth countertop, or a motor vehicle's body. If drops dry too quickly, the advantages of having that cleaner in liquid form is then largely lost. Re-wetting may be necessary. Streaking or even abrasion can result from use of a rag or other wiping implement. Undesirable residues of cleaner may be left on the surface.
[0007] Spray patterns from conventional sprayers can also be very uneven—coarse drops are often at the center and finer drops at the periphery of the spray pattern. This is especially noticeable when treating or cleaning absorbent materials such as fabric. The fine drops may dry quickly on the surface of the fabric, thereby becoming largely ineffective; the coarse drops may soak in. This inconsistency can require repeated spraying. Oftentimes, what results are patches of soaked and dry fabric.
[0008] Then, there are drops that reach the target and then leave. Large drops may contact the target surface and bounce, roll, or drip off. Drops moving at higher velocities may bounce or splatter. Even when conditions may seem right, a spray under moderate pressure and a target that is relatively absorbent—a large drop can move before it has time to start soaking.
[0009] Still another problem with fine sprays from conventional sprayers is that they can often be very hard to see—either when being dispensed or when they are on a surface. Thus, a person may not realize how much of the spray is volatilizing or moving off-target. Even on the target surface, it can be difficult to notice where there is over-coverage or under-coverage.
[0010] In short, there are numerous ways a dispensed drop from a conventional sprayer can miss its target. Moreover, even when that drop hits the target, the drop may be in an ineffective form—too dry; too fine; too heavy, etc. If this happens, economic, health, and environmental harm can result.
[0011] One way to solve many of the problems associated with conventional sprayers is to improve the quality of the spray. There can be several solutions: A first is dispensing drops that are not so fine. The slightly larger drops will be less likely to drift or quickly dry on the target surface. A second is dispensing drops at lower velocity. Lower velocity can reduce the likelihood that drops will break apart into small drops during delivery. Lower velocity also lessens the chance that drops will bounce off a target surface. A third is dispensing drops that are consistently sized. Drops of a consistent size can allow the spray operator to make consistent adjustments. For example, If finer drops are being produced but they are a consistent size, the spray nozzle can be brought closer to the target surface to minimize volatilization.
[0012] Foams can also help solve many of the problems associated with off-site movement, overspray, and coverage inconsistencies associated with dispensed chemicals. First, foams can evaporate and dry slower than liquids. This can be the case both in transit from the dispenser to the target and when the foam reaches the target. This has advantages both in reducing vaporization but also in keeping the active ingredients moist so they can do their work.
[0013] Second, foams can be a highly precise way to make an application. Foams can be highly effective when they are wiped or dabbed onto a surface. This can allow for very precise applications to very small targets. Third, a foam can be easily applied and then spread on a surface with a wiping implement such as a mop or rag, for example. Fourth, foams can cling tenaciously to surfaces, even to vertical and very slippery ones.
[0014] Fifth, foam can absorb shocks or blows very well in comparisons to liquids. This means that foam can be projected at a surface and not as easily bounce off it as spray drops. Thus, when foam hits a surface even at fairly high pressure, the foam tends to stay in place and even help cushion incoming foam. Sixth, foams can act as insulators and barriers—this is especially important in activities such as firefighting.
[0015] Seventh, foams remain highly visible, both when streaming from a nozzle and when adhering to an object. This makes it easier for the operator to observe over-coverage or under-coverage. Eighth, the characteristics of foams can be adjusted—from very wet foams to drier foams. This makes them highly flexible. A wetter foam has more weight and can generally be projected greater distances; it can hold more active ingredient. Dry foams are extremely light and can maintain their foam structure for long periods of time and can provide greater insulation. For these and many other reasons as discussed below, foams can be very useful.
[0016] The purpose of the present invention is to overcome limitations of prior art dispensing systems.
BRIEF SUMMARY OF THE INVENTION
[0017] This invention relates to a device for dispensing spray drops or foam. In one example, the dispenser can be powered with a battery and dispense at low pressure. The figures and descriptions that follow help describe aspects of the invention.
[0018] A first illustrative example of the invention is an electrically powered dispenser comprising: a pressurization system for automatically regulating a pressure level of a gas in a pressurizable space, the pressurization system being configured: to take a pressure reading of the gas, to make a determination if the pressure reading indicates a deviation from a desired pressure level, and based on the determination to make a decision selected from a list comprising at least the following: to start pressurization, to continue pressurization, to stop pressurization, or to do nothing.
[0019] In this first example, the decision to start pressurization is made if the pressure reading indicates the deviation, the deviation is below the desired pressure level, and pressurization is not ongoing; the decision to continue pressurization is made if the pressure reading indicates the deviation, the deviation is below the desired pressure level, and pressurization is ongoing; the decision to stop pressurization is made if the pressure reading does not indicate the deviation and pressurization is ongoing; and the decision to do nothing is made if the pressure reading does not indicate the deviation and pressurization is not ongoing.
[0020] According to variations or refinements to this first example, the list could be configured to have additional items: For example: the list can further comprise the decision to increase the rate of pressurization if the determination is that the pressure reading is below the desired pressure level and the deviation is significant.
[0021] The list can further comprise the decision to increase the rate of pressurization if the determination is that the pressure reading is below the desired pressure level and the deviation is significant. Significance of the deviation can depend on the size of the tank. For most human-carried systems, a deviation of 2 or 4 psi or greater can be considered significant. For larger ones, a deviation of more than 4 psi can be considered significant.
[0022] According to variations or refinements of this first example the pressurization system is sufficiently sensitive to indicate the deviation even if the deviation is minimal. Minimal can be, for example, between 0.1 and 1.0 psi; between 0.1 and 0.5 psi; or between 0.1 and 0.3 psi. Although not preferable, the pressurization system could be configured to sense only moderate deviations, for example, ones greater than 1.0 psi.
[0023] According to other variations or refinements of this first example, the desired pressure level can be, e.g., less than 40 psi; less than 30 psi; less than 20 psi; less than 15 psi; less than 10 psi; less than 8 psi; less than 5 psi; or less than 2.5 psi. Based on current nozzle tip technology, it is preferable for many uses to have the desired pressure level set lower than 15 psi or even 10 psi, in order to avoid excessive drift and off-target spray.
[0024] According to other variation or refinements of this first example, the desired pressure level is selectable, for example, by an operator. It can be selectable from at least 2 selectable pressure levels. It can also be selectable from at least 5, 10, 15, 20, or more pressure levels. The desired pressure is selectable, for example, by an operator using a manual adjustment mechanism. If the pressure level is selectable, It is also preferable to have a range of selectable pressure levels: e.g., selectable from at least 2 selectable pressure levels with at least one of those selectable pressure levels being less than 20 psi; less than 15 psi; less than 10 psi; less than 8 psi; or less than 5 psi.
[0025] According to other variations or refinements of this first example, one of the decisions that can be included in the list of decisions made by the pressurization system is to depressurize the pressurizable space. This decision is made if the pressure reading indicates the deviation, and the deviation is above the desired pressure level. Another decision included in the list can be the decision to depressurize if the electric dispenser system is turned off or if the electric dispenser has not operated for a specified period of time, such as 2, 4, 6, or 10 minutes.
[0026] According to other variations or refinements of this first example, another decision that can be included in the list of decisions made by the pressurization system is to increase the rate of pressurization. This decision is made if the pressure reading is below the desired pressure level, and the deviation is significant. Significant deviation can be, e.g., a deviation of 2 psi or greater; a deviation of 3 psi or great; or a deviation of 4 psi or greater.
[0027] According to other variations or refinements of this first example, the dispenser further comprises an outlet assembly for ejecting spray drops or the dispenser further comprises an outlet assembly for ejecting foam.
[0028] According other variations or refinements of this first example, the dispenser further comprises a supply tank further comprising a headspace, wherein the headspace forms at least a part of the pressurizable space. In other variations, a sampling tube forms or an air supply tube forms at least a part of the pressurizable space.
[0029] A second illustrative example of the invention is an electrically powered dispenser, comprising: a pressurization system for automatically regulating pressure in a pressurizable space, the pressurization system being configured to regulate pressure in the pressurizable space to achieve a desired a pressure level wherein the desired pressure level is 10 psi or less.
[0030] According to variations or refinements of this second example, the desired pressure level can be, e.g., 8 psi or less; 7 psi or less, 5 psi or less; or 2.5 psi or less.
[0031] A third illustrative example of the invention is an electrically powered dispenser, comprising: a supply tank, the supply tank further comprising a top with an opening for filling the supply tank; a reusable closure for sealing the opening; and a pressurizable space created when the reusable closure seals the opening; wherein the closure contains a pressurization system for automatically regulating a pressure level to seek a desired pressure level in the pressurizable space.
[0032] According to variations or refinements of this third example, the closure is an external closure on the supply tank; the external closure is a cap with a belly hanging within an interior of the cap, a skirt having a lower rim, wherein the belly is recessed within the interior in comparison to at least a portion of the lower rim.
[0033] According to variations or refinements of this third example: wherein the closure is an internal closure on the supply tank; wherein the structure of the closure is cylindrical and, when forming a seal on the supply tank, the closure shares a vertical axis with a cylindrically shaped supply tank.
[0034] A fourth illustrative example of the invention is an electrically powered dispenser, comprising: a pressurization system for automatically regulating pressure in a pressurizable space at a desired a pressure level wherein at least a portion of the pressurization system is located remotely from the supply tank.
[0035] According to variations or refinements of this fourth example: the remote portion of the pressurization system is an air pump. The air pump can be connected to the supply tank with an air supply tube. In another variation the remote portion is a sensing system. The sensing system can be connected to the supply tank with a sampling tube. The remote portion can be a control panel. The control panel can be electronically linked to a pump head mounted on the supply tank.
[0036] According to variations or refinements of this fourth example, the remote portion of the pressurization system is located remotely from the supply in a first and second remote location, wherein the pump head is located remotely from the supply tank in a first remote location and a control panel is located remotely from the supply tank in a second remote location.
[0037] The examples, variations, and refinements mentioned above can be combined in ways other than those stated. Other examples, variations, and refinements are explained below.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0038] FIG. 1A is a side view of an electrically powered pressurized tank dispenser.
[0039] FIG. 1B is a side view of the outlet assembly.
[0040] FIG. 2A is a side view of an electric pressurized tank dispenser with a wand.
[0041] FIG. 2B is a diagram showing three systems: a pressurization system; a pressurized fluid storage system; and an output system.
[0042] FIG. 2C is a schematic of an electrical system for the dispenser.
[0043] FIG. 2D is a side view of a pump head for the dispenser.
[0044] FIG. 2E is a top view of a pump head for the dispenser.
[0045] FIG. 2F is a side view of internal components of a pressurization system for the dispenser.
[0046] FIG. 2G is a side view of an outlet assembly.
[0047] FIG. 3A is a side view of an electrically powered pressurized tank dispenser with a conventional dip tube and nozzle.
[0048] FIG. 3B is a side view of an electrically powered pressurized tank dispenser for spraying liquid drops with a shoulder strap.
[0049] FIG. 4A is a side view of an electrically powered pressurized tank dispenser mounted in a backpack frame.
[0050] FIG. 4B is a front view of an electrically powered pressurized tank dispenser mounted in a backpack frame.
[0051] FIG. 5A is a side view of an electrically powered pressurized tank dispenser mounted on a cart.
[0052] FIG. 6A is an internal view of the components of the pump head for an electrically powered pressurized tank dispenser.
[0053] FIG. 6B is a top view of the pump head of an electrically powered pressurized tank dispenser.
[0054] FIG. 7A is a side view of an electrically powered pressurized tank dispenser with a wand with threads the supply tank shown in dashed line.
[0055] FIG. 7B is a side, sectional view of the housing of the pump head and the cover.
[0056] FIG. 8A is a side view of a vehicle with an electrically powered pressurized tank dispenser mounted on it.
DETAILED DESCRIPTION
[0057] FIGS. 1A and 1B show an electrically powered pressurized tank fluid dispenser 100 . The dispenser 100 can be especially suited to dispensing foam. The dispenser 100 might typically be carried in the hand by an operator and used for dispensing fluids for cleaning, treating, coating, etc.
[0058] The dispenser can include a supply tank 101 , a pump head 102 , and an outlet assembly 103 . The supply tank 101 can be of varying sizes. For many uses, a handheld dispenser 100 such as the one shown can contain about 250 ml to 3 liters. The tank 101 can be filled by unscrewing the pump head and filling the tank with a liquid 111 such as a solution.
[0059] The pump head 102 can include a pressurization system 106 to pressurize the tank 101 . The pressurization system 106 can have a control unit, a power source, a motor, and a pressurizer. (Most of the components of the pressurization system are not separately shown.) The control unit can control the pressurization system 106 and incorporate sensing units such as a pressure sensor 116 .
[0060] The power source is preferably a portable one such as a battery cell. The battery can be rechargeable. FIG. 1A shows a port 115 for a charging connector. The motor can drive the pressurizer. The pressurizer can be an air pump. FIG. 1A shows an inlet for the pressurizer 107 a for drawing in ambient air and an outlet 107 b for introducing pressurized air into the supply tank 101 , preferably into the headspace 108 .
[0061] The outlet assembly 103 in this example can be affixed to the pump head 102 . The outlet assembly 103 can include a mixing chamber 104 for creating or conditioning a foam fluid and a nozzle 126 . Opposite the outlet assembly 103 is a handle 105 for holding the dispenser 100 .
[0062] The dip tube 109 of the present invention can be a tube of a pliable material such as polyethylene with a vent 110 . The vent 110 in this example is a hole made in a splicer 112 which connects two sections 113 a , 113 b of the dip tube 109 . In operation, as liquid 111 under headspace 108 pressurization is forced into the dip tube 109 , the vent 110 can introduce a quantity of that air from the headspace 108 into the fluid stream 119 . The vent 110 can preferably be positioned so it can remain above the liquid 111 , i.e., in the headspace 108 , during dispenser 100 operation in order to prevent the liquid 111 in the supply tank 101 from blocking the entry of headspace 108 air into the vent 110 .
[0063] The dip tube 109 and splicer 112 can have an inside diameter of approximately 2 to 10 mm depending on various factors such as pressure, the volume of liquid 111 desired to be dispensed, and the size of the dispenser 100 .
[0064] For most hand carried dispensers such as this one, the vent 110 can be a very small opening into the splicer 112 —e.g., the vent 110 can be a hole with a diameter between approximately 0.3 mm and 2 mm and more preferably between 0.6 mm and 1.5 mm and even more preferably between 0.7 mm and 1.3 mm.
[0065] The dispenser 100 can be activated with a switch such as an on-off button 117 . Depressing the button 117 can do two things. First, it can activate the controller which can turn on the pressure sensor 116 . If the sensor 116 detects that pressure in the system is too low, the controller can activate the motor to increase pressurization in the head space 108 . Once pressure reaches a desired level, and assuming the operator still has the button 117 in the “on” position, the controller can open a check valve 118 causing liquid to be drawn into the dip tube 109 creating a fluid stream 119 flowing up the dip tube. As the fluid stream 119 passes through the splicer 112 , air from the headspace 108 can be drawn through the vent 110 into the dip tube 109 and mixed with the liquid 119 . This can create a fluid stream 119 with some bubbles (probably of varying sizes and quality). The fluid stream 119 can eventually pass through the check valve 118 and enter the mixing chamber 104 .
[0066] The mixing chamber 104 can be attached to the pump head in various ways such as by a threaded connection 125 . The mixing chamber 104 can have a tubular shape with a void 120 into which a cartridge 121 can be inserted as shown in FIGS. 1A and 1B . Preferably, the cartridge 121 can also be tubular and translucent or clear so that its contents can be viewed.
[0067] The cartridge 121 can contain a mixing media 122 such as stainless steel wool. The cartridge 121 can be from about 0.2 to 20 cm in length for many applications; and more preferably from about 1 to 10 cm; and still more preferably from about 2 to 7 cm. The diameter can be from about 0.2 to 5 cm for many uses and more preferably from 0.5 to 2. The cartridge 121 should preferably fit snugly in the void 120 . Different cartridge dimensions and mixing media could be appropriate for dispensers of different sizes and kinds. Alternative or additional mixing media could be screens, steel wool, reticulated foams, and so forth.
[0068] A mesh screen 123 a can enclose the proximate end and another mesh screen 123 b the distal end of the cartridge 121 . The screens 123 a , 123 b can be made of a variety of materials, e.g., wire cloth, plastic. A 304 Stainless Steel Wire Cloth Disc, 60×60 Mesh can be used for both the proximate and distal screens 123 a , 123 b.
[0069] The cartridge 121 can be held within the mixing chamber 104 by a retainer 124 —in this instance the retainer 124 is an O-ring. The retainer 124 and cartridge 121 should fit to help ensure that excessive fluid 119 does not bypass treatment by the mixing media 122 inside the cartridge 121 .
[0070] During operation, when the fluid stream reaches the mixing chamber 104 , it can be conditioned by the mixing media 122 . After conditioning in the mixing chamber 104 , the foam fluid can travel through the nozzle 126 which can resemble a compression fitting. The nozzle 126 can include a tubular shaped orifice 129 . The orifice can be approximately 0.1 to 2 cm in diameter and approximately 4 to 5 cm long.
[0071] The dispenser can function under very low pressures and still generate and dispense high quality foam. Table 1 shows pressure ranges that the dispenser could work at. These are ranked in order of preferability.
[0000]
TABLE 1
Pressure - Low End
Pressure - High End
preferability
mbar
psi
mbar
psi
preferable
7
0.1
2070
30
more preferable
14
0.2
1400
20
still more preferable
14
0.2
690
10
most preferable
14
0.2
670
under 10
[0072] Operating the dispenser at the lower pressure range, e.g., under 670 mbar or under 10 psi can be most preferable for many reasons. These include: the lower pressure range can require less power. Components such as the power source and motor can be more compact and lighter. The tank, fittings, etc., can be less robust, and pressure can be maintained more easily in the supply tank. All of these can reduce design and production costs. Lower pressure can be also be safer for users because lower pressure reduces the potential for tank bursts, leakage, and misdirection of high energy chemical streams. Moreover, lower pressure can be useful for the operator in doing cleaning, treating, coating, and so forth.
[0073] The controller can incorporate an adjustment mechanism so that the pressurization level can be adjusted. For instance, an adjustment mechanism such as a dial 128 with settings could be turned to select a pressure level, ranging from 1 to 3. Selecting level “One” could have the controller stop the motor when the sensor 116 indicates 200 mbar (2.9 psi); level “Two” when the sensor 116 indicates 400 mbar (5.8 psi); and level “Three” when the sensor 116 indicates 600 mbar (8.7 psi). (In another embodiment, the on-off button could incorporate the adjustment mechanism—light finger force on the button could select level 1 ; more force level 2 ; and still greater force level 3 .
[0074] Dispensing foam at level One, i.e., a maximum pressure of 200 mbar (2.9 psi) can be useful for dispensing relatively small amounts of foam or for dispensing with greater precision. Small, precise applications can be especially useful for treating small targets, e.g., cleaner to a small stain; herbicide to an isolated weed; ointment to a wound; soap or beauty care products to the hand or other parts of the body, and so forth. Such applications can virtually eliminate off-target movement of the applied foam material.
[0075] In addition to spot treatments, foam can be applied to large surfaces at this low setting. Because the dispenser is driven by a motor, a continuous stream of high quality foam could be dispensed for many minutes with limited volatilization. This could be useful for cleaning countertops, windows, etc.
[0076] The foam could be applied at close range—e.g., within a couple inches of a surface such as a countertop—or dispensed and allowed to fall onto the target surface for example dispensing foam cleaner on a floor. A sponge, a mop, other wiper could then be used to wipe the dispensed product on the surface.
[0077] Dispensing foam at level Two, i.e., a maximum pressure of 400 mbar (5.8 psi) can be useful for dispensing greater amounts of foam for spot treatments or for directing a foam stream at a surface. Level Two might be useful for directing a foam stream at a window at close range or to the fabric on a chair or sofa for cleaning or treating.
[0078] Dispensing foam at level Three, i.e., a maximum pressure of 600 mbar (8.7 psi) can be useful for directing a foam stream a greater distances. This setting could be used for applying foam soap at a vehicle or hitting a patch of weeds.
[0079] FIGS. 2A to 2G show an electrically powered pressurized tank dispenser 200 . The dispenser 200 shown in FIG. 2A can resemble the example shown in FIGS. 1A and 1B . Like dispenser 100 , dispenser 200 can have a supply tank 201 , a pump head 202 , and an outlet assembly 203 . However, dispenser 200 can also have a hose 234 and wand 235 . The tank 201 shown in FIG. 2A is also larger about 8 L or about 2.1 gallons and generally resembles the tank accompanying tank sprayer, Model #90162, Super Sprayer® available from H.D. Hudson Manufacturing Company of Chicago, Ill.
[0080] As shown in FIG. 2B , the dispenser 200 can be grouped into three systems: a pressurization system 204 ; a pressurized fluid storage system 205 ; and an output system 206 . The pressurization system 204 can pressurize the fluid storage system 205 . The output system 206 can withdraw the fluid from the storage system 205 , condition it, and dispense the conditioned fluid, for instance, as a liquid spray or a foam.
[0081] The pressurization system 204 in this example has electronic components and can be located primarily in the pump head 202 as shown in FIG. 2F . The pump head housing 208 can enclose most of the pressurization system 204 . The housing 208 can have an air inlet 209 (e.g., a hole in the wall of the housing 208 ) for entry of ambient air into the housing 208 . The pressurization system 204 can include an air pump motor 210 with an air intake 211 (for drawing air from inside the housing 208 into the motor 210 ) connected to a pressurized air tube 212 for transferring pressurized air from the motor 210 to the supply tank 201 ; and a sampling tube 213 that branches off the pressurized air tube 212 and connects to a controller 214 for purposes of sampling the pressurized air in the tank 201 . (The described connection of the pressurized air tube 212 and the sampling tube 213 to headspace 224 mean that those parts, like the headspace, can also be considered to be pressurized and part of a “pressurizable space” in the dispenser 200 that can be used to “push” a liquid or foam, for example, from the dispenser 200 .
[0082] FIG. 2C shows the schematic for the electronic components of the pressurization system 204 . The electronic components include: the air pump motor 210 ; the controller 214 including a voltage regulator 215 , a MOSFET 216 , a sensor (transducer) 217 , a comparator 218 , a diode 219 ; an on-off switch 240 ; an adjustment mechanism (potentiometer) 241 ; a battery 242 ; and a fuse 244 . The battery 242 can be rechargeable with a charging port 243 .
[0083] As with the pump head 102 shown in FIG. 1A , the pump head 202 can fit on the top of the tank 201 . The pump head 202 can have a handle 220 . The lower portion of the pump head 202 includes a threaded male plug 221 with a compressible washer or O-ring 222 . The threaded male plug 221 can fit into a threaded hole 223 in the top part of the tank 201 and create an airtight seal. At the lower end of the plug 221 can be the distal end of the pressurized air tube 212 for introducing air created by the pressurization system 204 into the supply tank 201 , preferably into the headspace 224 . In this way, the pump head 202 can replace the manual pump (not shown) that accompanies a tank sprayer such as Model #90182.
[0084] Many tanks such as the one shown in FIG. 2A have a cup or shroud at the top, often referred to as a “funnel top.” The Hudson tank sprayer, Model #90182 has such a funnel top 225 . The lower portion of the pump head housing 208 can fit down into the funnel top 225 . This can have advantages. By fitting portions of the pump head housing 208 down into the funnel top 225 , the weight of the pump head 202 can be lowered relative to the tank 201 . Moreover, having the pump head 202 cover the funnel top 225 lessens the amount of debris that can collect in the funnel top 225 . Having debris in the funnel top 225 can be inconvenient because it often has to be cleaned out before the tank 201 is refilled. To further limit the entry of debris into the funnel top 225 , the housing 208 can have a lip 226 that overhangs the funnel top.
[0085] An additional advantage of this configuration of the pump head 202 and funnel top 225 has to do with the air inlet 209 . As can be seen from FIGS. 2A and 2F , the air inlet 209 is located on the underside of the pump head 202 and is enclosed by portions of the pump head 202 and funnel top 225 . This location can help protect the air inlet 209 from ingress of dust or debris. The housing lip 226 can further protect the inlet 209 . However, in this example of the dispenser 200 , the pump head 202 should preferably not fit too tightly onto the tank 201 ; otherwise, the flow of ambient air to the air inlet 209 could be restricted.
[0086] There is not a universally accepted system for connecting a pump head to a tank in prior art tank sprayers. Many tank sprayers, especially those with a funnel tops, have a threaded plug like Model #90182. However, others have a threaded cap that fits on a tank that resembles the tank 101 of the handheld tank sprayer 100 shown in FIG. 1A . The pump head 202 can be adapted to fit on different kinds of tanks used with tank sprayers.
[0087] In addition to the pressurization and storage systems, the dispenser 200 can have an output system 206 as depicted in FIG. 2B . The output system 206 can draw a pressurized fluid from the supply tank 201 , condition it, and discharge it from the nozzle 237 . The output system 206 can resemble aspects of the one shown in FIG. 1A . The output system 206 can include a dip tube 227 , a splicer 228 with a vent 229 , a check (or discharge) valve 230 , and the outlet assembly 203 .
[0088] The dip tube 227 in this example can be made of two pieces of tubing each with an ID of approximately 3 mm. Each can attach to the splicer 228 . The splicer 228 can have an ID of approximately 2.3 mm. The splicer vent 229 can have an ID of about 0.9 mm.
[0089] The dip tube 227 can be connected to a tank fitting 232 attached to the wall of the tank 201 . See FIG. 2A . A reducer 233 can be used to attach the dip tube 227 to the tank fitting 232 that accompanies Model #90182. The output system 206 continues with a hose 234 attached to a wand 235 . The hose 234 and wand 235 available with Model #90182 can be suitable. The check valve 230 can be the same check valve 230 installed in the wand handle 246 of the wand 235 that accompanies Model #90182.
[0090] The outlet assembly 203 can generally be the same as the one shown in FIGS. 1A and 1B . It can have a mixing chamber 236 and nozzle 237 and dispense a foam. The nozzle 237 shown in FIG. 2G is slightly different from nozzle 126 : it can have two orifices 238 a , 238 b , each with an ID of about 2 mm. The orifices 238 a , 238 b , shown can be slightly angled away from each other on the output (distal) end to help prevent the streams of foam from colliding. In addition, the nozzle 237 can be secured to a male threaded distal end 250 of the mixing chamber 236 with a flareless fitting 239 . In constructing a prototype, the inventors used the following flareless fitting 239 , Nut for ½ in. Tube OD Easy-Align Brass Compression Tube Fitting available from McMaster Carr, located in Illinois, U.S.A. As with mixing chamber 104 shown in FIG. 1B , mixing chamber 236 can have a cartridge 248 with mixing media held in place by a retainer O-ring 249 . The threaded fitting 251 on the proximate end of the mixing chamber 236 can attach to the distal end of the wand tube 252 .
[0091] An operator can deploy the dispenser 200 as follows: the on-off switch 240 can be switched on. This can activate the controller 214 which can turn on the pressure sensor 217 . If the sensor 217 detects that pressure in the system is below a set pressure, the controller 214 can activate the motor 210 to increase pressurization in the head space 224 until the set pressure is reached. The set pressure is determined by the adjustment mechanism 241 . In this example, the adjustment mechanism 241 can be a knob that allows “infinite adjustability”—turning the knob clockwise can increase the set pressure; turning the knob counterclockwise can decrease the set pressure.
[0092] Once the set pressure is reached, the controller 214 can turn the motor 210 off. Typically, when starting a job, the operator might set the pressure with the adjustment mechanism 241 and then turn the switch 240 on to allow the pump system to reach the set pressure. To discharge foam, from the outlet assembly 203 , the operator can squeeze the lever 245 on the wand handle 246 to open the check valve 230 . With the check valve 230 open, fluid 244 can be drawn into the dip tube 227 creating a fluid stream flowing up the dip tube 227 . The fluid can be conditioned in the supply line and discharged as a foam out the nozzle 237 .
[0093] The inventors built and tested a prototype dispenser configured generally like dispenser 200 shown in FIGS. 2A to 2G . In addition to parts from the Hudson tank sprayer, Model #90182, and other parts listed above, the inventors used: an air pump motor, Model #T.1C48G2.1C 48N2.B12V, from Parker Hannefin. The pressure sensor 217 was a transducer with a stated maximum of 14.5 psi from Freescale Semi Conductor, Mfg, Part #MPX5100GP, purchased from DigiKey.
[0094] To test the prototype, the inventors mixed a solution and added it to the tank of the prototype. The solution contained tap water and 0.08% by volume of Jarfactant™ 225DK, available from Jarchem Industries, Inc., of Newark, N.J. With the adjustment mechanism 241 turned to maximum power, the system could eject streams of foam that generally broke into an even spray pattern of foam clusters or globs with a distance of approximately 7 to 12 feet. With maximum power the tank could maintain a pressure of about 6 psi with the dispenser in continuous operation.
[0095] Another example of the invention is shown in FIG. 3A . In this example, the dispenser 300 is configured as a system that can be preferable for spraying water (or other liquid) drops instead of foam. In this example, the pump head 302 can be the same as the one shown in FIGS. 2A and 2D to 2F , and can replace the manual pump head that accompanies Model #90182. The system can then function as an ultra low pressure sprayer.
[0096] The inventors tried out a dispenser configured generally like dispenser 300 a shown in FIG. 3A . The dip tube 327 had an ID of approximately 3 mm. The outlet assembly 303 had no mixing chamber but instead resembled an outlet assembly typical for most tank sprayers. The nozzle 337 used was a Tee Jet Nozzle, #8001 EVS. This is called an “Even Flat Spray Nozzle.” The resulting spray pattern appeared to be very even and had very few large- or uneven-size droplets, despite the fact that the pressurization system was producing pressure of only about 6 psi.
[0097] FIG. 3B shows another example, electric dispenser 300 a . The only major difference from the dispenser 300 shown in FIG. 3A is the attached shoulder strap 363 .
[0098] An electric dispenser prototype resembling dispenser 300 a was used in the field to do herbicide spraying in November of 2015. The prototype incorporated all of the original parts of the Hudson Model #90182 including the dip tube and wand. The only alteration was that the manual pump was replaced with the electric pump head 302 . Two different glyphosate herbicide solutions were used. The first tank solution contained approximately 10% Super Concentrate Killzall II Herbicide manufactured by Hi-Yield of Bonham, Tex., USA. (This herbicide has one or more surfactants and likely has anti-foaming agents included in the manufacturer's formulation.) The second spray solution contained approximately 8% Killzall Aquatic Herbicide, also from Hi Yield. This herbicide formulation contains no surfactant. Therefore, approximately 1% of a surfactant, Jarfactant™ 225DK, available from Jarchem Industries, Inc., of Newark, N.J., was added. This second spray solution contained no anti-foaming agent. Both solutions were at the maximum recommended label herbicide rate for foliar spot treatments. Both solutions included a marker colorant so that spray deposition could more easily be examined.
[0099] The blue nozzle tip that accompanied Model #90162 was used. (Although it had no markings, from a visual check, it appeared that the blue nozzle was a fan nozzle with an orifice size somewhat larger than the TeeJet® 8001 EVS. The knob was turned to approximately halfway, estimated to produce approximately 5 to 6 psi. The target weeds included Canada thistle ( Cirsium arvense ), bull thistle rosettes ( Cirsium vulgare ) and common mullein ( Verbascum thapsus ).
[0100] The coverage on the leaves of the weeds with the first spray solution was very even, and there was minimal beading on or dripping from the leaves. When the wand was passed once over a target plant, very distinct borders on the spray band could be observed. Coverage on lower leaves was good indicating that the spray could penetrate into the canopy of the weeds. The second spray solution with the added surfactant (and no anti-foaming agent) performed well. Foaming was minimal even though the mixture contained a surfactant and no anti-foaming agent. Coverage was still excellent.
[0101] What was also noteworthy in this field work was that in over two hours of spot spraying, the prototype electric dispenser maintained very constant pressures and consistent performance. The operator barely noticed engagement of the pump motor, suggesting that the electric pump easily handled the task of maintaining the appropriate pressure.
[0102] In another informal test under more controlled conditions indoors, the effects of tank pressure on spray drop quality was explored. To help understand this better, colored water was sprayed onto white paper at various pressure levels using the prototype electric dispenser resembling dispenser 300 a . For comparison purposes, in some of the tests, the manual pump for the Hudson Model #90162 was used. The pressure relief valve on the tank was removed and a pressure gauge with a range of 0-30 psi was installed in opening.
[0103] An even flat fan nozzle from TeeJet was used: the TP8001 EVS. With different testing events, the tank was pressurized to 4, 6, 7, 8, 10, 15, 20, 25, and 30 psi. The manual pump was tested at each of these pressure levels. Because the electric pump of the prototype electric dispenser could produce a maximum of about 10 psi, the electric dispenser was only used at pressure levels up to 10 psi.
[0104] A 12 foot long sheet of white paper 18 inches wide was laid out on the floor. A wooden rail was suspended above the paper. With an operator resting the spray wand on the rail, the nozzle was suspended about 8 in. above the floor. The operator then walked along side the rail and sprayed the colored water on the paper. The colored drops formed a spray band with a length of about 10 feet on the paper.
[0105] At about 4 psi, drop quality appeared to be poor. However, with just a small increase in pressure—at about 5 to 8 psi—a spray band with evenly distributed, similarly sized medium-sized drops was achieved. From 9 to 15 psi, spray quality again appeared to deteriorate with 3 distinct heavier bands noticeable within the main spray band. At 20 psi, these bands largely disappeared and a pretty even distribution of drops occurred. However, the drops were quite fine.
[0106] It was noticed during these tests that large numbers of fine spray drops were deposited outside the main spray bands when operating at higher pressures. These drops were heaviest on the side opposite the operator. Therefore another test was conducted. In this test, a spray band was sprayed perpendicular to the longer dimension of a paper sheet 18 in. wide and over 60 in. long. The same rail and spray procedure mentioned above were used to make a spray band. This test was also conducted indoors. Two pressures were used: 7 psi (using the electric dispenser) and 30 psi (using the same dispenser with the manual pump). The purpose of this test was to examine drop distribution over a wider area outside the main spray bands.
[0107] At 30 psi, the main spray band was approximately 14 to 16 inches wide. However, small drops could be seen well outside the main band. In fact, on the side opposite the operator, small drops could still be detected 30 inches from the centerline of the spray band. Most of these drops were very fine, exactly the kind of drop that could easily drift outdoors.
[0108] On the other hand, with the electric dispenser 300 a set at 7 psi the band was smaller with a total band width of about 8 to 10 inches. The drops sprayed at 7 psi were larger than those sprayed at 30 psi. On the side opposite the operator, no drops were observed beyond 14 inches from the centerline of the spray band. Moreover, the drops that did appear outside the main spray band were larger and thus of a size less likely to drift.
[0109] The results suggested with this informal test are surprising. The manufacturer of the 8001 EVS, TeeJet®, recommends using a minimum pressure of 20 psi. And indeed from about 9 psi to 20 psi, the quality of the spray band was not optimal. However, at ultra-low pressure between 5 and 8 psi, drop quality, consistency, and distribution were quite good. Therefore, ultra-low pressures can create high quality spray drops and spray patterns.
[0110] Just as important, when spray drops were produced within the manufacturer's recommended pressure range, e.g., at 30 psi using the manual pump, many more very fine drops were produced. Many of those fine drops landed well outside the main spray band. These fine drops are precisely the sort of drops that could land on non-target surfaces or that could easily drift. In contrast, when the electric dispenser was used to produce spray at ultra-low pressure of 7 psi, far fewer fine drops were observed outside the spray band.
[0111] This test suggests that the electric dispenser operating at ultra-low pressure is capable of producing high quality, well distributed drops, i.e., drops of similar sizes evenly distributed over the spray pattern) that are less likely to drift.
[0112] Another informal test explored the sensitivity of the control system in making small adjustments in pressure. (A prototype electric dispenser was again used.) This test was undertaken to help determine whether the control system had tight or sloppy operation. This inquiry was also undertaken to test the operator's subjective judgment during the field tests that the pump performed well at maintaining a nearly constant pressure and rarely ran for extended periods. For this test, an ultra-high accuracy pressure gauge was used, Ashcroft Type 1082, Grade 3A gauge with an accuracy of ±0.25 psi. The gauge had a range of 0 to 30 psi. 2 liters of water were added to a tank of a prototype dispenser resembling dispenser 300 . A TeeJet® 8008EVS nozzle tip was installed on the spray wand. The power level was set to maximum pressure. The pump was turned on and allowed to run until it stopped. The nozzle was pointed into a container, and the wand lever was depressed. Water was sprayed until the pump started again. The original gauge reading and the reading at the point at which the pump started again were noted. This was done a total of 3 times. Then, the pump was shut off and the pressure released from the tank. The process was repeated two more times for a total of three rounds and a total of 9 “re-pressurization events.” On average, the maximum pressure achieved was between 10.1 and 10.2 psi. When spraying with the wand reduced pressure in the tank, it took only a drop of slightly more than 0.2 psi on average before the pump re-engaged to add pressure to the tank. This test thus suggests that pressure control was very tight and controlled it within a range of about 0.3 psi.
[0113] In a related test the sensitivity of the adjustment mechanism was explored. For this test, the same ultra-high accuracy pressure gauge was used. 2 liters of water were added to the tank of a prototype electric dispenser resembling dispenser 300 . The knob (adjustment mechanism 341 ) was turned to the lowest setting. The prototype dispenser was turned on, and the pump was allowed to pressurize the tank. A reading was taken when the controller turned the pump off. Then, the knob was slowly turned until the pump engaged again. Another reading was taken after the pump stopped. This was repeated until the knob was turned as high as it could go. After the final reading was taken, the pump was turned off and the air released from the tank.
[0114] Three rounds of this test were done with the electric pump engaging 24, 25, and 27 times for an average including the initial pressurization of about 25 “pressurization events.” With the knob set at low, the pump pressurized the tank to an average of about 1.8 psi. With the knob set to high, the pump pressurized the tank to an average of 10.3 psi. This test indicates that quite fine adjustments in pressure could be made by turning the knob on the prototype dispenser.
[0115] FIGS. 4A and 4B show another example of the invention. Here, the dispenser 400 is configured the same as dispenser 300 but with some differences. Dispenser 400 can be used with a backpack frame 456 . The tank 401 can sit in a shallow pan 455 or other holder. The backpack can have a frame 456 that includes foam pads 457 and vertical support struts 458 . In this example, the struts 458 pass through holes in the foam 457 . Shoulder straps 459 can be attached to the struts 458 . For instance, the struts 458 can pass through grommets 460 in the straps 459 .
[0116] A cinching strap 461 can secure the tank to the frame 456 . The cinching strap 461 can be tightened or loosened with a cinching mechanism 462 such as an over-center buckle. With the cinching strap 461 loosened, the tank 401 can be placed on the backpack frame 456 and rotated to different positions. This can allow the tank fitting (not shown) and hose 434 to be positioned in a position convenient for the operator (not shown). For example, the tank fitting 432 can be positioned on the right side as shown in FIG. 5B so the hose 434 is positioned on the right side for right-handed users or positioned (not shown) on the left side so the hose 434 is positioned on the left side for left-handed users. For people who like to switch hands, the tank fitting 432 and hose 434 can be positioned in the middle facing back (not shown), so the wand 435 could be held in either hand. In addition, the tank and wand can be removed from the frame 456 and can function as a pressurized tank sprayer.
[0117] The dispenser 400 can function well as a backpack dispenser. With the dispenser 400 on, the operator can control output of spray or foam by using the lever 445 on the wand 435 . The operator can reach over a shoulder to the controls such as the on-off switch 440 or the adjustment knob 428 . Unlike with the typical manually pumped backpack sprayer, there is no pump lever, therefore one hand is freed. Moreover, there is no pump lever to hit obstructions or catch on brush. Finally, the backpack harness, etc., can be less substantial than the ones typical to most backpack sprayers because there is no need for a firm base to press against when pumping manually.
[0118] FIG. 5A shows a dispenser 500 mounted on a cart 560 . The dispenser 500 can sit in a shallow pan or other holder. A cinching strap 561 can hold the dispenser 500 in place.
[0119] FIG. 6A shows the internal pump mechanism of a dispenser 600 . The dispenser 600 can resemble those described in relation to FIGS. 1A to 5A but it can also have differences. With dispenser 600 , the sensor for the controller 614 and pump 610 can have separate tubes 612 a , 612 b connecting them to the tank 601 . The pressurized air tube 612 a that transfers air from the pump 610 can have a check valve 665 . The air tube 612 b for the sensor for the controller 614 does not in this example. The check valve 665 can prevent backflow into the pump 610 if the dispenser 600 is tipped, etc. In addition, FIG. 6B shows the top face of the pump head 602 . A readout 666 on the top face of the pump head 602 —in this case a digital one—can indicate the pressure in the tank 601 . The readout 666 can be helpful to the operator. For instance, when using a particular nozzle or application technique, the operator may want to use a particular pressure level and can set the adjustment knob 641 accordingly.
[0120] FIGS. 7A and 7B show an example of an electric dispenser, dispenser 700 . The dispenser 700 can resemble those described in relation to FIGS. 1A to 6B . As with dispensers 100 to 600 , dispenser 700 can have a pump head 702 that can function as a container for components of the pressurization system (not shown) and also can function as a reusable closure for the supply tank 701 . (The term “reusable closure” can distinguish the closure from a “single use closure.”) However, there can be some differences. The pump head 702 can a closure system with female threads 785 unlike, for example, pump head 302 which has male threads on the plug 221 . The female threads 785 can seal with the male threads 786 on the finish 787 of the supply tank. Thus, the pump head 702 can form a seal with the supply tank 701 and can function as a reusable cap closure (i.e., an “external closure” as opposed to, e.g., the internal closure provided by the threaded male plug 221 of dispenser 200 ).
[0121] The pump head 702 can be cylindrical and can share a vertical axis (identified dashed line “A”) with the cylindrically-shaped supply tank 701 . The upper part of the reusable closure or pump head 702 can enclose the container for the electronic components 795 (not separately shown) The lower part of the cylindrical wall of the pump head can form the skirt 788 that surrounds the finish 787 when the pump head seals the supply tank 701 .
[0122] The pump head 702 can have a belly 789 within the cap interior 792 that hangs in the fill opening 790 when the pump head is screwed onto the supply tank 701 . The belly 789 , however, can be constructed such that the belly 789 does not hang below the bottom rim 791 of the skirt 788 . Thus when the pump head 702 is removed from the supply tank 701 , it can be placed on a surface 794 without contaminating surfaces of the cap interior 792 .
[0123] This contrasts with conventional tank sprayers with manual pumps, which typically have a pump cylinder that projects down into the interior of the supply tank. When the pump is removed from a conventional tank sprayer filled with liquid, the pump cylinder will have beads of the liquid on its outer surface. The operator cannot lay the conventional pump on a surface without contaminating the pump cylinder or the surface on which it is laid. This makes refilling a conventional tank sprayer especially inconvenient in the field.
[0124] Another difference with dispenser 700 can be the position of the exit 793 for the air supply from the pump (not shown) to pressurize the supply tank 701 . In this example, the exit 793 can be located on the vertically oriented wall of the belly 789 . This location can be advantageous because it can be more protected from the contents of the supply tank 701 .
[0125] FIG. 8A shows a dispenser 800 . The dispenser 800 can resemble those described in relation to FIGS. 1A to 7B , but it can also have differences. The dispenser 800 can be mounted on a vehicle 877 . The pump head 802 can be a separate unit connected to a supply tank 801 by an air tube 812 a for the pump contained by the pump head 802 and a sampling tube 812 b for the sensor system (part of the sensor system can be located in enclosure associated with the control panel 878 ). The supply tank 801 can be significantly larger than one carried by a human—for example, for use on an all-terrain-vehicle, the supply tank can preferably have a capacity of between 3 and 30 gallons.
[0126] The air pump can be significantly larger in size which means it can readily be configured to generate more air flow, generate higher pressure, or both if desired. For example, the pump could be preferably be configured to produce pressures in the pressurizable space of between 1.5 psi and 30 psi. (Of course, still higher pressures could be achieved if necessary. If so, more robust components such as a metal supply tank and reinforced hoses can be used.)
[0127] To accommodate the larger air pump, other changes can be made: as examples, a larger power source can be installed (or the system can use of electric current generated by the vehicle); a sensor (or multiple sensors) can be utilized to sense a wider range of pressures; and the size of the pump head 802 housing can be increased to accommodate the larger components.
[0128] In addition, the pressurization system can be configured with electronic pressure relief. The electronic pressure relief can be performed with an air pump that can reverse flow. Alternatively, in another embodiment, the pressurization system can rely on an electronically activated pressure relief valve (not shown). The electronic pressure relief can depressurize the pressurizable space if the pressure level exceeds a desired pressure level. This feature might be especially useful for a dispenser 800 that can operate at higher pressure. For example, the operator may have set the desired pressure level at 30 psi and allowed the dispenser to be pressurized to that pressure level. However, the operator may determine that the pressure being used is too high for a given application. Then, the operator could use an adjustment mechanism to adjust the desired pressure level down, to say 10 psi. Instead of having to use the wand 835 to spray and reduce pressure (or to release pressure using a manual pressure relief valve (not shown)), the system could automatically release excess pressure and stop the release when the new desired pressure level of 10 psi is reached. In addition, the controller could be programmed to release all pressure from the pressurizable space anytime the switch is turned off (or the dispenser is not used for an extended period of time).
[0129] In addition, the air pump for dispenser 800 can incorporate a feature such as variable speed. At high speed the pump can move more gas into the pressurizable space. At low speed the pump can pump less gas but can do so against higher pressure levels in the pressurizable space. This can allow the rate of pressurization of the pressurizable space to be increased when, for example, pressure levels are low in that space. Then, when the pressure levels are high in the pressurizable space, pressurization can be automatically slowed to ensure full pressurization.
[0130] Still another difference shown in FIG. 8A can be the remote control panel 878 . The control panel 878 can include, for example, an on-off switch and an adjustment knob (not shown). The control panel enclosure can contain portions of the electronics for the pressurization system. An electric cable 880 can link the control panel 878 to the pump head 802 . The control panel 878 can be linked to the pump head in other ways, e.g., wirelessly.
[0131] The electric dispenser described in relation to FIGS. 1A to 8A can have a number of advantages over prior art ones. First, it can operate at ultra-low pressure, e.g., pressure below 10 psi. At these low pressures, the electric dispenser can produce a pattern of high quality, well distributed liquid spray drops. High quality can mean that the drops are not too big or too small. Well distributed drops can mean that drops of a certain size are not concentrated in any part of the spray pattern but are distributed evenly throughout the pattern. Drops produced at ultra-low pressure can have other advantages. Research indicates spray drops ejected from a nozzle at lower pressure have lower velocity. Drops having lower velocity break apart less as they leave the nozzle resulting in fewer fine drops. Fine drops can be problematic because they can easily drift or can dry too quickly when they hit the target (Dried systemic herbicide drops, for example, can crystallize and fall off leaves or may not be absorbed into the weed's vascular system.) Drops having lower velocity also tend to stay on leaves or foliage as opposed to high velocity drops which may bounce or glance off targets such as leaves. The informal tests conducted with a prototype electric dispenser indicated that the spray drops applied using the electric dispenser were retained well by plant foliage. Problems such as excessive dripping, beading, patchy coverage; or poor canopy penetration were not observed. The informal spray droplet tests indicated that the ultra-low pressure spray from the electric dispenser formed fewer fine droplets of a kind that can readily move outside the spray pattern.
[0132] Additionally, ultra-low pressure—even pressure levels below 2 psi can be useful for some spray treatments where a very slow and narrow spray stream is desirable. For example, when herbicide dispensers are used for basal bark treatments on trees, a lower portion of the trunk of the tree is sprayed with a ester herbicide that can soak through the bark. In this situations, herbicide sprayed at higher pressures and with greater flow using sprayers presently available on the market can be very wasteful. The broader spray pattern can miss the target stem, especially when the stem is a small one, e.g., under 2 inches. In addition, the spray can rapidly flow down the trunk onto the ground. This is wasteful and environmentally harmful. The electric sprayer can be configured to spray at pressure levels below 2 psi and even below 1 psi. Especially for basally treating small stems, these low pressure levels can be useful.
[0133] Second, an electric dispenser that operates at ultra-low pressure has other significant advantages. The electric dispenser can demand less power from the pressurization system and require less material strength for the dispenser components. This means the electric dispenser system can be lighter, less bulky, and less expensive to produce, and, if the dispenser is battery-powered, the dispenser can operate longer on a charge than conventional electric dispensers. The pump can also be a high volume, low pressure one which means the tank can be filled with air faster, and the pump itself can be a more economical one. In addition, extra components such as mechanical pressure relief valves can be unnecessary. The control system of the electric dispenser can limit the maximum pressure.
[0134] Third, pressure levels for the electric dispenser can be finely tuned to the desired pressure. Tests suggested the control system could maintain the pressure level when the pressure dropped by an average of approximately 0.2 psi. This consistency in pressure is important for the delivery of consistent spray drops.
[0135] It avoids, for example, the pressure fluctuations of conventional, manually pumped backpack sprayers and also avoids the steady pressure drop of manually pumped tank sprayers. The tight control can avoid the problem that sloppy control causes in a control system's feedback loop. It can mean that the power system is taxed less when trying to re-pressurize a tank during usage.
[0136] Fourth, the electric dispenser can allow for very tight controls on the amount of pressure used by an operator and minimize the potential for human error. For example, in the typical herbicide spraying context, the operator has a great deal of control over the amount of pressure used. This can be problematic. An unskilled or careless operator using prior art, high pressure spray systems can readily use excessive pressure. This can lead to excessive drift, especially because the creation of fine, drift-prone drops during a spraying operation may not be readily noticed by the operator because they can be hard to see.
[0137] Fifth, the electric dispenser can be highly versatile. In several examples above, the pump head contains the primary components of the pressurization system and could be used with a variety of pressurized fluid storage and output systems, including ones that are presently on the market. For example, a pump head according to the present invention designed for use with a pressurized tank sprayer and wand could be used with a variety of conventional tank sprayer systems currently on the market.
[0138] The user would only be required to unscrew the manual pump (which is done with each filling of the tank) and replace it with the electric pump head of the present invention. No other adaptation would be necessary. In addition, the pump head could be used with backpack systems; it could be readily incorporated into systems on carts or motorized vehicles.
[0139] Sixth, containing the pressurization system in the pump head as is done with several of the examples can have other advantages. It places the electronic components well above the liquid; therefore if leakage occurs, the electronic components are less likely to be harmed. Because the pump head can use the same orifice as is used for filling on a standard pressurized tank system, the number of orifices overall on the tank can be reduced. This minimizes the risk of leakage and is more economical. The high placement of the pump system also allows the tank to be filled to a higher level without risking backflow into the tubes connected to the electric pump or sensor.
[0140] Seventh, the electric dispenser can have a number of advantages over systems that use liquid pumps. Only air need pass through the pump of the examples above. This can reduce wear (especially if aggressive chemicals are dispensed), clogging, etc. A more consistent operating pressure can be maintained. A wider variety of liquids can be dispensed—ones with higher viscosity, more aggressive ones, abrasive suspensions, etc.
[0141] Eighth, the electric dispenser can function very well as a foam dispenser with a few changes in the componentry. Low pressure can produce high quality foam. High pressure can readily burst or shear bubbles in the foam as it exits a nozzle creating fine spray particles with the same drift problems associated with high pressure spray systems. Moreover, very high quality foam can be produced at pressure below 10 psi and even 5 psi. The electric dispenser can readily achieve these low pressures. The low pressures produced by the electric dispenser can be especially useful for the precise placement of foam onto surfaces, using for example wiping or dabbing techniques. Just as importantly, precise and constant low pressure levels can be maintained for long periods of time. Therefore, the dispensing operation does not have to be constantly interrupted with manual pump strokes necessary to maintain the appropriate pressure. At slightly higher pressures, e.g., preferably above 5 psi, and with the appropriate nozzle, foam streams could easily be projected over ten feet. Such foam streams can be used for foliar application operations.
[0142] Many other embodiments could be configured differently than as described above. The dispenser can be larger or smaller; carried by a person or animal with or without handles, straps, and so forth; it can be carried on wheels, skids, etc., on or in a vehicle such as a cart, trailer, motor vehicle, boat, robot, airplane, drone etc. different versions could be mounted on a wall or a countertop; a dashboard, and so forth. Several of the examples shown above show the components of the system contained within a pump head. However, the components can be configured in other ways too. In most of the examples above, the pump head housing also acts a removable closure for the fill opening of the supply tank. A dispenser can be made that has a conventional closure for the fill opening and the pump head can be independently mounted on the tank or remotely mounted. It can be configured so that its various components are in one or more remote units. For example, one or more parts of the control unit could be located remotely and connected with wire or wirelessly to the remaining components. Similarly, hoses or lines can connect one or more tanks, one or more pump heads and one or more outlet assemblies remote units. For example, the device could be a tank with an attached pump head connected to a hose with a wand at the distal end having an outlet assembly. The device could have one or more tanks; one or more pump heads, or one or more outlet assemblies. A common configuration might be to have one tank and pump head with multiple outlet assemblies or nozzles. Many of the devices described above operate with low pressure or ultra-low pressure. However, these systems could be readily adapted to be higher pressure systems. For example, with different batteries, motors, and transducers, higher pressures could readily be attainable, even in a dispenser carried by a human.
[0143] The electronics of the pressurization system can be configured differently than the ones described above. For example, a conventional pressure switch can be used to activate the pressurization system.
[0144] The above-discussed embodiments of the present invention generally relate to a dispenser for dispensing a liquid or foam. The invention should be understood to encompass these other uses although such other uses may not have been discussed.
[0145] The invention has been described with reference to various and specific non-limiting embodiments, examples and techniques. One of ordinary skill in the art will understand that reasonable variations and modifications may be made with respect to such embodiments and techniques without substantial departure from either the spirit or scope of the invention defined in the claims. For example, while suitable sizes and parameters, materials, and the like have been disclosed in the above discussion, it should be appreciated that these are provided by way of example and not of limitation as a number of other sizes and parameters, materials. | This invention relates to a device for dispensing spray drops or foam. A first illustrative example of the invention is an electrically powered dispenser comprising: a pressurization system for automatically regulating a pressure level of a gas in a pressurizable space, the pressurization system being configured: to take a pressure reading of the gas, to make a determination if the pressure reading indicates a deviation from a desired pressure level, and based on the determination to make a decision selected from a list comprising at least the following: to start pressurization, to continue pressurization, to stop pressurization, or to do nothing. According to variations or refinements of this first example the pressurization system is sufficiently sensitive to indicate the deviation even if the deviation is minimal. According to other variations or refinements of this first example, the desired pressure level can be, e.g., less than 10 psi. | 1 |
BACKGROUND
1. Technical Field
The present invention relates to the field of weaponry, and more particularly, to counting bullets in a magazine.
2. Discussion of Related Art
Weapon magazines usually lack indications of the remaining number of bullet, which may be very important and even crucial to the soldier.
WIPO publication No. 2008132739, which is incorporated herein by reference in its entirety, discloses a magazine status indicator.
BRIEF SUMMARY
Embodiments of the present invention provide an apparatus comprising: a housing attachable to a bottom of a magazine having a spring-loaded follower, the housing having a window; a platelet arranged to replace a bottom platelet of the magazine and comprising a connector connectable to the spring, and an aperture; means for measuring, through the aperture, a distance between the follower and a point in the housing, the means for measuring integrated within the housing; and means for displaying a number of bullets left in the magazine, through the window, according to the measured distance, wherein the apparatus is arranged to be added on the magazine and display the number of bullets left in the magazine.
These, additional, and/or other aspects and/or advantages of the present invention are: set forth in the detailed description which follows; possibly inferable from the detailed description; and/or learnable by practice of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be more readily understood from the detailed description of embodiments thereof made in conjunction with the accompanying drawings of which:
FIG. 1 is a high level schematic block diagram of an add-on apparatus and a magazine having a spring-loaded follower, according to some embodiments of the invention.
FIG. 2 is a schematic illustration of the apparatus, according to some embodiments of the invention; and
FIGS. 3A , 3 B, 4 A and 4 B are schematic illustrations of the magazine with the apparatus, according to some embodiments of the invention.
DETAILED DESCRIPTION
Before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of the components set forth in the following description or illustrated in the drawings. The invention is applicable to other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.
FIG. 1 is a high level schematic block diagram of an add-on apparatus 100 and a magazine 90 having a spring-loaded follower 96 , according to some embodiments of the invention. FIG. 2 is a schematic illustration of apparatus 100 , according to some embodiments of the invention. Apparatus 100 is arranged to be added on magazine 90 having spring-loaded follower 96 (see FIGS. 3A through 4B ) and display the number of bullets left in magazine 90 . Apparatus 100 comprises a housing 110 attachable to a bottom of a magazine (by clips or other connector types), and a platelet 120 arranged to replace a bottom platelet of magazine 90 and comprises a connector (not shown) connectable to spring 93 . Platelet 120 has an aperture 125 through which a distance 99 between follower 96 and a point in housing 110 is measured by means for measuring 130 integrated within housing 110 . Apparatus 100 further comprises means 140 for displaying a number of bullets left in magazine 90 , through a window 112 in housing 110 , according to measured distance 99 .
Measuring distance 99 may be carried out mechanically by an extendable strap 150 , or by sensors ( 160 , 170 ) as illustrated in the following figures.
FIGS. 3A and 3B are schematic illustrations of magazine 90 with apparatus 100 , according to some embodiments of the invention.
Means for measuring 130 may comprise a coiled elastic strap 150 having an inner end 151 fixated within housing 110 and an outer end 159 stretching through aperture 125 and engaged in an impermanent connection 155 with follower 96 . Impermanent connection 155 is arranged to allow disconnecting apparatus 100 from magazine 90 and reusing apparatus 100 with a different magazine.
Means for displaying 140 the number of bullets left in magazine 90 may comprise numbers 141 on a side of coiled elastic strap 150 that faces window 112 from inside housing 110 , the numbers increasing towards inner end 151 . The numbers may be printed, engraved or attached to strap 150 . The displayed area of strap 150 , i.e., the area facing window 112 , may be variously situated in respect to the coiled part of strap 150 —it may be in the back of the coiled part or along straight parts of strap 150 between inner end 151 and outer end 159 . Numbers 141 may have contrasting colors in respect to the back of the coiled part, or include other visibility enhancers such as phosphorous markings.
Outer end 159 of strap 150 is arranged to move together with follower 96 such as to uncoil coiled strap 150 and present higher numbers in front of window 112 upon an upward motion of follower 96 , and such as to allow coiled strap 150 to elastically re-coil and present lower numbers in front of window 112 upon a downward motion of follower 96 . (The directions are in respect to the Top and Bottom markings on FIG. 1 .)
The relative positions of window 112 and strap 150 may vary. Strap 150 may be arranged to extend along various paths. For example, window 112 may be positioned on a first narrow edge 101 of apparatus 100 and inner end 151 is fixated in a corresponding first side 102 of apparatus 100 , while aperture 125 may be positioned at an opposite narrow edge 108 of apparatus 100 and outer end 159 extend over opposite side 107 through aperture 125 to connect to follower 96 at the opposite narrow side in respect to window 112 .
Apparatus 100 may further comprises a support 153 positioned within housing 110 at a lower portion of opposite side 107 , and arranged to support extended elastic strap 150 .
Alternatively, outer end 159 may extend through a middle 156 of apparatus 100 , aperture 125 may be positioned in the middle of platelet 120 , and outer end 159 may pass through an inner space 157 of spring 93 and is connected to the middle of follower 96 .
Impermanent connection 155 may comprise a connection by a clip (not shown) connected to outer end 159 of strap 150 and operatively attached to follower 96 .
Impermanent connection 155 may comprise a magnetic connection between a magnet 152 connected to outer end 159 of strap 150 and follower 96 .
FIGS. 4A and 4B are schematic illustrations of magazine 90 with apparatus 100 , according to some embodiments of the invention.
Means for measuring 130 may comprise a rangefinder 160 positioned in housing 110 and arranged to optically measure distance 99 to follower 96 through aperture 125 . Means for displaying 140 the number of bullets left in magazine 90 may comprise a display 145 , and apparatus 100 may further comprise a controller 147 A (e.g., a printed circuit board—PCB) arranged to receive the distance measurement, calculate the number of bullets left in magazine 90 therefrom, and display the number on display 145 .
Means for measuring 130 may comprise a pressure sensor 170 such as a piezoelectric sensor, connecting platelet 120 to spring 93 and arranged to measure a pressure applied by spring 93 thereupon. Means for displaying 140 the number of bullets left in magazine 90 may be display 145 , and apparatus 100 may further comprise controller 147 B arranged to receive the pressure measurement, calculate the number of bullets left in magazine 90 therefrom, and display the number on display 145 .
Display 145 may comprise a white on black display for good night visibility, e.g., an OLED (Organic Light Emitting Diode) display. Other types of contrast may be implemented in display 145 to enhance visibility, e.g. phosphorous markings
In the above description, an embodiment is an example or implementation of the invention. The various appearances of “one embodiment”, “an embodiment” or “some embodiments” do not necessarily all refer to the same embodiments.
Although various features of the invention may be described in the context of a single embodiment, the features may also be provided separately or in any suitable combination. Conversely, although the invention may be described herein in the context of separate embodiments for clarity, the invention may also be implemented in a single embodiment.
Furthermore, it is to be understood that the invention can be carried out or practiced in various ways and that the invention can be implemented in embodiments other than the ones outlined in the description above.
The invention is not limited to those diagrams or to the corresponding descriptions. For example, flow need not move through each illustrated box or state, or in exactly the same order as illustrated and described.
Meanings of technical and scientific terms used herein are to be commonly understood as by one of ordinary skill in the art to which the invention belongs, unless otherwise defined.
While the invention has been described with respect to a limited number of embodiments, these should not be construed as limitations on the scope of the invention, but rather as exemplifications of some of the preferred embodiments. Other possible variations, modifications, and applications are also within the scope of the invention. Accordingly, the scope of the invention should not be limited by what has thus far been described, but by the appended claims and their legal equivalents. | A magazine add-on comprising a platelet arranged to replace the bottom platelet of the magazine and allow measuring the distance, e.g., via an aperture in the platelet, to the magazine's spring-loaded follower either mechanically by an elastic strap, optically by a rangefinder or by measuring the pressure applied by the spring on the platelet. The add-on further displays a number of bullets left in the magazine in a window, either mechanically by numbers on the back of the strap, or electronically on a display attached to the window and connected to the optical or pressure sensor. The add-on is reusable and may be separated and re-attached to various magazines. | 5 |
FIELD OF THE INVENTION
The present invention generally relates to network management of ISP (Internet Service Provider) networks, and more particularly to a method and system for detecting transmission of specific content over the network, such as the transmission of pirated copyrighted materials.
BACKGROUND OF THE INVENTION
A recurring problem in Internet usage is the transmission of unauthorized content. One very commercially important example of this problem relates to copyrighted materials. Copyrighted text, music and movies can be transmitted rapidly and cheaply over the Internet, allowing Internet users to easily obtain unauthorized or pirated copies to the detriment of copyright owners. Policing such unauthorized transmission is difficult for copyright owners, because the sources of copyrighted materials may be elusive, or indeed may be legitimate possessors of copyrighted materials but do not have authorization to permit copies to be made. Pursuing the illegal distributors of such materials is problematic because the users are often numerous and diffuse and individual legal action against multiple small users is expensive—as well as unsympathetic from a public relations standpoint when the users turn out to be teenagers or others whose motives are seldom to make a criminal profit.
Approaches to this problem at the source have included attempts to integrate copy-protection measures in the copyrighted materials, but these attempts have met with marginal success as hackers develop—and publish—countermeasures.
A second approach to dealing with the problem at its source is to try to identify Web sites and/or distribution networks/tools that contain copyrighted materials. For example, a form of structural comparison to detect copyright infringement is disclosed in Sergey Brin, James Davis and Hector Garcia-Molina, “ Copy Detection Mechanisms for Digital Documents,” Proceedings of the ACM SIGMOD Annual Conference, San Jose 1995 (May 1995). An available version of the paper can be found at http://dbpubs.stanford.edu:8090/pub/showDoc.Fulltext?lang=en&doc=1995-43&format=pdf&compression=&name=1995-43.pdf. This paper discloses a method which determines whether an identified document is a copy of a specific preidentified copyrighted article. As described in the paper “the service will detect not just exact copies, but also documents that overlap in significant ways.” However, the method requires that the document to be tested be available to start with, would seem to require every data transmission to be tested, and thus does not lend itself to real-time application on Web traffic being transmitted at the high data traffic rates of a typical ISP.
In another example, U.S. Pat. No. 6,658,423 to Pugh et al. discloses duplicate and near-duplicate detection techniques for operating a search engine which assign a number of fingerprints to a given document by extracting parts from the document, assigning the extracted parts to one or more of a predetermined number of lists, and generating a fingerprint from each of the populated lists. Two documents are considered to be near-duplicates if any one of their fingerprints matches. This technique is used to find mirrored Web sites, which either are identical to hosts or are “near-duplicate” copies with insignificant content differences from the host. However, the technique would not be a practical solution for locating illicit content transmitted over an ISP network, first, because it involves the work of completely crawling the Web (a process which is neither economical nor quick) to look for near-replicas of specific pages or portions of a Web site.
These approaches have the drawback that they either require both the copyrighted work and the suspected copy to be already available (Brin article) or they require web-crawling of the entire Web content to locate duplicates or near duplicates (Pugh patent). In addition, they do not deal with the majority of today's distribution of copyright infringement that occurs over Peer to Peer (P2P networks.
An approach which attempts to deal with the problem at the destination is to limit access to or block sites having copyrighted content. These approaches are problematic because the sites are often located outside of the US where copyright laws are not easily enforceable. In addition, techniques to block or limit access by US-based consumers can be thwarted either by the consumer or by the end site providing the content.
Other approaches have attempted to detect the Internet transmission of copyrighted material. These approaches require the participation of those managing transmission resources, such as ISPs, and have included deep packet inspection tools to look for specific protocol types or specific files. Other specialized network appliances have been used to investigate the payload of an IP packet to check for copyright infringement such as the comparing service VideoTracker™ offered by Vobile, Inc. of Santa Clara, Calif. While these approaches eliminate many of the drawbacks associated with the source and destination approaches listed above, the combination of vast amounts of content transmitted over the Internet, and high transmission speeds, require these prior art transmission inspection techniques to employ too many resources—both software and hardware—to cope with existing traffic throughput, and accordingly none of these prior art techniques can perform this detection function in a cost effective and timely manner. These prior art techniques have the further drawback that they require a detailed examination of transmissions of all customers—whether or not there is probable cause to believe they are infringing—which implicates issues of customer privacy.
While the detection of pirated copyrighted materials is an example that has high commercial visibility, there are other transmissions of content that are of interest. For example, law enforcement officials are interested in detecting the transmission of illicit content in the form of child pornography. As another example, national security officials, when permitted by governing law, may be interested in detecting the transmission of certain forms of content, such as that relating to bomb or weapons construction.
Accordingly, there remains a need for methods and systems capable of detecting the transmission of specific content, such as copyrighted content, over the Internet in a timely and cost effective manner while still preserving customer privacy.
Additionally, there remains a need for methods and systems which allow an ISP to offer a service to clients, such as copyright owners, to detect the transmission of content of interest, such as copyrighted content, over the ISP's network.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a method and system which are able to detect the transmission of content of interest, such as copyrighted content, which are able to operate in real time in a cost effective manner, which preserve customer privacy, and which make advantageous use of current technologies.
The present invention preferably uses a currently available real-time network data management device which is capable of analyzing the complete flow of data packets in a data stream. An example of such an existing device is the AT&T Gigascope data analyzer.
The method according to the invention proceeds by providing a set of rules to identify the traffic flow profile of illicit content, or the profile of a repeat or recidivistic copier of illicit content, such as a pirate of online copyrighted material. Such rules may be provided by observation or research relating to profile characteristics.
In one preferred embodiment of the invention, such rules are provided by adaptive rule making techniques. Using such techniques, rules are provided by collecting data regarding the traffic flows within the ISP broadband network, and using a device such as the Gigascope data analyzer to process the collected data in conjunction with other source data from related research suggesting profile characteristics. For example, adaptive rule making might proceed by positing an initial profile characteristic, assuming a data correlation to the characteristic, processing data to look for instances of the characteristic, testing the found instances to determine if the data possesses the profile characteristic, measuring a deviation, and modifying the characteristic and correlation to data to reduce the deviation and improve the match. As an illustrative example, it might be posited that movie copying correlates to a rule which identifies single user download times of more than an hour. Actual data analysis might adapt the rule to a better one that identifies download times of 30 minutes from a single site of certain file types associated with movies (e.g., mpeg files). Adaptive rule making permits the rules to get better with experience and follow changes in usage, as providers or users change patterns to escape detection.
The identification rules that are developed by adaptive rule making or otherwise are selected to have the characteristic that they can be applied to high speed data streams with a high speed data analysis tool such as the AT&T Gigascope analyzer, i.e., they involve relatively few tests, and tests that are able to be performed by analysis of streams of packets transmitted at high speeds. They also are selected to be effective in confirming the existence of a suspected data flow because the usage profiles they represent correlate well in reality with the existence of problematic content. In this sense, the identification rules perform as a set of real-time filters on the entirety of the data flow to identify those subsets of the data flow which are worth examining in further detail using slower but more thorough and exact tests for locating illicit content.
The identification rules that are developed by adaptive rule making or otherwise are applied to on-line data streams in the ISP network so that data streams that fit the profile are identified. In an embodiment of the invention, the identification rules are applied in an active, in-line deep packet inspection embedded within an ISP network element such as a core or gateway router.
Data streams that are so identified by the identification rules are then analyzed to determine if the content of the identified data streams matches the content of a database of preselected content, e.g., a database of copyrighted materials. In an embodiment of the invention the analyzing and matching steps are performed by a commercially available specialized digital fingerprinting device which stores digital fingerprints of items of preselected content, such as copyrighted materials, and compares them with digital fingerprints of the identified data streams.
If the content of the identified data stream is a positive match with a database item, e.g., is a copyright infringement, then a responsive action is taken. The responsive action, for example, might be to terminate the data transmission, to suspend the customer's account, or to report the existence of the match to an interested party, such as a copyright owner or a law enforcement or security official, or to store the positive match to compare to later matches that are detected in subsequent transmissions to the same user or from the same sender.
The system according to the invention comprises means for performing the method described above, i.e., means for storing a set of rules (for example, rules created by adaptive rule making) to identify the traffic flow profile of illicit content or of a repeat or recidivistic copier of illicit content, means for applying the rules to on-line data streams in the ISP network to identify data streams that fit the profile, means for analyzing the content of the identified data streams to determine if that content matches the content of a database of preselected content, e.g., a database of copyrighted materials, and means for taking an action in response if a positive match is found. The various means described in functional terms are, in specific embodiments of the invention, analytical devices such as the Gigascope processor, inspection devices embedded in ISP network elements such as core or gateway routers, and specialized digital fingerprinting devices.
The present invention thus can be seen to have many advantages: it is capable of identifying likely incidents of illicit content transmission, such as piracy of copyrighted material, confirming the presence of such content, and then taking action while preserving the privacy of those ISP customers who have no association with copyright infringement. Further, the present invention is able to achieve these advantages in a deployment that is economically and technically feasible, making use of existing network devices and not requiring extensive hardware or software development. The development of profile rules to identify instances of content abuse permits the method to be used on-line to monitor heavy ISP data traffic and to select the relatively small number of data streams that are problematic and deserve further analysis, which can then be performed using existing slower speed digital fingerprinting or computed hash value comparison devices that would be incapable by themselves of handling an ISP's vast amount of throughput.
The arrangement of the present invention lends itself as well to certain kinds of shared usage. For example, more than one ISP could share a single digital fingerprinting device to analyze identified data streams for matches with a single database of copyrighted materials, which would make it easier for copyright owners to register their content as by registering it just once with a central repository and not with each separate ISP.
These and other objects, advantages and features of the invention are set forth in the attached description.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing summary of the invention, as well as the following detailed description of the preferred embodiments, is better understood when read in conjunction with the accompanying drawings, which are included by way of example and not by way of limitation with regard to the claimed invention:
FIG. 1 is a diagram showing an example of ISP network elements together with an illustrative system according to the invention.
FIG. 2 is a schematic diagram of a method according to the invention.
FIG. 3 is a schematic diagram of a method for creating a heuristic or profile of data streams carrying illicit content over the network.
FIG. 4 is a diagram showing an example of the invention in a form shared by a plurality of ISPs.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows an illustrative ISP broadband network 10 operated by an Internet Service Provider (ISP). The ISP network 10 receives data streams 20 S, 30 S and 40 S from various Internet sources, illustratively shown as applications services devices 20 , VoIP telephony services devices 30 , and IPTV video services devices 40 . The ISP network 10 delivers data from devices 20 , 30 and 40 to residential users 50 and business users 60 connected respectively to residential gateway 50 G and business gateway 60 G.
As shown in FIG. 1 , network 10 typically includes an aggregation layer or region 70 containing aggregation or edge routers 70 R, which may be, for example, 7750 SR routers provided by Alcatel Lucent (ALU). The aggregation routers transmit data over links 70 L to local layer 80 containing distribution switches 80 R, which may be, for example, 7450 ESS routers provided by ALU. Data then proceeds over links 80 L to access nodes 90 , illustratively shown as an FTTx access node 90 F, an xDSL access node 90 D, or a GPON access node 90 G. The access nodes in turn send data over links 90 L to gateways 50 G, 60 G. The links 70 L and 80 L may be, for example, well known transmission links (e.g., fiber optic links), and are selected to have the capacity to handle the volume, QoS and delay constraints for anticipated traffic over network 10 , using design and traffic engineering criteria known by those of skill in the art.
The problem addressed by the present invention is that the data carried by ISP network 10 via routers 70 R, 80 R and links 70 L, 80 L may include preidentified content that is problematic in one way or another—it is copyrighted content being transmitted in violation of copyright rights, or it is pornographic content being transmitted in violation of pornography laws, or it is other content whose detection is of interest. It is desirable for the ISP to have the ability to detect the presence of such content as it is being transmitted over the network 10 and to take an appropriate responsive action.
Accordingly, the ISP network 10 has a content detection system 100 in accordance with the present invention. For illustrative purposes in FIG. 1 , the content detection system 100 is shown as removed from the remainder of network 10 , but in practice significant aspects of it will advantageously be integrated into preexisting network elements in a manner to be described below.
As shown in FIG. 1 , content detection system 100 includes a rule-supplying device 120 , which supplies network-layer profile rules R for identifying network-layer traffic that has a significant likelihood of correlating with one or more types of problematic application-layer content. Alternatively, the profile rules R may be designed to identify network-layer traffic the correlates with repeat or recidivistic transmission or receipt of problematic content. In a preferred embodiment to be described below, rule-supplying device 120 is a data analyzer receiving data transmissions over a fiber tap 110 from link 70 L and is arranged to adaptively generate the profile rules R using adaptive rule making techniques.
Profile rules R provided by data device 120 are sent to a rule-comparing device 130 , which applies the network-layer rules in a real-time application to high-speed streams of data being transmitted by the ISP network 10 , and identifies those streams Dp which conform to the profile rules.
As shown in FIG. 1 , in one embodiment configured to test the workability of the system, the rule-comparing device 130 comprises a mirrored network router 130 R, a duplicate of and connected to router 80 R, supplying a mirror copy of data streams in the network 10 , and a processor 130 P which analyzes those mirrored data streams to determine if any of them satisfy the profile rules R. In normal usage, the router 130 R will not be mirrored but will simply be a router 80 R and the processing of rule-comparing device 130 will take place directly within router 80 R. The streams Dp that satisfy the profile rules R and are identified by rule-comparing device 130 are delivered to a known content-matching device 140 . The identified data streams Dp will be a small subset of all the streams of data being transmitted, which means (a) that most traffic is unaffected, and (b) the identified data streams Dp can be provided at rates manageable by the processing operations of content-matching device 140 .
Content-matching device 140 includes a processor 140 P which analyzes the identified data streams Dp to determine if they contain any of the preidentified content in a content database 140 D. Content-comparing device 140 preferably is one that uses processor 140 P to reconstruct identified streams Dp and compare the content of the those streams with digital fingerprints and/or computed hash values of content stored in content database 140 D. The output of content-comparing device 140 is a signal Sm which indicates whether the content of the identified stream Dp, which has been analyzed by processor 140 D, has produced a positive match or not. Content-comparing device 140 may be a device such as the digital fingerprinting devices of Vobile, Inc. of Santa Clara, Calif.
If content-comparing device 140 produces a positive match, i.e., determines that the identified data stream Dp contains preidentified content, then the signal Sm is sent to a response unit 150 , with a processor 150 P, to cause one or more responsive actions to be taken. The responsive action, for example, might be to terminate the data transmission by means of a connection 150 C to network 10 , to suspend the customer's account, or to report via another connection 150 D the existence of the match to an interested party, such as a copyright owner or a law enforcement or security official. An additional responsive action, in a preferred embodiment of the invention, is to supply the signal Sm via another connection 150 E back to the rule-providing device 120 . There the positive match may be stored to compare it to later matches that are detected in subsequent transmissions to the same user or from the same sender, or as will be described below, to be used in adaptive rule making.
The content detection system 100 illustrated in FIG. 1 and described above performs a content detection method 200 , shown schematically in FIG. 2 . In step 210 , one or more profile rules R for identifying likely preidentified problematic content or repeat users of problematic content are provided, as in rule-providing device 120 . In step 220 , the profile rules are applied to the ISP data streams in a real-time application, as in rule-comparing device 130 , to identify any data streams D which respond to the rules R and thus may be considered likely to contain preidentified problematic content. In step 230 , preidentified content C such as fingerprints and/or computed hash values of copyrighted content is stored, as in database 140 D in content-matching device 140 . The storage step is an offline process dependent on device 140 and may be one in which content owners send the content to the ISP for storage, or one in which content owners may self-download content to database 140 D. In step 240 , content in the identified data streams D is matched with the stored content C, as in content-matching device 140 through the operation of processor 140 P. If there is a positive match, shown by branch Y, then in step 250 a responsive action may be taken. The responsive step may include terminating the transmission, or suspending the customer's account, or reporting via the existence of the match to an interested party, such as a copyright owner or a law enforcement or security official. Preferably, the result of the matching step 240 is also delivered via a return loop 260 to the rule-providing step 210 for use in adaptively modifying the profile rules, as in rule-providing device 120 , and improving their effectiveness in efficiently identifying data streams likely to have problematic content.
Rule-providing device 120 and rule-comparing device 130 preferably make use of a Data Stream Management System (DSMS) which monitors the transmitted data and evaluates streaming queries, which are usually expressed in a high-level language with SQL-like syntax. Streaming queries usually constitute an infrequently changed set of queries that run over a period of time, processing new tuple arrivals on-the-fly and periodically computing up-to-date results over recently arrived data. An example of such a data stream is the stream of packets transmitted in a Gigabit Ethernet communications network.
An example of a DSMS is the AT&T Gigascope data analyzer, whose operation is described for example, in U.S. Pat. No. 7,165,100 and in C. Cranor, T. Johnson, O. Spatscheck, and V. Shkapenyuk. Gigascope: High Performance Network Monitoring With An SQL Interface , in Proc. ACM SIGMOD Int. Conf. on Management of Data, pages 647-651, 2003. The Gigascope analyzer has the capability to look at every packet in a data stream and to provide answers to various queries, such as the amount of traffic of a specified data type that is transmitted from an identified origin to an identified destination. The Gigascope analyzer divides the query plan into a low-level component and a high-level component, denoted LFTA and HFTA, respectively. An LFTA query evaluates fast operators over the raw stream, such as projection, simple selection, and partial group-by-aggregation using a fixed-size hash table. Early filtering and pre-aggregation by the LFTAs are crucial in reducing the data volume fed to the HFTAs, which execute complex operators (e.g., expensive predicates, user-defined functions, and joins) and complete the aggregation. The Gigascope DSMS features a high-level query language with SQL-like syntax. Supported operators include projection, selection, aggregation, grouping, stream-merge, stream-join, and user-defined functions. The input and output of each operator (and each query) is a stream, which enables query composition and simplifies the semantics. The Gigascope analyzer provides a set of schemas corresponding to well-known protocols, protocol layers, and applications (e.g., Netflow® records, raw packets, layer-2-Ethernet, IP, TCP, UDP). This allows users to reference protocol-specific or application-specific fields in their queries without manually specifying how to extract them from the data packets. Since streams are unbounded, a blocking operator such as aggregation would never produce any output. Aggregation may be unblocked by defining windows over the stream by way of a temporal group-by attribute.
The DSMS is shown in FIG. 1 as including a processor 120 P and a database 120 D. The processor 120 P receives all of the data being transmitted over the fiber tap 110 from link 70 L to the data analyzer 120 . Processor 120 P also receives the signal Sm from content-comparing device 140 and has software program control of processor 120 P to review how well the rules correlate with results and to adaptively modify profile rules R to improve their capability for efficiently identifying content that has a predetermined probability or likelihood of correlating with one or more types of preidentified problematic content. It will be appreciated that different profile rules R will correlate with different content. Among the criteria to be considered in the adaptive rule making are:
(a) The ability of the rules to be applied in a real-time process on the vast quantities of high-speed data carried by an ISP, which suggests that simple counting or timing rules be used to minimize processor requirements. (b) The effectiveness of the rules in identifying the preidentified problematic content, which suggests that more complicated rules, or a larger set of rules, be used to improve correlations. (c) The nature of the content whose presence is to be detected, which suggests that different stored content C may respond to different kinds of rules. (d) The sensitivity of customer data, which suggests that the use of adaptive rules based on high-order network statistics as opposed to inspection of specific application-layer data to preserve customer privacy.
Resolving the criteria identified above to produce a workable set of profile rules is possible by application of known adaptive processes. Adaptive rule making methods are well known for identifying certain kinds of network traffic data patterns and for correlating them with specific events. For example, methods for detecting anomalous data stream patterns correlating with network failure are described in M. Thottan and C. Ji, Anomaly Detection in IP Networks , IEEE Transactions on Signal Processing, Vol. 51, No. 8, pp. 2191-2203, August 2003; L. Lewis and G. Dreo, Extending trouble ticket systems to fault diagnosis , IEEE Network, vol. 7, pp. 44-51, November 1993; A. Lakhina, M. Crovella and C. Diot, Characterization of Network - Wide Anomalies in Traffic Flows , IMC '04, Oct. 25-27, 2004, Taormina, Sicily, Italy; and A. Lakhina, M. Crovella and C. Diot, Diagnosing Network - Wide Traffic Anomalies , SIGCOMM '04, Aug. 30-Sep. 3, 2004, Portland, Oreg., USA. These methods, incorporated herein by reference, may be readily adapted to perform the steps of adaptive rule making method 300 shown in FIG. 3 . Using such techniques, rules are provided by collecting data regarding the traffic flows within the ISP broadband network using a device such as the Gigascope data analyzer to process the collected data in conjunction with other source data from related research suggesting profile characteristics.
As shown in FIG. 3 , method 300 proceeds in step 310 by positing an initial profile characteristic PC in the form of a network statistic test, rule or heuristic that can be performed on a data stream, e.g., “single user+download time>1 hour+any file type” and in step 320 by assuming a resulting correlation to the data characteristic, e.g., “corresponds to potential copyrighted movie infringement”. The initial profile characteristic may be obtained from one or more studies which have suggested possible characteristics of infringing transmissions.
In step 330 the method 300 processes data streams to identify instances of the posited profile characteristic, as in rule-comparing device 130 . In step 340 the identified data streams are tested, as in content-comparing device 140 , to determine if the identified data streams have the assumed resulting correlation, i.e., are movie infringements. In step 350 , the method proceeds by measuring a deviation based on a sample of such determinations, i.e., the difference between the measured results of a sample of tests and a desired result. For example, step 340 may determine that 30% of the rule-identified data streams correlate to infringements, and it is desired that 90% of identified data streams correlate to infringements (perhaps to avoid having too narrow a test that would fail to detect some infringements), in which example step 350 would provide a deviation of 60%.
In step 360 , the method proceeds by modifying the profile characteristic (and perhaps the resulting statement of correlation to data as well) in an effort to reduce the deviation and improve the ability of the profile characteristic to predict a match. The modified profile characteristic is looped back through return path 370 to step 310 (and 320 if a change to the correlative is made) to repeat steps 330 and 340 to determine if the modified profile characteristic produces a sample that reduces the deviation measured in step 350 . The construction and control of such iterative loops to produce convergent solutions are well known to those skilled in adaptive rule making. The use of method 300 permits profile characteristics to be improved based on actual network content, and to permit them to change as network usage changes (e.g., as copyright infringers change tactics). As an illustrative example, it might be found as a result of method 300 that movie infringement more closely correlates to a profile characteristic or detection rule as follows: “download times>30 minutes+a single site+file types associated with movies (e.g., mpeg files)”.
For ease of explanation, FIG. 1 shows content detection system 100 and its rule-providing device 120 , rule-comparing device 130 and content-comparing device 140 as separate from network 10 and router elements 80 R. Alternatively, and preferably, the various components of content detection system 100 may be incorporated into the network 10 in order to achieve cost and performance advantages. Thus, in actual network operation the mirrored router 130 R will be unnecessary, and data routers 80 R will directly provide their data streams for analysis by a processor such as processor 130 P to identify data streams Dp suspected of containing illicit content. Similarly, processors 120 P, 130 P and 140 P, shown as separate, may be merged into a single processor programmed to perform the adaptive rule making functions of rule-providing device 120 , the data stream identification functions of rule-comparing device 130 and the content matching functions of content-comparing device 140 . Such processors 120 , 130 and 140 may be integrated into routers 80 R, for example as part of the event monitoring service within the Element Management System (EMS) of a network element. A single DSMS, such as a Gigascope data analyzer, could be used both for adaptive rule making in device 120 and method 300 and for rule-comparing with real-time data streams in device 130 , feeding identified data streams Dp to a commercially available content-comparing device 140 , which can then provide a responsive signal if a match is found to be subsequently used to terminate the transmission or take other responsive steps. Such an integrated content detection system, it is expected, will identify data streams Dp with probable illicit content and then test them for a match with protected content in less than a second.
FIG. 4 illustrates a system 400 in which several ISPs, shown as ISP 1 , ISP 2 and ISPn, share a common content-comparing device 140 C with a common repository or digital library in database 140 Dc of preidentified content, e.g., copyrighted material, whose presence on ISP transmissions is sought to be detected, and a processor 140 Pc to determine if identified data streams are a match with content in the database 140 Dc. As shown in FIG. 4 , each ISP has its own rule-providing device 120 . 1 , 120 . 2 , 120 . n and rule-comparing device 130 . 1 , 130 . 2 , 130 . n . The separate ISPs send identified data streams Dp 1 , Dp 2 , Dpn to the common content-comparing device 140 C, which then determines, e.g., by digital fingerprinting methods, if any of the identified streams matches content in database 140 Dc. System 400 permits content owners to register their material just once, in common repository or digital library 140 Dc, for access by multiple ISPs and broad protection. The common content-comparing device 140 C may be provided, as shown in FIG. 4 , with a response unit 150 C that alerts the participating ISPs that a match has been found and that appropriate responsive action, as previously discussed, may be taken.
Thus, the invention describes a method and system enabling the transmission of preidentified content, such as copyrighted material, to be detected. While the present invention has been described with reference to preferred and exemplary embodiments, it will be understood by those of ordinary skill in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention include all embodiments falling within the scope of the appended claims. | A method and system for detecting the transmission of preidentified content, such as copyrighted material, over an Internet Service Provider (ISP) network. A set of rules is provided to identify one or more traffic flow profiles of data streams transmitting preidentified content. Preferably the rules are adaptively created through analysis of actual ISP data in conjunction with data suggesting an initial set of profile characteristics. The rules are applied to data streams being transmitted in the ISP network, so that data streams fitting one or more of the profiles are identified. A database contains, e.g., as digital signatures or fingerprints, one or more items of content whose transmission is sought to be detected. Data streams identified as matching a profile are analyzed to determine if their content matches an item of content in the database, and if so, an action is taken which may include interrupting the transmission, suspending an ISP account, or reporting the transmission. An ISP with a system performing this method may offer services to content providers, and a plurality of ISPs may jointly use a single database of preidentified content to be compared to each ISP's identified data streams. | 6 |
BACKGROUND OF THE INVENTION
Automatic pool covers, the subject of this invention, may be used in swimming pools of any mode of construction, but will probably find most application in vinyl lined pools and in upgrading existing pools.
Use of an automatic pool cover will provide considerable cost and aesthetic benefits in upgrading existing pools, since the automatic pool cover will provide a new vinyl surface as well as the designed cover feature. Thus, existing pools can be upgraded without even emptying the pool. In many cases, emptying a weakened in-ground pool will cause complete failure due to the external hydrostatic pressure. Use of the automatic pool cover in such a pool may extend its useful life considerably.
The automatic pool cover consists of two sections (FIG. 1B);
(a) the pool cover section with shape and dimensions defined by the surface configuration of the pool, and
(b) a membrane section with a shape defined by the interior surface of the pool and the shape of the pool cover.
The cover and membrane sections serve also to separate two compartments in the pool, namely the upper stored liquid compartment and a lower balancing liquid compartment. Water can be transferred by means of the external circulating pump from the balancing to the stored liquid compartment and vice versa. In the operating position all of the water is on the upper storage compartment, while in the covered position all of the water is in the balancing compartment. Thus, the pool can be maintained full at all times.
SUMMARY OF THE INVENTION
An object of this invention is to provide an automatic pool cover for considerably extending the useful life thereof.
A further object of this invention is to provide an automatic pool cover for maintaining hydrostatic pressure of the pool within a predetermined range, as well as controlling the shape and dimension of the cover of the pool.
BRIEF DESCRIPTION OF THE DRAWINGS
Various other objects, features and attendant advantages of the present invention will be more fully appreciated as the same becomes better understood from the following detailed description when considered in connection with the accompanying drawings, wherein like reference characters designate like or corresponding parts throughout the several views, and wherein:
FIG. 1A discloses a top plan view of the automatic pool cover of the present invention, while FIG. 1B is a view of the pool and pool cover of FIG. 1A taken along line I--I;
FIG. 2A discloses a cross-sectional view of the pressurized tensioning compartment of the present invention while FIG. 2B is a cross-sectional view of a pressurized compartment with corresponding air valves and vents;
FIGS. 3A and 3B illustrate the operation of the automatic pool cover of the present invention;
FIG. 4 sets forth an alternative embodiment of the pool cover of the present invention;
FIG. 5 discloses the location of the automatic pool cover during operation of the present invention;
FIG. 6A discloses a plan view of an alternate embodiment of the pressurized tensioning compartment of the present invention while FIG. 6B is a view taken along line VI--VI of FIG. 6A;
FIGS. 7A-7D set forth various bottom styles of pools, while FIGS. 8A-8E shows various embodiments of pool shapes and bottoms; and
FIG. 9 shows the liquid transfer system for the automatic pool cover of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In order to provide the desired operating characteristics and for aesthetic reasons, an essential feature of the membrane separating the two compartments 1, 2 is a well defined and structurally stable, but flexible pool cover element 3. Thus structural stability is provided by a pressurized tensioning compartment(s) 4 around the periphery of the cover section. Pressurization is provided by filling these compartments with water and adjusting to the desired pressure via filling connection members 4A.
From FIG. 2A it is noted that the pressurization results in an adjustment in the dimension of the cover at one end by as much as distance "X", as the compartment 4 takes on a circular shape.
A continuously connected outer compartment 4 may be provided, or more usually separate compartments may be constructed at the two ends and two sides as shown in FIG. 1A. Four compartments 4 are indicated in this figure. More compartments may be provided as necessary, for example, to achieve greater flexibility at changes in sections in the base of the pool.
Pressurizing all compartments 4 to achieve the desired shape and dimensions for the pool cover section serves to pull the top pool cover 3 taut as it floats on the surface of water in the balancing compartment 1 (FIGS. 2A and 2B). A similar analogy is provided by pressuring a car tube with air which forces the tube to assume the desired circular configuration and provides a greatly increased structural stability as a result. In the same way, pressurizing the tensioning compartments 4 of the pool cover 3 causes the cover to take the shape defined in manufacture to correspond with the surface shape of the pool 6. With separate compartments 4 the tensioning and dimensions can be adjusted to allow for the usual variability in construction.
The tensioning compartments 4 may be required to withstand pressures of at least 1.5 to 2 times (or even higher) normal tap water pressure as it is expected that normally tap water will be used to pressurize the compartments. Lower pressure limits may also be appropriate as greater experience is gained in the operation of the system. Alternatively, the compartments 4 can be filled with water and pressurized with air. This allows a more ready adjustment of the operating pressure through the use of conventional air valves in the water filling connection. As air is compressible it is much less likely that the safe working pressure of the compartments 4 will be exceeded. These adjustments are made only after a pool liner 7 and automatic pool cover 3 have been installed and the balancing compartment 4 of the pool has been filled with water.
The most suitable dimension for the pressure tensioning compartments 4 will depend on the size of the pool 6, the material of construction and thickness of the pool cover and other factors. However, circular diameters in the range of 3" to 24" may be appropriate for most applications.
Air vents 8 are located in the four corners of the cover section (or in other locations as found appropriate in practice) to enable trapped air to be released during installation and operation. These vents 8 consist of conventional removable plugs with seals.
Provisions can also be made in constructing pool cover sections for inserts 10 (as shown in FIG. 4) to clear pool ladders, etc. FIGS. 6A and 6B show a means whereby the drainage of water from above the cover can be facilitated by welding the tensioning compartment 4 together over a short section 4' opposite the overflow return line to the pump described hereinbelow and shown in FIG. 9. Likewise, flooding the cover 3 can be assisted by a similar arrangement at the inflow line from the pump.
As shown in FIGS. 1A and 1B, a membrane section 3A is attached to the pool cover 3 around the inside periphery of the tensioning compartment 4 and is also joined to the pool liner 7 to form a seal or joint 12 between the balancing and storage compartments 1, 2, respectively, of the pool. In one possible configuration the seal may be located at approximately half the height of the pool wall 14, or alternatively, may be attached at the upper edge of the pool by means of conventional methods used to attached pool liners (as shown in FIGS. 3A and 3B).
Where the membrane 3A is attached to the vinyl liner 7 (as shown in FIGS. 1A and 1B), the seal or joint 12 may be formed either in the workshop where the liner and pool cover are manufactured or, alternatively, at the construction site. The former method provides a better means of quality control, but the best method will depend on the particular circumstances of a given case. This means of attachment reduces the quantity of liner material required in any instance, but may be limited in application to new liner constructed pools since it may not be possible to reduce the water level in an existing liner pool sufficiently for hydrostatic head reasons. The seal or joint 12 is most effectively made in vinyl liner 7 by means of electronic or heat welding which requires a readily accessible clean dry surface.
Other advantages of locating the membrane seal or joint 12 in the vertical wall 14 section include:
(a) better control of the hanging membrane material, and
(b) allows for a light, ladder, and other wall fittings to be installed directly into the pool liner above the joint.
With the membrane attachment as shown in FIG. 3A and FIG. 1B, the hanging membrane material is kept away from the vertical wall 14 by the tensioning compartment 4 in the pool cover 3. The amount of hanging material is reduced and the position of attachment to the wall prevents loose material from building up against the wall as the cover rises.
The method of attachment shown in FIGS. 3A and 3B provides greater versatility, since it is not necessary to weld the membrane 3A to the liner material 7 (although this is still an acceptable method of attachment). This automatic pool cover 3 can be installed in existing as well as new pools with little difficulty. Conventional methods can be used for securing the end of membrane 3A to the top edge 16 of the pool 6. The loose hanging membrane material is kept clear of the wall 14 by attaching the other end to the pool cover 3 on the underside and behind the tensioning compartment 4. The two sections are electronically welded together in this position in the factory at the time of manufacture forming the complete automatic pool cover.
Once installed, it is possible to convert to the attachment arrangement shown in FIG. 3A by electronically welding the membrane 3A at the construction site to the pool liner along a line at approximately half the depth of the vertical wall section. This method of installation may prove more convenient in some applications than an automatic cover which is joined on the vertical wall in the factory prior to installation. The membrane 3A and liner 7 may be welded at other sections, as for example, installation of pool ladders, lights and other fittings as appropriate.
The membrane shape in all instances is determined by the internal and surface configurations of the particular pool applications. Since the cover section corresponds to the surface dimensions, the membrane 3A must be cut out to fit the internal dimensions of the pool 6 with the cover section located on the base of the pool as shown, for example, in FIG. 5. For the flat bottom and straight sloping rectangular pool (FIGS. 7D and 7C, respectively), the shape of the membrane is readily determined. Hopper pools and pools with non-rectangular surfaces (see FIGS. 7A and 7B, as well as FIGS. 8A-8E) present a more complex membrane shape configuration, but the same principle applies for determining the shape; namely, to fit the internal pool dimensions with the pool cover section 3 located flat on the base. When the automatic pool cover is installed and the pool is in operation ready for use, the pool cover 3 and membrane 3A will lie flat against the walls 14 and base of the pool without wrinkles. In the case of the hopper-style pools, some wrinkling of the cover section may appear in the deep water section at the hopper, but will not detract from the surface appearance of the pool, nor interface with the vacuum cleaning of the pool.
Polyvinyl chloride (vinyl) in thicknesses varying from 10 mills to 30 mills is almost exclusively used as the plastic lining material for lined swimming pools, above and below ground. This material is also a suitable material for construction of the automatic pool cover 3 which is the subject of this invention. Other materials of construction for the membrane material such as unreinforced and reinforced polymers, for example, polyethylene, polypropylene, butyl rubber, chlorinated polypropylene, hypalon, and ethylene-propylene diene monomer and others.
The same methods of fabrication already used by manufacturers of vinyl liners and swimming pool covers are applicable to automatic swimming pool covers. Lap welded seams are recommended in preference to butt welded seams to provide additional strength. Colored vinyl fabrics may be used for both the cover and membrane sections which will generally match the color of the vinyl liner used for pool construction. Translucent vinyl may also be used in the construction of the membrane section to facilitate inspection of the balancing compartment and to allow light transmission from a light fitting already installed in a vinyl liner or other form of pool construction. Translucent inspection and light fitting parts may also be welded into the membrane or pool cover for the same purpose.
Factory fabricated integral automatic pool covers and vinyl liners can be installed in a dry excavation using the same technique as for a conventional vinyl liner pool. A separate automatic pool cover can also be installed in a dry, previously lined excavation or dry pool to be reconditioned by use of the cover following a similar technique. Alternatively, the cover 3 can be installed in a full or partially filled pool.
In a dry excavation, the automatic cover 3 is unfolded with at least one person on each corner of the cover (or combined liner/cover). Each person moves to the appropriate corner of the pool and begins to push it into each corner to form a snug fit. When in place, the top of the membrane is temporarily held onto the attachment plate with weights. A vacuum cleaner is used to draw air out from under the cover and a broom is used to smooth out wrinkles in the cover so that it fits exactly in place.
The tensioning compartments 4 are then filled with water before filling the pool 6. When the pool is full, the membrane section 3A of the cover 3 can be secured in position permanently on an attachment plate which may then be covered with topping material such as wood, stones, pavings, etc. Water is then pumped from the upper storage section 2 to the balancing section 1 until the cover is exposed on the surface of the pool. In this position, the pressure in each tensioning compartment 4 is adjusted to give a snug fit with the wall 14.
When installing the automatic pool cover 3 in a full or partially full pool, the membrane section 3A is folded under the pool cover 3. The four corners are then carried to the corresponding corners of the pool and laid in position on the surface of the water. The ends of the membrane are temporarily held on the attachment plate with weights. Each tensioning compartment 4 is filled with water and the pressure adjusted to give a snug fit with the wall. As water is transferred from the balancing compartment to the upper storage compartment, the membrane is smoothed out against the wall using a broom.
In swimming pool applications, use of a flexible membrane to separate the balancing and stored liquid provides the possibility of utilizing the membrane as an automatic cover for safety and heat, water and chemical conservation purposes.
Design pumping rates for swimming pools normally aim to filter the entire content of the pool in 8-12 hrs. With the proposed design, a shorter turnover time is desirable, although during pumping of the contents from balancing compartment 1 to storage compartment 2, or vice versa, the main pool filter 20 shown in FIG. 9 may be bypassed. An inline self-cleaning cartridge filter or other type of coarse filter 22 may be provided to prevent transfer of sand and other coarse particles into the balancing compartment.
In this proposed design, higher pumping rates for transferring liquids between storage or balancing sections can be obtained by increasing line size, careful pump and coarse filter selection and bypassing the main filter 20 and heater 24 (if also provided). For this condition, a transfer time of approximately one hour would be desirable to secure the safety of the pool and to quickly make the pool ready for reuse.
A pressure switch 26 in the suction line 28 to the upper storage compartment may be used to automatically shut off the pump(s) 30 when all the liquid has been transferred to the balancing compartment 1. Automatic pressure or flow switching may be provided to terminate transfer from the balancing to the storage compartment in a coordinated manner. Block valves, 3-way and bypass valves 32 can be provided as shown in FIG. 9.
A drain valve 34 is provided in the pump discharge line 36. Because of hydrostatic pressure, single vinyl liner pools cannot generally be emptied. This objection is overcome with the proposed design, as the lower compartment can be emptied through the pump drain valve 34, while a separate clean water supply is provided to the upper compartment. The rates of the two flows can be balanced so that the upper compartment fills at the same rate as the lower compartment is emptied.
Likewise, with the upper membrane on the surface, a separate water supply can be used to wash the cover, while the pump section is connected to the overflow line and the drain valve is open.
The pool can be operated in a shallow mode for the convenience and safety of young children by transferring water from the balancing to the storage compartment or vice versa until the depth of water above the pool cover is suitable for this purpose (18"-24"). The pump can then be stopped or placed in recycle mode to maintain this depth until the pool required to be covered or returned to its normal function.
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. | An automatic cover for a liquid storage container and a method of control corresponding thereto including a cover disposed within the container, a membrane connected to a portion of the storage container and connected along a peripheral portion of the membrane to the cover, the membrane and the cover separating the storage container into a liquid storage compartment and a liquid balancing compartment, a pressurized mechanism connected to the peripheral portion of the membrane for controlling the shape and dimension of the cover and a member for feeding balancing liquid to and for withdrawing balancing liquid from the liquid balancing compartment in such a manner that hydrostatic pressure of the storage container is maintained within any predetermined range. | 4 |
[0001] This application claims the benefit of U.S. Provisional Application Number 60/759,601 filed on Jan. 17, 2006.
FIELD OF THE INVENTION
[0002] The present invention relates to spiro compounds, processes for their preparation, pharmaceutical compositions containing them as active ingredient, methods for the treatment of disease states such as cancers associated with protein tyrosine kinases, especially epidermal growth factor (EGF) and vascular endothelial growth factor (VEGF), to their method of use as medicaments and to their method of use in the manufacture of medicaments for use in the production of inhibition of tyrosine kinase reducing effects in warm-blooded animals such as humans.
BACKGROUND OF THE INVENTION
[0003] Protein tyrosine kinases have been identified as key players in cellular regulation. They are involved in immune, endocrine, and nervous system physiology and pathology and thought to be important in the development of many cancers. Protein tyrosine kinases represent a diverse and rapidly expanding superfamily of protein, including both transmembrane receptor tyrosine kinases and soluble cytoplasmic enzymes also known as nonreceptor tyrosine kinases.
[0004] Receptor tyrosine kinases are large enzymes which span the cell membrane and possess an extracellular binding domain for growth factors such as epidermal growth factor (EGF) and an intracellular portion which functions as a kinase to phosphorylate tyrosine amino acids in proteins and hence to influence cell proliferation. It has also been shown that epidermal growth factor receptor (EGFR) which possesses tyrosine kinase activity is mutated and/or over expressed in many human cancers such as brain, lung, squamous cell, bladder, gastric, breast, head and neck, oesophageal, gynecological and thyroid tumors. EGFR is the archetypal member of receptor tyrosine kinase family comprised of four closely related receptors called EGFR, HER2 (human EGF-related receptor), HER3 and HER4 (Pinkas-Kramarski R, Eilam R, Alroy I, Levkowitz G, Lonai P, Yarden Y. Differential expression of NDF/neuregulin receptors ErbB-3 and ErbB-4 and involvement in inhibition of neuronal differentiation. Oncogene 1997; 15:2803-2815). All of these transmembrane receptors contain an intrinsic kinase activity that modifies tyrosine residues on the receptor itself as well as on downstream signaling molecules. This kinase activity is stimulated when members of the EGF family of growth factors bind to the receptor. Ligand-induced EGFR activation initiates a signaling cascade that activates gene expression and induces cellular responses such as cell cycle progression or differentiation. Aberrant activation of this highly regulated signaling pathway is believed to contribute to many tumorigenic processes, including enhanced cellular proliferation, protection from apoptosis, tumor cell invasion and metastasis (Huang S M, Harari P M. Epidermal growth factor receptor inhibition in cancer therapy: biology, rational and preliminary clinical results. Invest New Drugs 1999; 17:259-269).
[0005] Each receptor is composed of three domains-an extracellular ligand-binding domain, a transmembrane domain, and an intracellular tyrosine kinase domain. The active receptor is a dimmer, which can be formed by combinations of identical receptor pairs (homodimerization) or different receptor pairs (heterodimerization). EGFR has two main ligands, epidermal growth factor (EGF) and transforming growth factor (TGF). Following binding of a ligand, the receptor dimerizes, which results in activation of the intracellular tyrosine kinase. This begins a number of phosphorylation events that, in turn, initiate a cascade of intracellular signaling process.
[0006] Accordingly, it has been recognized that inhibitors of receptor tyrosine kinases are useful as a selective inhibitors of the growth of mammalian cancer cells.
[0007] Normal angiogenesis plays an important role in a variety of processes including embryonic development, wound healing and several components of female reproductive function. Undesirable or pathological angiogenesis has been associated with disease states including diabetic retinopathy, psoriasis, cancer, rheumatoid arthritis, atheroma. Tumor angiogenesis, the formation of new blood vessels and their permeability is primarily regulated by (tumor-derived) vascular endothelial growth factor (VEGF), which acts via at least two different receptors: VEGF-R1 (fms-like tyrosine kinase, Flt-1); and VEGF-R2 (kinase domain region, KDR/fetal liver kinase-1, Flk-1). The VEGF KDR receptor is highly specific for vascular endothelial cells (for review, see: Farrara et al. Endocr. Rev. 1992, 13, 18; Neufield et al. FASEB J. 1999, 13, 9).
[0008] VEGF is another kind of receptor protein tyrosine kinases. A large number of human tumors, especially gliomas and carcinomas, express high levels of VEGF and its receptors. This has led to the hypothesis that the VEGF released by tumor cells stimulates the growth of blood capillaries and the proliferation of tumor endothelium in a paracrine manner and through the improved blood supply, accelerate tumor growth.
[0009] It has now been found that spiro compounds of formula I, described below, are a new class of compounds that have advantageous pharmacological properties and inhibit the activity of tyrosine kinases, for example, the activity of the EGFR and VEGFR tyrosine kinases, the activity of other receptor tyrosine kinases, such as c-kit, PDGF, FGF, SRC etc. They may also be irreversible inhibitors of tyrosine kinase.
[0010] Examples of spiro compounds that are similar in structure to those of the present invention are disclosed in the following literatures: WO9510519, WO9639407, WO0153273, WO03014108, WO20026073167, JP05221947, JP2004099609, EP0341493, EP0357047, EP0623585, EP611137, JMC 37, 3344 (1994), Tetrahedron Letter, 41, 8173-8176, JACS, 119, 7615-7616 and Heterocycles, 52, 595-598 with the following structures:
[0011] Examples of non-spiro compounds of quinazoline derivatives that are similar in structure to those of the present invention are disclosed in the following patent applications: EP0357047, EP 0566226, EP 0602851, EP 0635507, EP 0635498, EP 0520722, WO9633980, WO9738983, WO9738994, WO0047212, WO0121596, WO0132651, and WO02092577.
SUMMARY OF THE INVENTION
[0012] The present invention relates to spiro compounds of formula I
[0013] Wherein
[0014] a is 1, 2, 3, 4 or 5;
[0015] b and c are each independently 1, 2, or 3;
[0016] When X and Y are selected from (i) X combines Y to be an oxygen or methylene, (ii) X is hydrogen, Y is hydrogen, (iii) X is hydrogen, Y is hydroxy or its optical isomer; R′ and R″ are not presented;
[0017] When X and Y are selected from (iv) X is hydrogen, Y is O, S or its optical isomer position, (v) X and Y are both O, or S, or (vi) X is O and Y is S; R′ and R″ are each independently halogeno-lower alkyl, lower alkyl, lower alkoxy, hydroxy, lower alkylhydroxy; optionally R′ and R″ combine to form a 5 to 7 membered ring with X, Y and the spiro carbon which ring, may be unsubstituted or substituted independently by up to three substituents;
[0018] R is selected from:
[0019] R a is selected from lower alkylenyl, lower alkenlenyl or lower alkynlenyl;
[0020] R b is selected from halogen, hydroxy, methanesulfonate, toluenesulfonate, aryl or heterocyclyl;
[0021] W is selected from O, S, —NR c or —CHR c ;
[0022] G is selected from N, —C—CN or —CR c ;
[0023] Z is selected from O, S, —NR d or —CHR d ;
[0024] R c is selected from H, lower alkyl;
[0025] R d is selected from H, lower alkyl, amino or alkylamino;
[0026] R 1 , R 3 , and R 4 are each independently selected from H, halogen, halogeno-lower alkyl, lower alkyl, lower alkoxy, lower alkoxyalkoxy, lower alkenyl, or lower alkynyl;
[0027] R 2 is selected from H, halogen, halogeno-lower alkyl or lower alkyl;
[0028] Or a pharmaceutically acceptable salt thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0029] The present invention is the direct to novel compounds which can inhibit protein tyrosine kinases, especially EGFR and VEGFR tyrosine kinases, and methods of use of these compounds for inhibition of tyrosine kinases in the treatment of a neoplastic or proliferative or inflammatory diseases, or transplantation disorders which are all caused by excess or inappropriate tyrosine kinases in a mammal in need thereof.
[0030] In a compound of formula I:
[0031] Wherein
[0032] a is 1, 2, 3, 4or5;preferably a is 1, 2or 3;
[0033] b and c are each independently 1, 2, or 3; preferably b and c are 1 or 2;
[0034] When X and Y are selected from (i) X combines Y to be an oxygen or methylene, (ii) X is hydrogen, Y is hydrogen, (iii) X is hydrogen, Y is hydroxy or its optical isomer; R′ and R″ are not presented; these moieties are selected from ketone, methylene as well as hydroxy and its optical isomers;
[0035] When X and Y are selected from (iv) X is hydrogen, Y is O, S or its optical isomer position, (v) X and Y are both O or S, or (vi) X is O and Y is S; R′ and R″ are each independently halogeno-lower alkyl, lower alkyl, lower alkoxy, hydroxy, lower alkylhydroxy; optionally R′ and R″ combine to form a 5 to 7 membered ring with X, Y and the spiro carbon which ring, may be unsubstituted or substituted independently by up to three substituents; preferably these moieties are selected from alkoxy or its optical isomers, and alkyl or cyclic ketal, thioketal, thioxolane which may be unsubstituted or substituted with lower alkyl, aryl or heterocyclyl;
[0036] R is selected from:
[0037] R a is selected from lower alkylenyl, lower alkenlenyl or lower alkynlenyl; preferably R a is lower alkylenyl;
[0038] R b is selected from halogen, hydroxy, methanesulfonate, toluenesulfonate, aryl or heterocyclyl; preferably R b is halogen or hydroxy;
[0039] W is selected from O, S, —NR c or —CHR c ; preferably W is O,
[0040] G is selected from N, —C—CN or —CR c ; preferably G is N;
[0041] Z is selected from O, S, —NR d or —CHR d ; preferably Z is O or —NR d ;
[0042] R c is selected from H, lower alkyl; preferably R c is H;
[0043] R d is selected from H, lower alkyl, amino or alkylamino; preferably R d is H;
[0044] R 1 , R 3 , and R 4 are each independently selected from H, halogen, halogeno-lower alkyl, lower alkyl, lower alkoxy, lower alkoxyalkoxy, lower alkenyl, or lower alkynyl; preferably R 1 , R 3 , and R 4 are each independently halogen, lower alkyl or lower alkoxy;
[0045] R 2 is selected from H, halogen, halogeno-lower alkyl or lower alkyl; preferably R 2 is H or fluorine;
[0046] Or a pharmaceutically acceptable salt thereof. The term “lower alkylenyl”, as used herein, unless otherwise indicated, includes 1 to 6 saturated —CH 2 —radicals.
[0047] The term “lower alkenlenyl”, as used herein, unless otherwise indicated, includes lower alkylenyl groups, as defined above, having at least one carbon-carbon double bond, such as —CH 2 —CH═CH—.
[0048] The term “lower alkynlenyl”, as used herein, unless otherwise indicated, includes lower alkylenyl groups, as defined above, having at least one carbon-carbon triple bond, such as —CH 2 —C≡C—.
[0049] The term “halogen”, as used herein, unless otherwise indicated, includes fluoro, chloro, bromo or iodo. Preferred halogens are fluoro, chloro and bromo.
[0050] The term “halogeno-lower alkyl”, as used herein, unless otherwise indicated, includes 1 to 6 halogen substituted lower alkyl, such as trifluoromethyl, pentafluoroethyl.
[0051] The term “lower alkyl”, as used herein, unless otherwise indicated, includes 1 to 6 saturated monovalent hydrocarbon radicals having straight or branched moieties, including, but not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, and the like.
[0052] The term “lower alkenyl”, as used herein, unless otherwise indicated, includes lower alkyl groups, as defined above, having at least one carbon-carbon double bond, such as —CH 2 —CH═CH 2 .
[0053] The term “lower alkynyl”, as used herein, unless otherwise indicated, includes lower alkyl groups, as defined above, having at least one carbon-carbon triple bond, such as —CH 2 —C≡CH.
[0054] The term “lower alkylhydroxy”, as used herein, unless otherwise indicated, includes-lower alkyl-OH groups wherein lower alkyl is as defined above The term “lower alkoxy”, as used herein, unless otherwise indicated, includes —O— lower alkyl groups wherein lower alkyl is as defined above.
[0055] The term “lower alkoxyalkoxy”, as used herein, unless otherwise indicated, includes —O— lower alkyl-O— lower alkyl groups wherein lower alkyl is as defined above, such as —OCH 2 CH 2 OCH 3 .
[0056] The term “aryl”, as used herein, unless otherwise indicated, includes an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, such as phenyl or naphthyl, preferably phenyl, and is unsubstituted or substituted by one or two substituents, selected from halogen, halogeno-lower alkyl, lower alkyl, lower alkenyl, lower alkynyl, cyano, lower alkylcyano, hydroxy, lower alkoxy, carboxy, carboxyalkyl, amino, carbamoyl, cabamate, ureido, mercapto, sulfo, lower alkysulfinyl, lower alkanesulfonyl, sulfonamide; aryl includes one aromatic ring fused with an aliphatic ring, such as a saturated or partially saturated ring, such as tetrahydronaphthyl.
[0057] The term “heterocyclyl”, as used herein, unless otherwise indicated, includes non-aromatic, single and fused rings suitably containing up to four heteroatoms in each ring, each of which independently selected from O, N and S, and which rings, may be unsubstituted or substituted independently by, for example, up to three substituents. Each heterocyclic ring suitably has from 4 to 7, preferably 5 or 6, ring atoms. A fused heterocyclic ring system may include carbocyclic rings and need include only one heterocyclic ring which may be partially saturated or saturated. The heterocyclyl includes mono, bicyclic and tricyclic heteroaromatic ring systems comprising up to four, preferably 1 or 2, heteroatoms each selected from O, N and S. Each ring may have from 4 to 7, preferably 5 or 6, ring atoms. A bicyclic or tricyclic ring system may include a carbocyclic ring. Carbocyclic ring includes cycloalkyl, cycloalkenyl or aryl ring. examples of heterocyclyl groups include but not limited: azetidine, pyrrolidine, pyrrolidione, piperidine, piperidinone, piperazine, morpholine, oxetane, tetrahydrofuran, tetrahydropyran, imidazolidine, pyrazolidine and hydantoin, pyrrole, indole, pyrazole, indazole, trizole, benzotrizole, imidazole, benzoimdazole, thiophene, benzothiophene, thiozole, benzothiozole, furan, benzofuran, oxazole, bezoxazole, isoxazole, tetrazole, pyridine, pyrimidine, trizine, quinoline, isoquinoline, quinazoline, indoline, indolinone, benzotetrahydrofuran, tetrahydroquinoline, tetrahydroisoquinoline, methylene-dioxyphenyl. The heterocyclic and heterocyclic rings may be optionally substituted and substituents selected from the group defined above as substituents for aryl.
[0058] Several in vitro tyrosine kinase inhibition activities can be measured according to the description in Rewcastle, G W, J. Med. Chem. 1996, 39, 918-928 and Edwards M, International Biotechnology Lab 5 (3), 19-25, 1987. Oncogene, 1990, 5: 519-524. The Baculovirus Expression System: A Laboratory Guide, L. A. King 1992. Sambrook et al, 1989, Molecular cloning-A Laboratory Manual, 2nd edition, Cold Spring Harbour Laboratory Press. O'Reilly et al, 1992, Baculovirus Expression Vectors-A Laboratory Manual, W. H. Freeman and Co, New York.
[0059] Receptor tyrosine kinase can be obtained in partially purified form from A-431 cells similar to those described by Carpenter et al., J. Biol. Chem., 1979, 254, 4884, Cohen et al., J. Biol. Chem., 1982, 257, 1523 and by Braun et al., J. Biol. Chem., 1984, 259, 2051. Some of these tests can also be contracted with Upstate Ltd for screening.
[0060] The following in vitro results are activities of some compounds in present invention against human tumor NSCLC A549 cell line and colon LOVO cell line in MTT assay.
A549 (IC50, nM) LOVO (IC50, nM) Example 20 0.0619 0.0375 Example 21 0.0421 0.139 Example 22 0.0359 0.0329 Example 23 0.0893 0.219 Example 24 0.0375 0.165 Example 25 0.0573 0.0954 Example 26 0.091 0.0376 Example 27 0.212 0.0978 Example 28 0.096 0.0376 Example 29 0.104 0.0934 Example 30 0.0749 0.0272 Example 31 0.0546 0.098 Example 32 0.028 0.032 Example 33 0.0519 0.118 Example 34 0.034 0.171 Example 35 0.0402 0.0318 Example 36 0.022 0.057 Example 37 0.132 0.0553 Example 38 0.073 0.143 Example 39 0.023 0.03 Example 40 0.042 0.029 Example 41 0.075 0.129
[0061] Animal antitumor activity testing can be conducted as follows:
[0062] The compounds were mixed with Tween 80 and 0.5% CMC as suspensions. Kunming male mice (19-21 g) were used. Ascitic fluid of mice HAC liver cancer was diluted with 0.9% NaCl solution (1:4), and injected 0.2 ml to each mouse subcutaneously. The whole animals (n=20) were separated evenly as test and control group randomly. The test group was administered drugs orally at 5-500 mg/Kg dosage once a day from second day after injection of tumor for seven days. The body weight of each animal was monitored everyday. The animals were sacrificed after ten days and each tumor was extracted and weighted for both groups and calculated the difference in percentage for antitumor activity.
[0063] The compounds were mixed with tween 80 and 0.5% CMC as suspensions. Nude female mice (17-19 g) were used. Ascitic fluid of human LOVO colon cancer was diluted with 0.9% NaCl solution (1:4), and injected 0.2 ml to each mouse subcutaneously. The whole animals (n=12) were separated even as test and control group randomly. The test group was administered drugs orally at 5-500 mg/Kg dosage once a day from second day after injection of tumor for eighteen days. The animals were sacrificed at 21st days and each tumor was extracted and weighted for both groups and calculated the difference in percentage for antitumor activity.
[0064] A compound of formula I can be administered alone or in combination with one or more other therapeutic agents, possible combination therapy taking the form of fixed combinations or administration of a compound of the invention and one or more other therapeutic agents being staggered or given independently of one another, or the combined administration of fixed combinations and one or more other therapeutic agents.
[0065] A compound of formula I can besides or in addition be administered especially for tumor therapy in combination with chemotherapy, radiotherapy, surgical intervention, or a combination of these. Long term therapy is equally possible as is adjuvant therapy in the context of other treatment strategies, as described above. Other possible treatments are therapy to maintain the patient's status after tumor regression, or even chemopreventive therapy, for example in patients at risk.
[0066] A compound according to the invention is not only for management of humans, but also for the treatment of other warm-blooded animals, for example of commercially useful animals. Such a compound may also be used as a reference standard in the test systems described above to permit a comparison with other compounds.
[0067] Salts are especially the pharmaceutically acceptable salts of compounds of formula I. Suitable pharmaceutically acceptable salts will be apparent to those skilled in the art and include those described in J. Pharm. Sci., 1977, 66, 1-19, such as acid addition salts formed with inorganic acid e.g. hydrochloric, hydrobromic, sulphuric, nitric or phosphoric acid; and organic acids e.g. succinic, maleic, acetic, fumaric, citic, tartaric, benzoic, p-toluenesulfonic, methanesulfonic or naphthalenesulfonic acid. Other salts may be used, for example in the isolation or purification of compounds of formula (I) and are included within the scope of this invention.
[0068] The compounds of this invention may be in crystalline or non-crystalline form, and, if crystalline, may optionally be hydrated or solvated. This invention includes within its scope stoichiometric hydrates as well as compounds containing variable amount of water.
[0069] The invention extents to all isomeric forms including stereoisomers and geometic isomers of the compounds of formula (I) including enantimers and mixtures thereof e.g. racemates. The different isomeric forms may be separated or resolved one from the other by conventional methods, or any given isomer may be obtained by conventional synthetic methods or by stereospecific or asymmetric syntheses.
[0070] Those skilled in the art will recognize various synthetic methodologies that may be employed to prepare non-toxic pharmaceutically acceptable prodrugs of the compounds encompassed by Formula I. Those skilled in the art will recognize a wide variety of non-toxic pharmaceutically acceptable solvents that may be used to prepare solvates of the compounds of the invention, such as water, ethanol, mineral oil, vegetable oil, and dimethylsulfoxide.
[0071] The compounds of general Formula I may be administered orally, topically, parenterally, by inhalation or spray or rectally in dosage unit formulations containing conventional non-toxic pharmaceutically acceptable carriers, adjuvants and vehicles. Oral administration in the form of a pill, capsule, elixir, syrup, lozenge, troche, or the like is particularly preferred. The term parenteral as used herein includes subcutaneous injections, intradermal, intravascular (e.g., intravenous), intramuscular, spinal, intrathecal injection or like injection or infusion techniques. In addition, there is provided a pharmaceutical formulation comprising a compound of general Formula I and a pharmaceutically acceptable carrier. One or more compounds of general Formula I may be present in association with one or more non-toxic pharmaceutically acceptable carriers and/or diluents and/or adjuvants and if desired other active ingredients. The pharmaceutical compositions containing compounds of general Formula I may be in a form suitable for oral use, for example, as tablets, troches, lozenges, aqueous or oily suspensions, dispersible powders or granules, emulsion, hard or soft capsules, or syrups or elixirs.
[0072] Compositions intended for oral use may be prepared according to any method known to the art for the manufacture of pharmaceutical compositions and such compositions may contain one or more agents selected from the group consisting of sweetening agents, flavoring agents, coloring agents and preserving agents in order to provide pharmaceutically elegant and palatable preparations. Tablets contain the active ingredient in admixture with non-toxic pharmaceutically acceptable excipients that are suitable for the manufacture of tablets. These excipients may be for example, inert diluents, such as calcium carbonate, sodium carbonate, lactose, calcium phosphate or sodium phosphate; granulating and disintegrating agents, for example, corn starch, or alginic acid; binding agents, for example starch, gelatin or acacia, and lubricating agents, for example magnesium stearate, stearic acid or talc. The tablets may be uncoated or they may be coated by known techniques to delay disintegration and absorption in the gastrointestinal tract and thereby provide a sustained action over a longer period. For example, a time delay material such as glyceryl monosterate or glyceryl distearate may be employed.
[0073] Formulations for oral use may also be presented as hard gelatin capsules wherein the active ingredient is mixed with an inert solid diluent, for example, calcium carbonate, calcium phosphate or kaolin, or as soft gelatin capsules wherein the active ingredient is mixed with water or an oil medium, for example peanut oil, liquid paraffin or olive oil. Aqueous suspensions contain the active materials in admixture with excipients suitable for the manufacture of aqueous suspensions. Such excipients are suspending agents, for example sodium carboxymethylcellulose, methylcellulose, hydropropylmethylcellulose, sodium alginate, polyvinylpyrrolidone, gum tragacanth and gum acacia; dispersing or wetting agents may be a naturally-occurring phosphatide, for example, lecithin, or condensation products of an alkylene oxide with fatty acids, for example polyoxyethylene stearate, or condensation products of ethylene oxide with long chain aliphatic alcohols, for example heptadecaethyleneoxycetanol, or condensation products of ethylene oxide with partial esters derived from fatty acids and a hexitol such as polyoxyethylene sorbitol monooleate, or condensation products of ethylene oxide with partial esters derived from fatty acids and hexitol anhydrides, for example polyethylene sorbitan monooleate. The aqueous suspensions may also contain one or more preservatives, for example ethyl, or n-propyl p-hydroxybenzoate, one or more coloring agents, one or more flavoring agents, and one or more sweetening agents, such as sucrose or saccharin.
[0074] Oily suspensions may be formulated by suspending the active ingredients in a vegetable oil, for example arachis oil, olive oil, sesame oil or coconut oil, or in a mineral oil such as liquid paraffin. The oily suspensions may contain a thickening agent, for example beeswax, hard paraffin or cetyl alcohol. Sweetening agents such as those set forth above, and flavoring agents may be added to provide palatable oral preparations. These compositions may be preserved by the addition of an anti-oxidant such as ascorbic acid.
[0075] Dispersible powders and granules suitable for preparation of an aqueous suspension by the addition of water provide the active ingredient in admixture with a dispersing or wetting agent, suspending agent and one or more preservatives. Suitable dispersing or wetting agents and suspending agents are exemplified by those already mentioned above. Additional excipients, for example sweetening, flavoring and coloring agents, may also be present.
[0076] Pharmaceutical compositions of the invention may also be in the form of oil-in-water emulsions. The oily phase may be a vegetable oil, for example olive oil or arachis oil, or a mineral oil, for example liquid paraffin or mixtures of these. Suitable emulsifying agents may be naturally-occurring gums, for example gum acacia or gum tragacanth, naturally-occurring phosphatides, for example soy bean, lecithin, and esters or partial esters derived from fatty acids and hexitol, anhydrides, for example sorbitan monoleate, and condensation products of the said partial esters with ethylene oxide, for example polyoxyethylene sorbitan monoleate. The emulsions may also contain sweetening and flavoring agents.
[0077] Syrups and elixirs may be formulated with sweetening agents, for example glycerol, propylene glycol, sorbitol or sucrose. Such formulations may also contain a demulcent, a preservative and flavoring and coloring agents.
[0078] The compounds may also be administered in the form of suppositories for rectal or vaginal administration of the drug. These compositions can be prepared by mixing the drug with a suitable non-irritating excipient which is solid at ordinary temperatures but liquid at the rectal or vaginal temperature and will therefore melt in the rectum or vagina to release the drug. Such materials include cocoa butter and polyethylene glycols.
[0079] The pharmaceutical compositions may be in the form of a sterile injectable aqueous or oleaginous suspension. This suspension may be formulated according to the known art using those suitable dispersing or wetting agents and suspending agents which have been mentioned above. The sterile injectable preparation may also be sterile injectable solution or suspension in a non-toxic parentally acceptable diluent or solvent, for example as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that may be employed are water, Ringer's solution and isotonic sodium chloride solution. In addition, sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose any bland fixed oil may be employed including synthetic mono- or diglycerides. In addition, fatty acids such as oleic acid find use in the preparation of injectables.
[0080] Compounds of the invention may also be administered transdermally using methods know to those skilled in the art (see, for example: Chien; “transdermal Controlled Systemic Medications”; Marcel Dekker, Inc.; 1987. Lipp et al. WO 94/04157 3Mar. 1994).
[0081] Compounds of general Formula I may be administered parenterally in a sterile medium. The drug, depending on the vehicle and concentration used, can either be suspended or dissolved in the vehicle. Advantageously, adjuvants such as local anesthetics, preservatives and buffering agents can be dissolved in the vehicle.
[0082] For administration to non-human animals, the composition may also be added to the animal feed or drinking water. It will be convenient to formulate these animal feed and drinking water compositions so that the animal takes in an appropriate quantity of the composition along with its diet. It will also be convenient to present the composition as a premix for addition to the feed or drinking water.
[0083] For all regimens of use disclosed herein for compounds of formula I, the daily oral dosage regimen will preferably be from 0.01 to 200 mg/Kg of total body weight. The daily dosage for administration by injection, including intravenous, intramuscular, subcutaneous and parenteral injections, and use of infusion techniques will preferably be from 0.01 to 200 mg/Kg of total body weight. The daily rectal dosage regimen will preferably be from 0.01 to 200 mg/Kg of total body weight. The daily vaginal dosage regimen will preferably be from 0.01 to 200 mg/Kg of total body weight. The daily topical dosage regimen will preferably be from 0.01 to 200 mg administered between one to four times daily. The transdermal concentration will preferably be that required to maintain a daily dose of from 0.01 to 200 mg/Kg. The daily inhalation dosage regimen will preferably be from 0.01 to 200 mg/Kg of total body weight.
[0084] It will be understood, however, that the specific dose level for any particular patient will depend upon a variety of factors including the activity of the specific compound employed, the age, body weight, general health, sex, diet, time of administration, route of administration, and rate of excretion, drug combination and the severity of the particular disease undergoing therapy.
[0085] Preferred compounds of the invention will have certain pharmacological properties. Such properties include, but are not limited to oral bioavailability, low toxicity, low serum protein binding and desirable in vitro and in vivo half-lives.
[0086] Assays may be used to predict these desirable pharmacological properties. Assays used to predict bioavailability include transport across human intestinal cell monolayers, including Caco-2 cell monolayers. Toxicity to cultured hepatocyctes may be used to predict compound toxicity. Penetration of the blood brain barrier of a compound in humans may be predicted from the brain levels of the compound in laboratory animals given the compound intravenously.
[0087] Serum protein binding may be predicted from albumin binding assays. Such assays are described in a review by Oravcova, et al. (Journal of Chromatography B (1996) volume 677, pages 1-27).
[0088] Compound half-life is inversely proportional to the frequency of dosage of a compound. In vitro half-lifes of compounds may be predicted from assays of microsomal half-life as described by Kuhnz and Gieschen (Drug Metabolism and Disposition, (1998) volume 26, pages 1120-1127).
[0089] Representative illustrations of the preparation of the present invention are given in Scheme I-Scheme II. Those having skill in the art will recognize that the starting materials may be varied and additional steps may be employed to produce compounds encompassed by the present invention.
[0090] The following examples selected from Formula I, but not limited, can be prepared similarly according to the methods described in Scheme I-Scheme II.
[0091] R is selected from: -----: Substituting position
[0092] In some cases protection of certain reactive functionalities may be necessary to achieve some of above transformations. In general the need for such protecting groups will be apparent to those skilled in the art of organic synthesis as well as the conditions necessary to attach and remove such groups. Those skilled in the art will recognize that in certain instances it will be necessary to utilize different solvents or reagents to achieve some of the above transformations.
[0093] The disclosures in this application of all articles and references, including patents, are incorporated herein by reference in their entirety.
[0094] The invention is illustrated further by the following examples, which are not to be construed as limiting the invention in scope or spirit to the specific procedures described in them.
[0095] The starting materials are and various intermediates may be obtained from commercial sources, prepared from commercially available organic compounds, or prepared using well know synthetic methods.
[0096] Representative methods for preparing intermediates of the invention are set forth below in the examples.
[0097] The following abbreviations have been used and others are all standard chemical formula representation.
EtOH: ethanol MeOH: methanol RT: room temperature TSA: n-Toluenesulfonic acid DIPEA: diisopropylethylamine DCM: Dichloro methane EtOAc: ethyl acetate DMF: N,N-dimethylformamide MsCl: Methanesulfonyl chloride TsOMe: methyl 4-methylbenzene- sulfonate eq: equivalent, g: gram, ml: milliliter μL: microliter (A) (B) 10-benzyl-5,8-Dioxa-10-azadispiro 5,8-Dioxa-10-azadispiro[2.0.4.3] [2.0.4.3]undecane undecane
EXAMPLE 1
10-(2-hydroxyethyl)-5,8-Dioxa-10-azadispiro[2.0.4.3]undecane
[0098] 10-benzyl-5,8-Dioxa-10-azadispiro[2.0.4.3]undecane (A) (1.0 g, similar prepared according to JMC 37, 3344) was mixed with Pd—C (10%, 600 mg) in EtOH (40 ml) and hydrogenated under H 2 at 50 psi for 5 hour. The reaction was filtered through Celite and evaporated to give 5,8-Dioxa-10-azadispiro[2.0.4.3]undecane (B).
[0099] The compound (B) (100 mg) was mixed with 2-Bromoethanol (100 mg) and K 2 CO 3 (120 mg) in Acetonitrile. The reaction was refluxed overnight and filtered, the filtrate was evaporated and purified on silica gel column to give the titled product. Mass: (M+1), 200
EXAMPLE 2
10-(3-hydroxypropyl)-5,8-Dioxa-10-azadispiro[2.0.4.3]undecane
[0100] The compound (B) (100 mg) was mixed with 3-Bromopropanol (120 mg) and K 2 CO 3 (120 mg) in Acetonitrile. The reaction was refluxed overnight and filtered; the filtrate was evaporated and purified on silica gel column to give the titled product. Mass: (M+1), 214
EXAMPLE 3
5-(2-hydroxyethyl)-5-azaspiro[2.4]heptan-7-one
[0101] The above product from Example 1 (100 mg) was mixed with 1N HCl (4 ml) and acetone (20 ml). The reaction was refluxed overnight and evaporated. The solution was basified with 2N NaOH and extracted with EtOAc. The combined organic layer was washed with H 2 O followed by brine, dried over Na 2 SO 4 and evaporated. The residue was purified by column chromatography to give title compound. Mass: (M+1), 156
EXAMPLE 4
5-(3-hydroxypropyl)-5-azaspiro[2.4]heptan-7-one
[0102] The title compound was prepared by similar manner to Example 3, starting from the compound of Example 2. Mass: (M+1), 170
EXAMPLE 5
5-(2-hydroxyethyl)-5-azaspiro[2.4]heptan-7-ol
[0103] 5-(2-Hydroxyethyl)-5-azaspiro[2.4]heptan-7-one (100 mg) was dissolved into Methanol (8 ml) and stirred at RT. NaBH 4 (100 mg) was added to the reaction and stirred at RT for 30 minutes. The reaction was evaporated and purified by column chromatography to give title compound. Mass: (M+1), 158
EXAMPLE 6
5-azaspiro[2.4]heptan-7-ol
[0104] 5-benzyl-5-azaspiro[2.4]heptan-7-one was prepared by similar manner to Example 3, starting from 10-benzyl-5,8-Dioxa-10-azadispiro[2.0.4.3]undecane (A). 5-benzyl-5-azaspiro[2.4]heptan-7-one (100 mg) then was dissolved into Methanol (8 ml) and stirred at RT. NaBH 4 (100 mg) was added to the reaction and stirred at RT for 30 minutes. The reaction was evaporated and purified by column chromatography to give 5-benzyl-5-azaspiro[2.4]heptan-7-ol (85 mg) that was mixed with Pd—C (10%, 100 mg) in EtOH (15 ml) and hydrogenated under H2 at 50 psi for 5 hour. The reaction was filtered through Celite and evaporated to give the title compound as an oil. Mass: (M+1), 115
EXAMPLE 7
2-(5-azaspiro[2.4]heptan-5-yl)ethanol
[0105] 5-benzyl-5-azaspiro[2.4]heptan-7-one (300 mg) was mixed with hydrazine (600 mg) and NaOH (300 mg) in H 2 O (2 ml). The mixture was refluxed for overnight and purified by column chromatography to give 5-benzyl-5-azaspiro[2.4]heptane that was hydrogenated at 50 psi with Pd—C (10%, 80 mg) in EtOH (15 ml) for overnight followed by filtration through Celite to give 5-azaspiro[2.4]heptane. This product was mixed with 2-Bromoethanol and K 2 CO 3 in Acetonitrile. The reaction was refluxed overnight and filtered, the filtrate was evaporated and purified on silica gel column to give the titled product. Mass: (M+1), 142
EXAMPLE 8
3-(5-azaspiro[2.4]heptan-5-yl)-1-propanol
[0106] The title compound was prepared by similar manner to Example 7, by use of 3-Bromopropanol. Mass: (M+1), 156
EXAMPLE 9
5-benzyl-7-methoxy-5-azaspiro[2.4]heptane
[0107] 5-Benzyl-5-azaspiro[2.4]heptan-7-ol (200 mg) was dissolved into DMF (4 ml) and cooled at 0° C. NaH (120 mg) was added to the reaction and stirred for 10 minutes. To the reaction was added TsOMe (200 mg), the solution was heated at 80° C. for two hours. The reaction was quenched with water and extracted with EtOAc followed by washing with water, then brine and dried over Na 2 SO 4 and evaporated to give the titled product. Mass: (M+1), 158
EXAMPLE 10
7-methoxy-5-azaspiro[2.4]heptane
[0108] The title compound was prepared by similar manner to Example 1, starting from the compound of Example 9. Mass: (M+1), 128
EXAMPLE 11
10-benzyl-5,8-Oxathiolane-10-azadispiro[2.0.4.3]undecane
[0109] 5-Benzyl-5-azaspiro[2.4]heptan-7-one (100 mg) was mixed with 2-Mercaptoethanol (300 mg) and TSA (10 mg) in Toluene. The reaction was refluxed overnight with a Dean-Stark adaptor. The reaction was washed with NaHCO 3 solution, evaporated and purified on silica gel column to give the titled product. Mass: (M+1), 262
EXAMPLE 12
5,8-Oxathiolane-10-azadispiro[2.0.4.3]undecane 10-benzyl-5,8-Oxathiolane-10-azadispiro[2.0.4.3]undecane (100 mg) was mixed with Pd—C (80 mg, 10%) and HCOONH 4 (110 mg) in EtOH. The reaction was refluxed for 1.5 hour and filtered through Celite and evaporated. The residue was washed through a layer of silica gel to give the titled product. Mass: (M+1), 172
EXAMPLE 13
5,9-Dioxa-11-azadispiro[2.0.4.3]dodecane
[0110] 5-Benzyl-5-azaspiro[2.4]heptan-7-one (100 mg) was mixed with 1,3-propanediol (200 mg) and TSA (10 mg) in Toluene. The reaction was refluxed overnight with a Dean-Stark adaptor. The reaction was washed with NaHCO 3 solution, evaporated and purified on silica gel column to give 11-benzyl-5,9-Dioxa-11-azadispiro[2.0.4.3]dodecane that was hydrogenated similarly to Example 1 to give the titled product. Mass: (M+1), 170
EXAMPLE 14
5,9-Dioxa-7,7-dimethyl-11-azadispiro[2.0.4.3]dodecane
[0111] The title compound was prepared by similar manner to Example 13, starting from the compound of 2,2-Dimethyl-1,3-propanediol. Mass: (M+1), 198
EXAMPLE 15
11-(2-hydroxyethyl)-5,9-Dioxa-11-azadispiro[2.0.4.3]dodecane
[0112] 5,9-Dioxa-11-azadispiro[2.0.4.3]dodecane (100 mg) was mixed with 2-Bromoethanol (100 mg) and K 2 CO 3 (120 mg) in Acetonitrile. The reaction was refluxed overnight and filtered, the filtrate was evaporated and purified on silica gel column to give the titled product. Mass: (M+1), 214
EXAMPLE 16
11-(2-hydroxyethyl)-5,9-Dioxa-7,7-dimethyl-11-azadispiro[2.0.4.3]dodecane
[0113] 5,9-Dioxa-7,7-dimethyl-11-azadispiro[2.0.4.3]dodecane (100 mg) was mixed with 2-Bromoethanol (100 mg) and K 2 CO 3 (120 mg) in Acetonitrile. The reaction was refluxed overnight and filtered, the filtrate was evaporated and purified on silica gel column to give the titled product. Mass: (M+1), 242
EXAMPLE 17
10-(3-amino-5-triflouro-phenyl)-5,8-Dioxa-10-azadispiro[2.0.4.3]undecane
[0114] 3-Bromo-5-trifouroaniline (200 mg) was mixed with DIPEA (1.5 eq) in DCM (10 ml) at 0° C. To the reaction was added benzylchloroformate (1.1 eq) and stirred at RT for one hour. The reaction was washed with water, brine and dried over Na 2 SO 4 then evaporated. The residue was purified by column chromatography to give the product (190 mg) that was mixed with 5,8-Dioxa-10-azadispiro[2.0.4.3]undecane (75 mg), Pd(dbda)3 16 mg), X-Phos (28 mg) and t-BuONa (50 mg) in toluene (15 ml). The reaction was heated at 60° C. overnight and evaporated and purified on silica gel column to give the 10-(3-CBZ-amino-5-triflouro-phenyl)-5,8-Dioxa-10-azadispiro[2.0.4.3]undecane (80 mg). This product was mixed with Pd—C (40 mg, 10%), HCOONH 4 (160 mg) and MeOH (10 ml). The reaction was refluxed for one hour and filtered through Celite and evaporated. The residue was mixed with water and extracted with EtOAc then purified with silica gel column to give the titled product. Mass: (M+1), 315
EXAMPLE 18
5-(3-amino-5-triflouro-phenyl)-5-azaspiro[2.4]heptan-7-one
[0115] The title compound was prepared by similar manner to Example 3, starting from the compound of Example 17. Mass: (M+1), 271
EXAMPLE 19
5-(3-amino-5-triflouro-phenyl)-5-azaspiro[2.4]heptan-7-ol
[0116] The title compound was prepared by similar manner to Example 5, starting from the compound of Example 18. Mass: (M+1), 273
EXAMPLE 20
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[3-(5,8-Dioxa-10-azadispiro[2.0.4.3]undecane) propoxy]quinazolin-4-amine
[0117] 2-Amino-4-methoxy-5-benzyloxybenzamide (JMC, 20, 146) (5 g) was mixed with triethylorthoformate (15 ml) and refluxed overnight. The reaction solution was cooled and triturated with EtOAc (40 ml) then filtered to give 7-methoxy-6-benzyloxyquinazolone (3.2 g). This product was mixed with DIPEA (15 ml) and to the solution was added POCl 3 (3 ml) slowly. The reaction mixture was refluxed for 30 minutes and cooled, then poured into a stirred mixture of ice and CHCl 3 . The solution was further extracted with CHCl 3 three times and washed with H 2 O followed by brine, dried over Na 2 SO 4 and evaporated to give a light brown solid as the chloride for next step without further purification.
[0118] The above chloride (2 g) was mixed with 3-chloro-4-flouroaniline (1.3 g) in 2-propanol (30 ml) and the reaction was refluxed for 2 hours and cooled to RT. The precipitate was filtered and mixed with TFA (4 ml) and refluxed for 1 hour. The solvent was evaporated under reduced pressure and the residue was washed with EtOAc to furnish N-(3-chloro4-fluorophenyl)-7-methoxy-6-hydroxy-quinazolin-4-amine (1.3 g) that was mixed with K 2 CO 3 (1.1 g) and 3-bromopropanol (850 μL) in DMF (5 ml). The reaction was heated at 80° C. overnight and poured into water and the precipitate was filtered to give N-(3-chloro4-fluorophenyl)-7-methoxy-6-(2-hydroxyethoxy)-quinazolin-4-amine (1 g). This hydroxy compound (350 mg) was mixed with DIPEA (350 μL) in DCM (10 ml) and cooled at 0° C, to the mixture was added MsCl (85 μL) and stirred for 2 hours. The reaction was evaporated with silica gel (2 g) and purified with silica gel column, then mixed with 5,8-Dioxa-10-azadispiro[2.0.4.3]undecane (B) (120 mg) and DIPEA (120 μL) in 2-propanol (10 ml). The reaction was refluxed overnight and evaporated then purified with silica gel column to give the titled product. Mass: (M+1), 515
EXAMPLE 21
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[2-(5,8-Dioxa-10-azadispiro[2.0.4.3]undecan)ethoxy]quinazolin-4-amine
[0119] The title compound was prepared by similar manner to Example 20, by using 2-bromoethanol instead of 3-bromopropanol. Mass: (M+1), 501
EXAMPLE 22
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[3-(5-azaspiro[2.4]heptan-7-one) propoxy]quinazolin-4-amine
[0120] The title compound was prepared by similar manner to Example 3, starting from the compound of Example 20. Mass: (M+1), 471
EXAMPLE 23
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[2-(5-azaspiro[2.4]heptan-7-one)ethoxy]quinazolin4-amine
[0121] The title compound was prepared by similar manner to Example 3, starting from the compound of Example 21. Mass: (M+1), 457
EXAMPLE 24
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[3-(5-azaspiro[2.4]heptan-7-ol)propoxy]quinazolin-4-amine
[0122] The title compound was prepared by similar manner to Example 5, starting from the compound of Example 22. Mass: (M+1), 473
EXAMPLE 25
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[2-(5-azaspiro[2.4]heptan-7-ol)ethoxy]quinazolin-4-amine
[0123] The title compound was prepared by similar manner to Example 5, starting from the compound of Example 23. Mass: (M+1), 459
EXAMPLE 26
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[3-(7-methoxy-5-azaspiro[2.4]heptane) propoxy]quinazolin4-amine
[0124] The title compound was prepared by similar manner to Example 9, starting from the compound of Example 24. Mass: (M+1), 487
EXAMPLE 27
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[2-(7-methoxy-5-azaspiro[2.4]heptane)ethoxy]quinazolin-4-amine
[0125] The title compound was prepared by similar manner to Example 9, starting from the compound of Example 25. Mass: (M+1), 473
EXAMPLE 28
N-(3-ethynylphenyl)-7-methoxy-6-[2-(5,8-Dioxa-10-azadispiro[2.0.4.3]undecane)ethoxy]quinazolin-4-amine
[0126] Ethylene glycol (30 ml) was mixed with pyridine (8 ml) and cooled at 0° C. To the mixture was added benzol chloride (7.5 ml) and stirred for 4 hours. The reaction was mixed with EtOAc and acidified with 2N HCl followed by washing with water, then brine and dried over Na 2 SO 4 and evaporated for next step without further purification.
[0127] The above product (4.6 g) was mixed with DIPEA (6.1 ml) in DCM (30 ml) and cooled at 0° C. for 15 minutes. MsCl (2.3 ml) was added into the solution and stirred for 40 minutes, the reaction was washed with NaHCO 3 solution followed by washing with water, then brine and dried over Na 2 SO 4 and evaporated to give the mesylate product for next step without further purification. Ethyl 3-hydroxy-4-methoxybenzonate (3.4 g) was mixed with above mesylate product and K 2 CO 3 in DMF (20 ml), the reaction was heated at 80° C. for two hours. The solvent was removed under reduced pressure and extracted with EtOAc followed by washing with water, then brine and dried over Na 2 SO 4 and evaporated to give 3-(2-benzoyloxy)ethoxy-4-methoxy-ethyl benzoate (4 g) for next step without further purification.
[0128] The above benzoate (2.5 g) was dissolved into acetic acid (4 ml) and stirred at 0° C. To the reaction was added HNO 3 (60%, 8 ml) and stirred at 0° C. for 15 minutes, then stirred at RT for 30 minutes. The reaction was poured into ice-water and the precipitate was filtered to give a yellow solid that was mixed with Iron powder (2 g) and NH 4 Cl (250 mg) in EtOH (30 ml). The reaction was refluxed for 2 hours and filtered through Celite and evaporated, then extracted with EtOAc followed by washing with water, then brine and dried over Na 2 SO 4 and evaporated to give ethyl 2-amino4-methoxy-5-(2-benzoyloxy)ethoxy benzoate (2 g) for next step without further purification. This benzoate compound (2 g) was mixed with HCOONH 4 (1.5 g) in HCONH 2 (3 ml) and heated at 170° C. overnight. The reaction was cooled and poured into water (15 ml) and the solid was filtered and dried at 120° C. for 4 hours, then it was mixed with DIPEA (10 ml) and to the solution was added POCl 3 (2 ml) slowly. The reaction mixture was refluxed for 30 minutes and cooled, then poured into a stirred mixture of ice and CHCl 3 . The solution was further extracted with CHCl 3 three times and washed with H 2 O followed by brine, dried over Na 2 SO 4 and evaporated to give 6-(2-benzoyloxy)ethoxy-7-methoxy-4-chloro quinazoline for next step without further purification.
[0129] The above chloride (1 g) was mixed with 3-ethynylaniline (0.5 g) in 2-propanol (10 ml) and the reaction was refluxed for 2 hours and cooled to RT. The precipitate was filtered and mixed with KOH (500 mg), H 2 O (1 ml) and MeOH (10 ml), then stirred at RT overnight. The reaction was evaporated and extracted with EtOAc followed by washing with water, then brine and dried over Na 2 SO 4 and purified with silica gel column to give N-(3-ethynylphenyl)-7-methoxy-6-(2-hydroxy)ethoxy-quinazolin-4-amine (400 mg). This compound (350 mg) was mixed with DIPEA (350 μL) in DCM (10 ml) and cooled at 0° C., to the mixture was added MsCl (85 μ) and stirred for 2 hours. The reaction was evaporated with silica gel (2 g) and purified with silica gel column, then mixed with 5,8-Dioxa-10-azadispiro[2.0.4.3]undecane (B) (120 mg) and DIPEA (120 μL) in 2-propanol (10 ml). The reaction was refluxed overnight and evaporated then purified with silica gel column to give the titled product. Mass: (M+1), 473
EXAMPLE 29
N-(3-ethynylphenyl)-7-methoxy-6-[2-(5-azaspiro[2.4]heptan-7-one)ethoxy]quinazolin-4-amine
[0130] The title compound was prepared by similar manner to Example 3, starting from the compound of Example 28. Mass: (M+1), 429
EXAMPLE 30
N-(3-ethynylphenyl)-7-methoxy-6-[2-(5-azaspiro[2.4]heptan-7-ol)ethoxy]quinazolin-4-amine
[0131] The title compound was prepared by similar manner to Example 5, starting from the compound of Example 29. Mass: (M+1), 431
EXAMPLE 31
N-(3-trifluoromethylphenyl)-7-methoxy-6-[2-(5,8-Dioxa-10-azadispiro[2.0.4.3]undecane)ethox quinazolin-4-amine
[0132] The title compound was prepared by similar manner to Example 21, by using 3-triflouromethylaniline instead of 3-chloro-4-flouroaniline. Mass: (M+1), 517
EXAMPLE 32
N-(3-bromophenyl)-7-methoxy-6-[2-(5,8-Dioxa-10-azadispiro[2.0.4.3]undecane)ethoxy]quinazolin-4-amine
[0133] The title compound was prepared by similar manner to Example 21, by using 3-bromoaniline instead of 3-chloro-4-flouroaniline. Mass: (M+1), 527
EXAMPLE 33
N-(3,4-dichlorophenyl)-7-methoxy-6-[2-(5,8-Dioxa-10-azadispiro[2.0.4.3]undecane)ethoxy]quinazolin4-amine
[0134] The title compound was prepared by similar manner to Example 21, by using 3,4-dichloroaniline instead of 3-chloro-4-flouroaniline. Mass: (M+1), 517
EXAMPLE 34
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[3-(5,8-Oxathiolane-10-azadispiro[2.0.4.3]undecane)propoxy]quinazolin-4-amine
[0135] The title compound was prepared by similar manner to Example 11, starting from the compound of Example 22. Mass: (M+1), 515
EXAMPLE 35
N-(2-fluoro-4-bromophenyl)-6-methoxy-7-[3-(5,8-Dioxa-10-azadispiro[2.0.4.3]undecane)propoxy]quinazolin-4-amine
[0136] The title compound was prepared by similar manner to Example 20, starting from the compound of 2-Amino-5-methoxy-4-benzyloxybenzamide (JMC, 20, 146) and using 2-fluoro-4-bromoaniline. Mass: (M+1), 559
EXAMPLE 36
N-(2-fluoro-4-bromophenyl)-6-methoxy-7-[2-(5,8-Dioxa-10-azadispiro[2.0.4.3]undecane)ethoxy]quinazolin-4-amine
[0137] The title compound was prepared by similar manner to Example 35, by using 2-bromoethanol. Mass: (M+1), 545
EXAMPLE 37
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[2-(5,8-Oxathiolane-10-azadispiro[2.0.4.3]undecane)ethoxy]quinazolin-4-amine
[0138] The title compound was prepared by similar manner to Example 34, starting from the compound of Example 23. Mass: (M+1), 517
EXAMPLE 38
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[2-(5,9-Dioxa-11-azadispiro[2.0.4.3]dodecane)ethoxy]quinazolin-4-amine
[0139] The title compound was prepared by similar manner to Example 13, starting from the compound of Example 23. Mass: (M+1), 515
EXAMPLE 39
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[2-(5,9-Dioxa-7,7-dimethyl-11-azadispiro[2.0.4.3]dodecane)ethoxy]quinazolin4-amine
[0140] The title compound was prepared by similar manner to Example 14, starting from the compound of Example 23. Mass: (M+1), 543
EXAMPLE 40
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[3-(5,9-Dioxa-11-azadispiro[2.0.4.3]dodecane)propoxy]quinazolin-4-amine
[0141] The title compound was prepared by similar manner to Example 13, starting from the compound of Example 22. Mass: (M+1), 529
EXAMPLE 41
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[3-(5,9-Dioxa-7,7-dimethyl-11-azadispiro[2.0.4.3]dodecane)propoxy]quinazolin-4-amine
[0142] The title compound was prepared by similar manner to Example 14, starting from the compound of Example 22. Mass: (M+1), 557
EXAMPLE 42
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[3-(5-azaspiro[2.4]heptane)propoxy]quinazolin-4-amine
[0143] This compound was prepared by similar manner to Example 20, by using 5-azaspiro[2.4] heptane instead of 5,8-Dioxa-10-azadispiro[2.0.4.3]undecane (B). Mass: (M+1), 457
EXAMPLE 43
N-(3-chloro-4-fluorophenyl)-7-methoxy-6-[2-(5-azaspiro[2.4]heptane)ethoxy]quinazolin-4-amine
[0144] This compound was prepared by similar manner to Example 21, by using 5-azaspiro[2.4] heptane instead of 5,8-Dioxa-10-azadispiro[2.0.4.3]undecane (B). Mass: (M+1), 443
EXAMPLE 44
5-benzyl-7-methylene-5-azaspiro[2.4]heptane
[0145] 5-benzyl-5-azaspiro[2.4]heptan-7-one (300 mg) was dissolved into anhydrous tetrahydrofuran (10 ml) and Nysted reagent (1.5 eq, 20% solution) was added to the reaction. The reaction was stirred at RT for two days and quenched with NH 4 Cl solution and extracted with EtOAc followed by washing with water, then brine and dried over Na 2 SO 4 and purified with silica gel column to give the titled compound. Mass: (M+1), 200
EXAMPLE 45
7-methylene-5-azaspiro[2.4]heptane
[0146] The title compound was prepared by similar manner to Example 12, starting from the compound of 5-benzyl-7-methylene-5-azaspiro[2.4]heptane. Mass: (M+1), 110
EXAMPLE OF SALT FORMATION
[0147] Compound from example 20 (100 mg) was dissolved into EtOAc (1 ml) and to the solution was added 2N HCl/Ether solution (0.5 ml). The solution was evaporated to give a off white solid as its HCl salt.
[0148] The other pharmaceutical acceptable salts, such as hydrobromic, sulphuric, nitric, phosphoric acid; or succinic, maleic, acetic, fumaric, citic, tartaric, benzoic, p-toluenesulfonic, methanesulfonic, naphthalenesulfonic acid salt can be prepared in the similar manner.
EXAMPLE OF FORMULATION
[0149] The following are the examples of the formulations and these are purely illustrative and in no way to be interpreted as restrictive.
FORMULATION EXAMPLE 1
[0150] Each capsule contains:
Compound Example 20 100.0 mg Corn starch 23.0 mg Calcium carboxymethyl cellulose 22.5 mg Hydroxypropylmethyl cellulose 3.0 mg Magnesium stearate 1.5 mg 150.0 mg
FORMULATION EXAMPLE 2
[0151] A solution contains:
Compound Example 20 1 to 10 g Acetic acid or sodium hydroxide 0.5 to 1 g Ethyl p-hydroxybenzoate 0.1 g Purified water 88.9 to 98.4 g 100.0 g
FORMULATION EXAMPLE 3
[0152] A powder for admixing with feedstuff contains:
Compound Example 20 1 to 10 g Corn starch 98.5 to 89.5 g Light anhydrous silicic acid 0.5 g 100.0 g | The present invention relates to spiro compounds of formula I, processes for their preparation, pharmaceutical compositions containing them as active ingredient, methods for the treatment of disease states such as cancers associated with protein tyrosine kinases, especially epidermal growth factor (EGF) and vascular endothelial growth factor (VEGF), to their method of use as medicaments and to their method of use in the manufacture of medicaments for use in the production of inhibition of tyrosine kinase reducing effects in warm-blooded animals such as humans. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of application Ser. No. 12/487,489, filed Jun. 18, 2009.
BACKGROUND
[0002] Lacerations and other wounds which compromise the integrity of the skin are common enough that most people have experienced them, from the mundane, such as a skinned knee, to the life-threatening, such as a stab wound or a serious burn. Many breaks to the skin raise the possibility of disfigurement through scarring.
[0003] The development of scar tissue is a defensive response to an injury in that it repairs a breach in the skin, eliminating a site of potential infection and reinjury. However, the rampant formation of scar tissue can result in a tough dermal surface lacking the color or consistency of the surrounding skin. Because the flexibility and elasticity of scar tissue differs from that of natural skin, scar tissue can ultimately limit the lives of those who are affected. Scar tissue is generally tougher than the skin tissue in the surrounding area. This is especially true of scar tissue where the skin is subjected to deformation and elastic stresses, such as on or behind the knee or elbow. Such areas can be subject to tear at the skin/scar tissue border. Scar tissue, particularly new scars, covering areas having natural grooves to facilitate bending, such as the lines on the palms of the hands, are often weak at these flex lines. Stretching caused by opening and closing the hand can rupture the scar tissue at these natural grooves, resulting in an accumulation of scar tissue on either side of the groove, causing newly formed tissue in the groove even to have even greater susceptibility to tearing with hand motion. In general, the natural topography of a wound site can increase the likelihood of retearing, resulting in long healing times.
[0004] The lack of flexibility and suppleness of scar tissue is complicated by the fact that scarred areas can become naturally contracted during and after formation as the scar becomes thick, leathery, and inelastic. As a result, the motion of those who have extensive skin injury, such as burn victims, can be severely restricted. A severely burned hand can become frozen in a grasp. Scar tissue due to burns around the waist can prevent torsional motions that most people take for granted.
[0005] Some preparations for treating wounds are formulated to have a positive effect on the properties of the scar tissue formed during healing. For example, some wound dressings have functions such as reducing wound drying and preventing ultraviolet light exposure. Such formulations can prevent repeated cracking and drying, resulting in, among other things, the formation of scar tissue having improved flexibility, elasticity and color characteristics relative to scar tissue formed in the absence of the formulation.
[0006] Some formulations are made of strictly organic materials, such as gels. Gels have properties which make them suitable as wound dressings. They can cool wounds by contacting them directly, yet keep them free from contamination. Another useful property of gels is their consistency: many gels are similar to skin in elasticity and deformability, and they can bend, bunch and stretch with the skin and tissue surfaces to which they are attached without causing tearing or stress at the site of the healing wound.
[0007] However, gels can dry out rapidly with time, break down structurally and/or chemically, and they generally must be reapplied, which can be a painful process for the patient, especially if the consistency of the dressing has become stiff due to drying. Some gels can absorb moisture, developing a soft or liquid consistency. Once the gel consistency has been compromised, the potential for bacterial infection increases.
[0008] Siloxane gels have been found to be generally superior to other types of gel products in the treatment of wounds and scar tissue. Siloxane gels function by forming a silicone-based polymer matrix over a wound site. Polymer precursors, such as dimethicone, dimethicone crosspolymer, and other siloxanes, are contained in a spreadable preparation which is applied to a wound site. Some polymer precursor formulations include fumed silica. The preparation also contains a volatile component which begins to evaporate upon the application of the preparation to a wound site. The polymer matrix begins to form upon the evaporation of volatile compounds from the spreadable preparation. The preparations are, in many cases, thixotropic, particularly if the formulation contains fumed silica. Thixotropic formulations change from a stiff consistency to a fluid-like consistency upon the application of stress, such as application to a wound, and revert to a stiffer, less fluid consistency once the stress is removed. This property gives siloxane gel precursor formulations the ability to spread easily into a relatively thin layer over a wound and remain in place without oozing away from the wound site, all with a minimum of stress and shear at the wound site.
[0009] Another advantage of siloxane gels is that some have been shown to have a beneficial effect on the properties of scar tissue as it is being formed, diminishing the degree of scarring and improving the texture of scar tissue that does form, such that the ultimate appearance of the healed wound is more like surrounding skin. For instance, some siloxane preparations, when applied to developing or newly formed scar tissue, have demonstrated the ability to cause excellent fading, and even near disappearance of the scar with constant application.
[0010] Unlike other spreadable preparations on the market for aiding in the healing of wounds, once a degree of polymerization has taken place to form the siloxane polymer matrix, the resultant gel generally has the ability to retain its consistency over time. Furthermore, the unapplied product can be easier to store and use than other types of gels because it can be applied as siloxane polymer matrix precursors which do not “set” until after application.
[0011] Because siloxane gels have such beneficial effects upon developing scar tissue, it is desirable that such a preparation also have the ability to include additives which impart additional useful functions to the gel. For example, while the foregoing silicone-based formulations demonstrate superior scar reduction properties, developing scar tissue is susceptible to change in color and/or texture, as well as other types of damage, such as thermal damage, upon exposure to ultraviolet and other wavelengths of radiation. It is thus desirable to incorporate sun screening compounds into the formulation which will be retained upon matrix formation. Furthermore, burns and other injuries which are best served by the topical application of gels can continue to be very painful, even after the wound has begun to scar over. However, the application of the matrix forming preparation can prevent the topical application of pain relievers: unlike bandage-type coverings, most topical gels cannot be simply lifted and resituated. It can thus desirable that matrix forming preparations comprise at least one pain alleviating compound.
[0012] Unfortunately, the use of siloxane matrix precursors has severely limited the variety of additives which can be included in silicone wound dressings. Many desirable additives are not readily solvated in the mix of matrix precursors, such as dimethicone and other siloxanes which comprise the spreadable preparation. For example, many effective and commonly used sunscreen additives, such as, for example, Octocrylene, Octinoxate, Octisalate and Oxybenzone may not sufficiently dissolve in the pre-polymerized preparation. Other examples of desirable additives having poor solubility in the pre-polymerization preparation include cortisone-type compounds which reduce pain and inflammation, such as, for example, Hydrocortisone acetate.
[0013] A method exploiting the advantages of siloxane matrix-forming wound preparations, yet allowing the inclusion of otherwise insoluble additives in silicone wound dressing formulations would be welcomed as a significant advance in the art of wound dressing preparation.
BRIEF DESCRIPTION OF THE INVENTION
[0014] It has been found, surprisingly, that the use of certain volatile coagents (in addition to the volatile component) with certain actives, which are otherwise of limited or no solubility in the matrix precursors, enables the incorporation of the actives into a silicone matrix. This is all the more surprising in that the complex which enables the incorporation of the active into the forming matrix actually retains a good degree of volatility, even though complexed with the active, and even though it would be expected that the developing matrix would hinder the ability of the complexed coagent to evaporate. Surprisingly, the volatile coagent is not incorporated within the matrix with the active. Instead, the insoluble active, which is insoluble in the matrix precursors without the coagent, remains incorporated within the matrix during its formation, even though the volatile coagent does not remain complexed to the active, but disjoins and is lost to evaporation. Even more surprising, the active can have mobility within the matrix resulting in the ability to migrate through the gel to the wound site, as evidenced by the effectiveness of analgesic additives. Furthermore, it would be expected that the vapor pressure of the volatile coagent would be reduced upon complexing with the active, and by being incorporated, with the active, within the developing siloxane matrix. Yet it retains sufficient vapor pressure such that it can evaporate away cleanly. The use of volatile coagents, such as those identified herein, permits the incorporation of diverse additive types into silicone matrix-forming formulations. The present invention enables the incorporation of insoluble actives into a mixture of silicon precursors, greatly extending the usefulness of siloxane gel wound healing technology.
DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 —Drying test results. The lowest, middle and highest curves graphically depict the drying results of the sunscreen, analgesic and control gels respectively.
DETAILED DESCRIPTION OF THE INVENTION
Siloxane Matrix Precursors
[0016] The matrix forming composition of the present invention comprises siloxane matrix precursors, a volatile component, an active component, and a volatile coagent. The volatile component and volatile coagent partially or fully evaporate from the composition once the composition is applied to a wound or scar site, leaving behind 1) components which participate in matrix formation as well as 2) one or more active components which reside in the matrix. Generally, the components which participate in the matrix formation are one or more siloxanes, one or more of which have organic characteristics, i.e., comprising organic components, such as bearing hydrocarbyl groups. Preferred are polydimethylsiloxanes such as dimethicone and dimethicone cross polymer. A polymer matrix can be formed with the use of other polydimethyl siloxanes instead of or in addition to dimethicone and dimethicone crosspolymer. In particular, it is believed that polymerization involving other polysiloxanes, and in particular, other dialkylpolysiloxanes, can form a matrix exhibiting the advantages of the present invention when used with the volatile components, volatile coagents and actives listed below. Such matrices are within the ambit of the present invention. The fumed silica gives the prepolymerized composition a thixotropic consistency. Fumed silica also participates structurally in the gel, but its contribution to or participation in the polymerization process, if any, is unclear. Provided that a volatile component is present, the matrix precursors in the preparation generally can be stored at room temperature (25 K) for extended periods of time, such as 1, 2, 4, 6, 12 months or even longer without undergoing significant polymerization. It is preferred that the matrix precursors comprise a crosspolymer component, such as dimethicone crosspolymer, as well as dimethicone. In some embodiments, the siloxane component is present in weight percentages in the range of from about 25 to 60 wt %. In preferred embodiments, the siloxane component is present in the range of from 30 to 50 wt %. In more preferred embodiments, the siloxane component is present in amounts in the range of from about 35 to 45 wt %. The preferred siloxane component is dimethicone. The cross polymer component is preferably present in amounts in the range of from about 0.5 to about 8 wt %, and more preferably in the range of from about 1.5 to 5 wt %.
Volatile Component
[0017] The composition of the present invention comprises a volatile component (distinguished from volatile coagent, discussed below). The volatile component generally begins to vaporize upon application of the composition to the wound site. In some embodiments, the formation of the siloxane matrix can begin immediately upon commencement of evaporation, proceeding with further evaporation. In other embodiments, the siloxane matrix begins to form appreciably at some time during the evaporation of the volatile component, with only negligible formation prior to the time. In preferred embodiments, the volatile component has limited or no participation in polymerization, but readily solvates or dissolves in the matrix precursors. Preferred examples are volatile siloxane compounds which have little or no participation as reactants in siloxane polymerization. For example, cyclic siloxanes generally exhibit good solvation and volatility characteristics in siloxanes, and their participation in matrix formation is generally relatively low due to the fact that all silane oxygen atoms are unavailable for polymerization. More preferred is a cyclopentasiloxane which bears constituents comprising hydrogen or hydrocarbyl groups of less than four carbon atoms. Constituents comprising hydrogen or hydrocarbyl groups of one carbon atom are most preferred. Preferred amounts of volatile component are in the range of from about 12 to about 45 wt %. More preferred are amounts in the range of from about 15 to 28 wt %, most preferred are amounts in the range of from about 20 to 25 wt %.
[0018] The volatile component is preferably present in amounts such that the volatile component is more than 50 percent evaporated after 15 minutes at one or more temperatures in the range of from about 30 to 40 C.
[0019] In general, the volatile component functions such that upon its partial or entire evaporation, the polymer matrix begins to form. Thus, in some embodiments, the presence of the volatile can act to fully or partially inhibit the polymerization process, such that upon beginning to volatilize, the rate of polymerization increases. In general, the composition of the present invention is not limited to the compounds specifically described above, but broadly comprises compounds which can be used in relative amounts such that they fully or partially inhibit the formation of the siloxane matrix prior to wound application, but begin to evaporate upon the application of the preparation to a wound, having fully or partially evaporated by the completion of siloxane matrix formation. In some embodiments, the volatile component evaporation plateaus with time prior to complete evaporation. In other embodiments, the evaporation of the volatile component continues after the siloxane matrix is completely formed. It is preferable that the volatile component evaporate to within less than 5% of its original weight (storage concentration) within 3 hours, but in some embodiments, the volatile evaporates to within greater than 10, 20 and 30% of its original weight within 3 hours. In some embodiments, the weight percent of the volatile component concentration prior to use and during storage is in the range of from about 5 to about 40%. In other embodiments, the weight percent of the volatile component concentration prior to use and during storage is in the range of from about 15 to about 35%, In preferred embodiments, the volatile component concentration prior to use and during storage is in the range of from about 18 to about 30%.
Actives and Volatile Coagent
[0020] The wound healing preparation of the present invention comprises a volatile coagent. Without desiring to be bound by theory, it is thought that the volatile coagent aids in solvating the active in the matrix precursors. It has been found that certain compounds which function as volatile coagents with certain actives have the ability to volatilize appreciably despite the facts that they are chemically associated with the active which is surrounded by a growing matrix, and which itself is not ultimately volatilized.
[0021] Many common ultraviolet absorbers are not readily soluble in solutions comprising siloxane matrix precursors. However, it has been found that many ultraviolet absorbers can be solvated in siloxane matrix precursor solutions in the presence of myristate esters. For example, well known Escalol ultraviolet absorbers, having the following diverse structures can be introduced into siloxane matrices:
Octocrylene (ISP Escalol 597):
[0022]
Octinoxate (ISP Escalol 557):
[0023]
Octisalate (ISP Escalol 587):
[0024]
Oxybenzone (ISP Escalol 567):
[0025]
[0026] In one embodiment, the active is an ultraviolet absorbing compound comprising at least one aromatic ring. In a more preferred embodiment the active comprises one or more Escalol compounds, available from ISP Chemicals, and the volatile coagent is an ester of 1) a linear acid having a carbon chain length in the range of from about 6 to 13 carbon atoms and 2) methanol, ethanol, or a secondary alcohol having a total carbon content in the range of from about 3 to about 8 carbon atoms. In a more preferred embodiment, the volatile coagent is a myristate ester of methanol, ethanol, or a secondary alcohol having a total carbon content in the range of from about 3 to about 8 carbon atoms, and the active is an Escalol compound. In a yet more preferred embodiment, the volatile coagent is isopropyl myristate, and the active is Octocrylene (ISP Escalol 597), Octinoxate (ISP Escalol 557), Octisalate (ISP Escalol 587), or Oxybenzone (ISP Escalol 567). The sunscreen active or actives present in the formulation can be present in a combined amount in the range of from about 5 to 40 wt %, with amounts in the range of from 15 to 35 wt % being more preferable. In some embodiments, the sunscreen actives are present in amounts in the range of from 25 to 30 wt %.
[0027] In general, the volatile coagent preferably comprises an ester of 1) a linear acid having a carbon chain length in the range of from about 6 to 13 carbon atoms and 2) methanol, ethanol, or a secondary alcohol having a total carbon content in the range of from about 3 to about 8 carbon atoms; and more preferably isopropyl myristate; a glycol comprised of a linear chain of three or more carbons and one or more hydroxyl groups; and wherein all hydroxyl groups are on adjacent carbons including an end carbon; and more preferably pentylene glycol; or a substituted or unsubstituted isosorbide; and preferably Dimethyl isosorbide.
[0028] Many common anti-inflammatory compounds are based on the steroid compound structure. It has been found that some steroids having low solubility in solutions of siloxane matrix precursors can be solvated in siloxane matrix precursor solutions in the presence of glycol and/or isosorbide compounds.
[0029] In one embodiment, the active is a steroid compound, and the volatile coagent is a glycol comprised of a linear chain of three or more carbons and one or more hydroxyl groups; and wherein all hydroxyl groups are on adjacent carbons including an end carbon. In a more preferred embodiment, the volatile coagent is a glycol comprised of a linear chain of from about 3 to 7 carbons and two hydroxyl groups, one attached to each terminal carbon, and the active is a steroid compound. In a yet more preferred embodiment, the volatile coagent is pentylene glycol, and the active is dihydrocortisone acetate.
[0030] In one embodiment, the active is a steroid compound, and the volatile coagent comprises a substituted or unsubstituted isosorbide. In a more preferred embodiment, the active is a cortisone, and the volatile coagent comprises a disubstituted isosorbide. In a yet more preferred embodiment, the volatile coagent is dimethyl isosorbide and the active is dihydrocortisone acetate.
[0031] In one embodiment, the active is a hydrocortisone compound and actives comprising both a glycol compound and an isosorbide compound are used. In a preferred compound, the active is Hydrocortisone acetate.
[0032] The steroid compound is preferably present in an amount which is in the range of from 0.1 to 8 wt %. More preferred is an amount in the range of from about 0.5 to 3 wt %.
[0033] The glycol and the isosorbide are present in amounts in the range of from 5 to 40 wt % percent (combined weight, if both are present). In preferred embodiments, both are present, each in amounts in the range of from 5 to 50 wt %. In other embodiments, the glycol and the isosorbide are present in amounts in the range of from 0 to 15 wt %, with a total weight % in the range of from 10 to 25.
[0034] It should be noted that the glycol and isosorbide components can be used with sunscreen actives instead of isopropyl myristate if a deeper penetration is desired.
[0035] The composition of the present invention can be prepared by mixing together the matrix precursors such as, for example, fumed silica, dimethicone and dimethicone cross polymer; and the volatile component, such as, for example, cyclopentasiloxane. The foregoing compounds can be mixed together to form a siloxane base. The active component is generally mixed with the volatile coagent to form a mixture which is added to the siloxane base before introducing it into the balance of the composition. In one embodiment, the base contains only cyclopentasiloxane and dimethicone crosspolymer. The mixture is then combined with the base. In general, it is desirable to premix the active with the volatile coagent. However, in some cases, it can be permissible to combine the volatile coagent with all ingredients except the active, adding the active to the preparation in a final step.
Example 1
30 SPF Sunscreen Scar Gel
[0036] Scar Gel with 10.0% Octocrylene, 7.5% Octinoxate, 5.0% Octisalate, 6.0% Oxybenzone, 8.0% isopropyl myristate, 36% dimethicone, 3.5% fumed silica, 2% dimethicone crosspolymer and 22% cyclopentasiloxane. All percentages wt/wt. Octocrylene, Octinoxate, Octisalate and Oxybenzone provide UVA and UVB resistance. They were premixed with isopropyl myristate. The mixture was added to a combination of cyclopentasiloxane and dimethicone crosspolymer. Fumed silica was added next to the overall mixture using a high-shear mixing process (an eductor). The dimethicone is added last, and the mixture is mixed until homogeneous, resulting in a viscous, opaque gel, with no lumps or visible separation. The formulation has an SPF rating of 30 or higher. A drying test was performed (time take to reach a constant weight) (see FIG. 1 ), and the formulation dried in essentially the same amount of time as the formulation in the absence of the Octocrylene, Octinoxate, Octisalate, Oxybenzone and isopropyl myristate (control formulation). The addition of the sunscreen additives does not appreciably slow the drying of the formulation.
Example 2
Hydrocortisone Acetate Scar Gel
[0037] Scar Gel with 1.0% hydrocortisone acetate, 5.0% propylene glycol, 8.0% dimethyl isosorbide, 12.0% pentylene glycol, 45.0% dimethicone, 3.0% fumed silica, 2.0% dimethicone crosspolymer, and 24.0% cyclopentasiloxane. All percentages are wt/wt. The hydrocortisone acetate was pre-mixed into the pentylene glycol, dimethyl isosorbide and propylene glycol and warmed slightly to obtain good mixing before adding to a main batch. The main batch was prepared using a high-shear mixing apparatus (an eductor). No lumps or visible particles were observed. The resulting batch was uniform and slightly opaque. A drying test was performed (see FIG. 1 ), and the formulation dried in essentially the same amount of time as the formulation in the absence of the dihydrocortisone acetate, propylene glycol and dimethyl isosorbide (control formulation). The addition of the pain/itch reliever does not appreciably slow the drying of the formulation.
Example 3
Experimental Details of the Drying Tests
“30 SPF Sunscreen Silicone Scar Gel” Details
[0038] The “30 SPF Sunscreen Silicone Scar Gel,” described in Example 1, above, contains the ingredients of the Control Formula Scar Gel” with the addition of the following FDA approved sunscreen actives: 10.0% Octocrylene, 7.5% Octinoxate, 5.0% Octisalate and 6.0% Oxybenzone. Also, 8.0% of Isopropyl Myristate, an emollient ester, was added as a dispersing agent.
“1% Hydrocortisone Acetate Silicone Scar Gel” Details
[0039] The “1% Hydrocortisone Acetate Silicone Scar Gel,” described in Example 2, above, contains the ingredients of the Control Formula Scar Gel” with the addition of 1% w/w of Hydrocortisone Acetate, an FDA approved anti-inflammatory agent. Also, 5.0% of Propylene Glycol (a humectant and skin conditioning agent) and 10.0% of Dimethyl Isosorbide, a solvent which is a dimethyl ether of an anhydride of an isomer of sorbitol, used for better skin penetration of the Hydrocortisone Acetate.
Procedure:
[0040] The 30 plastic weigh boats were labeled and accurately weighed on an O'Haus EP114 analytical balance. Samples of the Control Formula Scar Gel” were spread out in a thin film on ten plastic weigh boats and the initial weights recorded (T=0). The samples were placed into the Lunaire Environmental Chamber set at 35° C. then removed and weighed at 5, 10, 40, 60, 180, 240, 300 and 1440 minute intervals. The process was repeated for the “30 SPF Sunscreen Silicone Scar Gel” and the “1% Hydrocortisone Acetate Silicone Scar Gel”. The results of the comparative study are listed below in TABLE 1—Control Formula Scar Gel Evaporation Study Results; TABLE 2—30 SPF Sunscreen Silicone Gel Evaporation Study Results and TABLE 3—1% Hydrocortisone acetate Silicone Gel Evaporation Study Results. The data from each table has been tabulated and displayed graphically in FIG. 1 .
Equipment Used:
[0041] (30) 5.25″×3.50″×1.0″ plastic weigh boats
(1) Calibrated O'Haus EP114 Explorer Pro analytical balance
(1) Lunaire Environmental Chamber Model # GE0932M-4 set at 35° C.
Results
[0042]
[0000]
TABLE 1
Control Formula Scar Gel
Evaporation Study Results
Empty Weigh
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Boat
T = 0
T = 5
T = 10
T = 40
T = 60
T = 180
T = 240
T = 300
T = 1440
(g)
(g)
(g)
(g)
(g)
(g)
(g)
(g)
(g)
(g)
KCG Sample 1
3.1621
3.3948
3.3888
3.3863
3.3786
3.3723
3.2731
3.2722
3.2722
3.2715
KCG Sample 2
3.2660
3.3410
3.3385
3.3358
3.3286
3.3278
3.3075
3.3052
3.3031
3.3015
KCG Sample 3
3.5625
3.6590
3.6570
3.6555
3.6472
3.6430
3.6074
3.6067
3.6067
3.6067
KCG Sample 4
3.4816
3.5715
3.5669
3.5621
3.5523
3.5500
3.5213
3.5200
3.5198
3.5201
KCG Sample 5
3.5648
3.6670
3.6596
3.6549
3.6450
3.6412
3.6140
3.6140
3.6132
3.6121
KCG Sample 6
3.5218
3.6102
3.6050
3.5910
3.5660
3.5630
3.5600
3.5599
3.5558
3.5558
KCG Sample 7
3.3741
3.4565
3.4500
3.4459
3.4308
3.4244
3.4101
3.4099
3.4098
3.4098
KCG Sample 8
3.4364
3.4865
3.4849
3.4828
3.4738
3.4688
3.4585
3.4580
3.4583
3.4568
KCG Sample 9
3.4109
3.4724
3.4698
3.4684
3.4585
3.4547
3.4391
3.4383
3.4382
3.4383
KCG Sample 10
3.4674
3.5153
3.5137
3.5113
3.5032
3.4953
3.4903
3.4888
3.4889
3.4888
Note:
“T” equals the time interval, in minutes, at which the weights were determined.
[0000]
TABLE 2
30 SPF Sunscreen Silicone Scar Gel
Evaporation Study Results
Empty Weigh
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Boat
T = 0
T = 5
T = 10
T = 40
T = 60
T = 180
T = 240
T = 300
T = 1440
(g)
(g)
(g)
(g)
(g)
(g)
(g)
(g)
(g)
(g)
SSG Sample 1
3.3015
3.4060
3.4032
3.4035
3.3963
3.3931
3.3799
3.3799
3.3793
3.3760
SSG Sample 2
3.6727
3.7753
3.7735
3.7723
3.7651
3.7619
3.7477
3.7477
3.7474
3.7438
SSG Sample 3
2.9276
3.0600
3.0568
3.0574
3.0490
3.0449
3.0259
3.0256
3.0255
3.0215
SSG Sample 4
3.2265
3.3601
3.3571
3.3548
3.3453
3.3410
3.3224
3.3230
3.3230
3.3200
SSG Sample 5
3.2729
3.4094
3.4000
3.3956
3.3829
3.3796
3.3595
3.3598
3.3601
3.3599
SSG Sample 6
3.3635
3.5084
3.5008
3.4980
3.4815
3.4768
3.4557
3.4500
3.4490
3.4700
SSG Sample 7
3.5379
3.6744
3.6721
3.6699
3.6617
3.6579
3.6396
3.6380
3.6373
3.6340
SSG Sample 8
3.7732
3.8523
3.8514
3.8498
3.8426
3.8399
3.8312
3.8307
3.8307
3.8275
SSG Sample 9
3.0460
3.1585
3.1567
3.1549
3.1472
3.1434
3.1301
3.1292
3.1292
3.1260
SSG Sample 10
2.9573
3.0348
3.0333
3.0318
3.0254
3.0221
3.0151
3.0142
3.0140
3.0100
Note:
“T” equals the time interval, in minutes, at which the weights were determined.
[0000]
TABLE 3
1% Hydrocortisone Acetate Silicone Scar Gel
Evaporation Study Results
Empty Weigh
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Weight at
Boat
T = 0
T = 5
T = 10
T = 40
T = 60
T = 180
T = 240
T = 300
T = 1440
(g)
(g)
(g)
(g)
(g)
(g)
(g)
(g)
(g)
(g)
HAG Sample 1
3.1592
3.3599
3.3561
3.3524
3.3365
3.3373
3.3089
3.2583
3.2580
3.2582
HAG Sample 2
3.3183
3.4122
3.4094
3.4063
3.3935
3.3874
3.3742
3.3688
3.3642
3.3639
HAG Sample 3
3.4812
3.5898
3.5860
3.5827
3.5672
3.5611
3.5361
3.5380
3.5380
3.5353
HAG Sample 4
3.5457
3.6612
3.6580
3.6559
3.6394
3.6318
3.6052
3.6058
3.6054
3.6032
HAG Sample 5
3.4292
3.5117
3.5086
3.5071
3.4935
3.4881
3.4719
3.4742
3.4742
3.4751
HAG Sample 6
3.6278
3.7158
3.7118
3.7085
3.6952
3.6885
3.6712
3.6716
3.6723
3.6723
HAG Sample 7
3.5343
3.6615
3.6587
3.6554
3.6400
3.6314
3.6007
3.6030
3.6018
3.6002
HAG Sample 8
3.3502
3.4862
3.4820
3.4778
3.4624
3.4536
3.4204
3.4221
3.4204
3.4201
HAG Sample 9
3.5731
3.7100
3.7070
3.7048
3.6927
3.6831
3.6450
3.6450
3.6450
3.6449
HAG Sample 10
3.4784
3.5971
3.5942
3.5890
3.5806
3.5707
3.5412
3.5430
3.5410
3.5392
Note:
“T” equals the time interval, in minutes, at which the weights were determined.
Calculations
[0043] The Percent Weight Loss values were calculated as follows:
[0000]
%
Weight
Loss
=
(
Wght
.
at
T
=
0
-
Wght
.
of
Empty
Weigh
Boat
)
-
(
Wght
.
at
T
=
n
-
Wght
.
of
Empty
Weigh
Boat
)
(
Wght
.
at
T
=
0
-
Wght
.
of
Empty
Weigh
Boat
)
×
100
[0044] Where n is the weight recorded at times of 5, 10, 40, 60, 180, 240, 300 and 1440 minutes.
[0045] Example: The percent weight loss for “1% Hydrocortisone Acetate Silicone Gel at T=5 minutes would be determined accordingly.
[0000]
%
Weight
Loss
=
(
3.3599
g
-
3.1592
g
)
-
(
3.3561
g
-
3.1592
g
)
(
3.3599
g
-
3.1592
g
)
×
100
=
1.8934
%
[0046] The Percent Weight Loss values were averaged for each of the three products at the appropriate time interval (5, 10, 40, 60, 180, 240, 300 and 1440) and displayed in graphically, see FIG. 1 .
Conclusion
[0000]
1. The Control Formula Scar Gel, the “30 SPF Sunscreen Silicone Scar Gel” and the “1% Hydrocortisone Acetate Silicone Scar Gel” all reached relatively stable dried weights at the 180 minute mark.
Example 4
Experimental Details of the SPF Tests
[0000]
Title: Evaluation of the Static Sun Protection Factor (SPF) of a Sunscreen-Containing Formula
Objective: To measure the Static SPF of an over-the-counter (OTC) sunscreen-containing formula and the 8% Homosalate Standard (HMS) in human volunteers according to the FDA Final Monograph
Test Product: Test Formulation—Expected SPF 30
Study Design: Non-randomized, with blinded evaluations
Results: Five subjects completed the test. The mean SPF of the test product, Test Formulation, was 33.1 (n=5, SD=2.0). The test product would be likely to meet FDA Final Monograph requirements for labeling as Static SPF 30+. 1
Adverse Experiences: No Adverse Experiences were reported
Summary:
[0054] On the first day of the study each subject received a series of UV doses from a xenon arc solar simulator to an unprotected site on the mid-back. On the second day the minimal erythema dose (MED) was determined as the lowest UV dose which produced mild erythema reaching the borders of the exposure site. Then 100 mg of the test product and 100 mg of the HMS standard were applied to separate, adjacent 50 cm2 areas of the mid-back (8% Homosalate (HMS) Standard provided by Cosmetech Laboratories, Inc., Fairfield, N.J.).
[0055] The test product had an expected SPF of 30 and the HMS standard sunscreen had an expected SPF of 4. After a 15-minute drying period UV doses ranging from 0.76 to 1.32 times the product of the MED and 30 were administered to the test sunscreen-protected area. UV doses ranging from 0.64 to 1.56 times the product of the MED and 4 were administered to the HMS standard sunscreen-protected area. A series of UV doses were also administered to a second unprotected site. On the third day the MED was determined for the sunscreen-protected sites and the unprotected site. The SPF of each sunscreen was calculated as the ratio of the MED for each sunscreen-protected site to the final MED.
[0056] Detailed procedures for determining the Static Sun Protection Factor according to the FDA Sunscreen Monograph) are described in the PROTOCOL.
[0057] Details of calibrations for Lamps 1, 2, 7, 8, 10, 13 and 14 are shown in the LAMP CALIBRATIONS.
[0058] According to the FDA Final Monograph), the labeled SPF must be calculated as follows:
[0000] Labeled SPF=Mean SPF Value−A Rounded down to the nearest whole number
[0000] For SPF values>31, the test product may be labeled as SPF 30+
Where
[0000]
A=ts/sqrt(n) and represents the 95% confidence interval.
t=upper 5% of student's t distribution
s=Standard Deviation
n=Number of Subjects
[0063] For the panel to be valid, the SPF of the HMS standard sunscreen must fall within the standard deviation range of the expected SPF (i.e. 4.47±1.279) and the 95% confidence interval for the mean SPF of the HMS standard sunscreen must contain the value 4.
Results:
[0064] Five subjects, 2 men and 3 women, who provided written, informed consent, completed the study. Subjects who completed all procedures included 2 with skin type I, 2 with skin type II and 1 with skin type III.1 Ages ranged from 21 to 38 years and the mean age was 30.4 (n=5, SD=7.1). Subject demographic and static SPF results are listed in Table 1.
[0065] The mean static SPF of the test product, Test Formulation, was 33.1 (n=5, SD-2.0). The mean SPF of the HMS standard was 4.4 (n=5, SD=0.4).
Protocol Deviation:
[0066] Protocol Deviations were reported for Subject 04. The Repeat MED and Final SPF evaluations were performed outside of the 22 to 24 hour time frame (21:50 and 21:54 respectively). This Protocol Deviation did not affect study results.
Enrollment:
[0067] Subject 03 was disqualified during Day 1 procedures for a prohibited medication and Subjects 05 and 06 were disqualified due to procedural error. Data for these subjects were not included in this report.
[0000] TABLE 1 Subject Demographic and Static SPF Data for Test Formulation and HMS Standard SRL2008-105: Formulated Solutions, LLC HMS Test HMS Subject SRL Skin Final MED Formulation Standard #* ID# Age Sex Type Lamp (sec) SPF SPF 01 1792 21 F I 8 10 34.50 4.40 02 1702 27 F II 2 10 32.10 4.00 04 373 38 M II 10 10 30.00 4.40 07 1803 29 M III 1 13 34.54 4.38 08 895 37 F I 2 8 34.50 5.00 Mean = 30.4 Mean = 33.1 Mean = 4.4 SD = 7.1 SD = 2.0 SD = 0.4 n = 5 n = 5 n = 5
Subject 03 disqualified—prohibited med
Subject 05 disqualified—procedural error
Subject 06 disqualified—procedural error
Conclusion:
[0068] The test product, Reference Test Formulation, would be likely to meet the FDA Final Monograph requirements for labeling as Static SPF 30+. 1
REFERENCES
[0000]
1. U.S. Food and Drug Administration. Sunscreen Drug Products for Over-the-Counter Human Use; Final Monograph; 21CRF Parts 310, 352, 700 and 740. Federal Register 64 (98) May 21, 1999. pp. 27666-27693
Protocol
[0000]
Objective: To measure the static sun protection factor (SPF) of an over-the-counter (OTC) sunscreen-containing formula according to the FDA Final Monograph 1
Test Product: Expected SPF 30
Study Design: Non-randomized, with blinded evaluations
Subjects: Five qualified male and/or female volunteers with the skin types I, II and/or III1 will be completed for the test product. With permission from the Sponsor, up to 20 additional subjects may be enrolled to complete requirements for FDA Final Monograph testing. 1
Introduction:
[0074] The FDA Final Monograph) describes the procedures for determining the Static sun protection factor. The Static SPF is defined by the ratio of the minimal erythema dose of ultraviolet radiation for sunscreen-protected skin to that for unprotected skin. The minimal erythema dose (MED) is the dose of ultraviolet (UV) radiation that produces mild erythema (sunburn) with clearly defined borders, 22 to 24 hours after administration. Timed UV radiation doses were administered using a xenon arc lamp that simulated solar radiation. The technician monitored the output of the solar simulator using a calibrated radiometer to insure that the erythemally effective irradiance was constant. Readings of erythemally effective irradiance were recorded.
Objective:
[0075] The objective of this test was to measure the Static SPF of an over-the-counter (OTC) sunscreen-containing formula according to the FDA Final Monograph 1 .
Design:
[0076] This was a non-randomized study with blinded evaluations.
Subjects:
[0077] Subjects included up to 25 healthy male and female volunteers completed per product with skin types I, II and/or III 1 (See below).
[0000]
Erythema and Tanning Reactions
Skin Type
to First Sun Exposure in Sprinq*
I
Always burns easily; never tans
II
Always burns easily; tans minimally
III
Burns moderately; tans gradually
IV
Burns minimally; always tans well
*Subject-reported responses to 1 hour of summer sun exposure
[0078] Subjects reported any OTC or prescription medication used within the week before and during study participation. Subjects also satisfied the following criteria:
Inclusion Criteria:
[0000]
At least 18 years old, providing legally effective, written informed consent
Willing and able to keep study appointments and follow instructions
Good general health
Willing to avoid sun and tanning lamp exposure during the study
Exclusion Criteria:
[0000]
History of abnormal response to UV radiation or sensitivity to any ingredient of the test products
Sunburn, suntan, active dermal lesions, uneven skin tones or any condition such as nevi, blemishes or moles that might interfere with study procedures
Use of any medication that might affect study results, e.g. photosensitizers, antihistamines, analgesics or anti-inflammatory drugs
Pregnancy, nursing or any condition that might increase the risk of study participation
Tanning bed or tanning lamp exposure in the last 3 months
Study Procedures:
[0088] All procedures (product application, UV doses and evaluations) were performed with the subjects in the same position.
Day 1:
Subject Enrollment
[0089] Prospective subjects reported to the testing laboratory and received a complete explanation of study procedures. If they desired to participate and agreed to the conditions of the study, subjects signed a written, witnessed consent form and a permission to release personal health information form, and provided a brief medical history. The back, between the belt-line and shoulder blades, were examined for uneven skin tones and blemishes, using a Woods lamp. The technician completed the Subject History Form and qualified subjects were enrolled in the study. Subject numbers were assigned in the order of study enrollment.
MED Dose Administration
[0090] A timed series of 5 UV doses, increasing in 25 percent increments, were administered to the mid-back, just below the shoulder blades and above the belt-line. UV doses for the MED, the time doses were completed and lamp readings were recorded on the MED form.
[0091] Subjects were instructed to avoid UV exposure, photosensitizers, analgesics, antihistamines and anti-inflammatory medications and to return to the testing laboratory 22 to 24 hours after completion of UV doses.
Day 2:
MED Determination
[0092] Subjects returned to the testing laboratory within 22 to 24 hours after completion of MED doses for evaluation of responses and were questioned non-directively to assess compliance, to identify concomitant medications and to monitor for adverse experiences. A trained evaluator graded responses of the UV exposed sites, under warm fluorescent or tungsten illumination of 450 to 550 lux, using the grading scale shown in Table 1.
[0000]
TABLE 1
Grading Scale for Erythema Responses to UV Doses
Administered to Untreated Sites and Sunscreen Treated Sites
0
No erythemal response
1
Minimally perceptible erythema
2
Mild erythema with clearly defined borders
3
Moderate erythema with sharp borders*
4
Dark red erythema with sharp borders*
5
Dark red erythema with sharp borders and possible edema*
6
Intense erythema with sharp borders and edema*
*If moderate, dark red or intense erythema did not reach borders of exposed site, an explanation was to be provided in the comments section of evaluation forms
[0093] The MED was determined as the first exposure site in the series that produces an erythema grade of at least 2 (Mild erythema with clearly defined borders). The progression of erythema grades was to be consistent with the UV doses administered.
[0094] If there were pronounced tanning responses, the subject was to be considered likely Type IV and not qualified for the study. In this case the subject was to be dropped from the study and replaced. Grades for each UV-exposed site, any comments and the evaluation time were recorded.
[0095] If required for practical scheduling, the subject was permitted to leave the testing laboratory at this point and return within one week for completion of Day 2 procedures.
Application of Products for SPF Determination
[0096] If the study participation of the subject has been interrupted, the subject was to be questioned non-directively to assess compliance, identify concomitant medications and monitor for adverse experiences.
[0097] The study technician drew 50 cm 2 rectangles in the designated locations on the subject's back between the belt-line and shoulder blades using a template and an indelible marker. The technician then applied 100 mg of test product in its designated rectangle and 100 mg of the HMS standard in an adjacent rectangle. The sunscreens were applied by “spotting” the material across the area and gently spreading, using a finger cot, until a uniform film is applied to the entire area.
[0098] The technician documented product formula designations, test site locations and application time.
UV Doses for Static SPF Determinations
[0099] After at least 15 minutes, the technician administered a series of 7 progressively increasing, timed UV doses to the sites treated with the test products. The dose series was determined by the product of the expected SPF of each test product, the subject's MED and the following number:
[0000]
Multiple of Subject's MED and Expected SPF (SPF > 15)
0.76
0.87
0.93
1.00
1.07
1.15
1.32
[0100] The technician documented UV doses, times completed and lamp effective irradiance readings for each test product.
UV Doses for the HMS Standard
[0101] At least 15 minutes after the application of the HMS standard, the technician administered 7 progressively increasing timed UV doses to the HMS standard site. The dose series was determined by the product of the HMS standard SPF (4), the subject MED and the following numbers:
[0000]
Multiple of Subject MED and HMS Standard (SPF = 4)
0.64
0.80
0.90
1.00
1.10
1.25
1.56
[0102] The technician documented the UV doses for the HMS standard, time completed and the lamp effective irradiance reading.
UV Doses for Repeat MED Determination
[0103] The technician administered a timed series of 5 UV doses, increasing by 25 percent increments, to an unprotected area of the mid-back. The series of 5 doses included the original MED in the center as follows:
[0000]
Multiple of Original MED
0.64
0.80
1.00
1.25
1.56
[0104] UV doses for the repeat MED, time completed and the lamp effective irradiance were recorded.
[0105] The technician instructed subjects to return to the testing laboratory for evaluation within 22 to 24 hours after completion of the UV doses for the static SPF, HMS standard SPF and the repeat MED.
Day 3:
Evaluation of Responses to UV Doses for Static SPF and Repeat MED
[0106] Subjects returned to the testing laboratory and were questioned non-directively to assess compliance, to identify concomitant medications and to monitor for adverse experiences. A trained evaluator, who did not participate in product applications or administration of UV doses graded all sites that received UV doses, using the scale shown in Table 1. The technician who applied the test product and administered the UV doses was permitted to assist the evaluator, but the technician not permitted to influence the evaluator in the grading of UV responses. Grades of the responses of all sunscreen-treated sites were recorded.
SPF Computation:
[0107] The technician determined the repeat MED as above and computed the SPF values for each subject.
[0108] The final MED was to be the repeat MED, unless the repeat MED could not be determined. In that case the initial MED would be used as the final MED.
[0109] SPF values were calculated as the ratio of the MED for sunscreen-protected sites to the final MED.
[0110] The labeled SPF were calculated as follows, based on 20 subjects:
[0000] Mean SPF Value−A(rounded down to nearest whole number)
Where
[0000]
A=ts/sqrt(n)
t=upper 5% of student's t distribution
s=Standard Deviation
n=Number of Subjects
[0115] For the panel to be valid the SPF of the HMS standard sunscreen must fall within the standard deviation range of the expected SPF (i.e. 4.47±1.279) and the 95% confidence interval for the mean SPF of the HMS standard sunscreen must contain the value 4.
Adverse Experiences:
[0116] Any adverse experiences were to be documented in the subject file and immediate medical attention obtained if appropriate. Any serious adverse experience defined as life-threatening or requiring emergency measures was to be reported to the sponsor within 24 hours. All adverse experiences were to be reported to the sponsor.
Replacement of Subjects:
[0117] Any subject disqualified due to non-compliance or adverse experience was to be replaced. Subjects whose data did not permit successful computation of SPF values were to be replaced.
REFERENCES
[0000]
1. U.S. Food and Drug Administration. Sunscreen Drug Products for Over-the-Counter Human Use; Final Monograph; 21CRF Parts 310, 352, 700 and 740. Federal Register 64 (98) May 21, 1999. pp. 27666-27693
[0000]
LAMP CALIBRATIONS
Apr. 17, 2008
Calibration of Lamps 1, 2, 7, 8, 10 and 14 (Calibration Date)
Lamp 1 S/N
Lamp 2 S/N
Lamp 7 S/N
Lamp 8 S/N
Lamp 10 S/N
Lamp 14 S/N
4533 Filter
4534 Filter
9533 Filter
9560 Filter
9655 Filter
11476 Filter
010806 Bulb
05144 Bulb
080105 Bulb
121805 Bulb
081806C Bulb
07072-2 Bulb
Requirements
322470
322474
323771
323769
323774
323006
Colipa 2006
FDA 2007
Range (nm)
(Jan. 19, 2008)
(Apr. 07, 2008)
(Apr, 16, 2008)
(Apr. 16, 2008)
(Apr. 14, 2008)
(Dec. 9, 2007)
[1] %
[2] %
Relative % contribution to erythemal effectiveness
<290
0.01
0.00
0.087%
0.012%
0.019%
0.01
<0.1
<0.1
290-300
5.8
4.7
6.7%
6.5%
4.7%
7.1
1.0-8.O
46.0-67.0
290-310
60.6
56.5
61.8%
60.4%
56.7%
62.7
49.0-65.0
29D-320
89.2
86.3
89.3%
87.5%
86.8%
89.0
85.0-90.0
80.0-91.0
290-330
94.3
92.1
94.1%
93.1%
92.5%
93.9
91.5-95.5
86.5-95.5
290-340
96.3
94.5
96.0%
95.6%
94.8%
95.8
94.0-97-0
90.5-97.0
290-350
97.7
96.5
97.4%
97.4%
96.7%
97.4
—
93.5-98.6
290-400
100.0
100.0
99.9%
100.0%
100.0%
100.0
99.9-100
93.5-100.0
Ratios (%)
UVAII/UV
26.5
23.3
25.3
30.2%
25.3
24.6
≧20
—
UVAI/UV
62.0
68.0
64.6
60.9%
64.6
65.4
≧60
—
Absolute Values
Total Power
98
111
96
128
138
147
<150
<150
(mw/cm 2 ) | Disclosed is 1) a method for greatly increasing the solubility of useful actives in siloxane matrix-forming preparations, and 2) the associated preparations, themselves. Volatilizing coagents are utilized to give novel gels containing heretofore siloxane-insoluble additives. | 0 |
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