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BACKGROUND
[0001] Various types of devices may be used to prevent or defend against flooding of areas or structures. Many such devices, such as traditional sand bags, may be filled with materials and stacked to create a wall or barrier against flood waters. However, sand bag barriers require inordinate amounts of labor to create large flood protection barriers that require tall barriers or barriers that extend laterally for protracted lengths. The present invention is a bag designed for emergency flood protection by an individual consumer, such that it can be easily deployed, filled, and positioned. The present invention provides for ease of use by the consumer, such that the consumer can fill the bag at a rapid rate and position the bag is a safer manner than other flood protection bag currently on the market. Additionally, the present invention can be can be broken down by the consumer by use of an opening component on the bottom of the bag and therefore constitutes a one-piece, reusable flood bag.
BRIEF DESCRIPTION OF THE DRAWINGS
[0002] Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
[0003] FIG. 1 is an overhead perspective view of an exemplary deployment of a series of seventeen flood bag devices in an in-use configuration comprising a wall of the devices that provide a barrier against flood waters in accordance with various embodiments of the present disclosure.
[0004] FIG. 2 is a perspective view of the linear configuration of FIG. 1 showing the attachment of multiple flood bag devices to other flood bags by means of a series of straps integrated into the front face of the bags in accordance with various embodiments of the present disclosure.
[0005] FIG. 3 is a perspective view of a variation of the configuration of FIG. 2 showing the attachment of multiple flood bag devices to other flood bags by additional means of hook-and-loop fasteners, such as Velcro®, in accordance with various embodiments of the present disclosure.
[0006] FIG. 4 is a close-up perspective view of the exemplary configurations of FIG. 2 and FIG. 3 showing a detail of the connection of multiple flood bag devices in accordance with various embodiments of the present disclosure.
[0007] FIG. 5 is a perspective view of an individual flood bag from the configurations of FIG. 1 , FIG. 2 , FIG. 3 and FIG. 4 showing the various side, bottom and neck panels of the bag.
[0008] FIG. 6 is a perspective view of the individual flood bag shown in FIG. 5 showing the various side and bottom dimensions.
[0009] FIG. 7 is a perspective view of another individual flood bag from the configurations of FIG. 1 , FIG. 2 , FIG. 3 and FIG. 4 showing a closed aperture on the bottom of the bag in accordance with various embodiments of the present disclosure.
[0010] FIG. 8 is a perspective view of the individual flood bag shown in FIG. 7 and further showing the opening of the aperture on the bottom of the bag that allows the contents of the bag to be emptied by way of the opened aperture in accordance with various embodiments of the present disclosure.
[0011] FIG. 9 is an overhead perspective view from a removed distance of several sets of configurations of the flood bag devices shown in FIG. 1 that are conjoined to form a protracted wall of the devices in accordance with various embodiments of the present disclosure.
[0012] FIG. 10 is an overhead perspective view from a removed distance of several sets of configurations of the flood bag devices shown in FIG. 1 that are conjoined to form a protracted wall of the devices in a curved alignment in accordance with various embodiments of the present disclosure.
DETAILED DESCRIPTION
[0013] The present disclosure generally relates to apparatus, devices, and systems for providing protection of areas and structures from flood waters. More specifically, the present disclosure discloses an apparatus that can be readily deployed, easily filled and attached to like apparatuses to create a floodwater barrier of a desired lateral length. In addition, each apparatus can be easily emptied and removed from the barrier to be reused in a subsequent application.
[0014] In the following discussion, a general description of the embodiments of a flood bag apparatus for creating a variable-length flood barrier is provided. With reference to FIG. 1 , shown is a drawing of an example of an exemplary deployment of a series of seventeen flood bag devices [ 101 ] in an in-use configuration. As depicted in FIG. 1 , each flood bag [ 101 ] is aligned with an adjoining flood bag and releasably connected to another flood bag to create a configured barrier or wall [ 102 ] of flood bags. The wall [ 102 ] of flood bags [ 101 ] provides an extended barrier against flood waters. In some embodiments, the wall [ 102 ] of flood bags [ 101 ] may be positioned on a slope of terrain above potentially encroaching flood waters.
[0015] Referring next to FIG. 2 , shown is a detailed perspective view of the linear configuration of FIG. 1 showing the attachment of multiple flood bags [ 101 ] to other flood bags by, for example, employing a series of straps [ 103 ] and buckles [ 104 ] integrated into the front face [ 105 ] of the bags [ 101 ]. As shown in FIG. 2 , in embodiments there may be a series of straps [ 103 ] integrated into face [ 105 ] of bag [ 101 ], and the straps may be aligned vertically. As further shown in FIG. 2 , in embodiments one or more of the straps [ 102 ] may be positioned on the face [ 106 ] of the neck [ 107 ] of bag [ 101 ], and the remaining straps [ 103 ] may be positioned on the face [ 109 ] of the body [ 110 ] of bag [ 101 ]. As further shown in FIG. 2 , in embodiments a corresponding bag [ 108 ] to which the bag [ 101 ] is attached may be have a series of buckles [ 104 ] integrated into face [ 105 ] of bag [ 108 ], and the buckles may be aligned vertically. As further shown in FIG. 2 , in embodiments one of the buckles [ 104 ] may be positioned on the face [ 112 ] of the neck [ 113 ] of bag [ 108 ], and the remaining buckles [ 104 ] may be positioned on the face [ 105 ] of the body [ 106 ] of bag [ 108 ].
[0016] Referring to FIG. 3 , shown is a drawing of a variation of the configuration of FIG. 2 showing the attachment of multiple flood bag devices to adjoining flood bags by additional means of hook-and-loop fasteners [ 114 ], such as Velcro®. As depicted in FIG. 3 , in embodiments a first bag [ 114 ] may have the “hook” side [ 115 ] of the attachment on a side of the bag, and the adjoining bag [ 101 ] may have the “loop” side[ 116 ] of the attachments on a side of the bag [ 101 ] that abuts first bag [ 114 ]. The attaching of multiple bags is to ensure that the bags are properly aligned and adjoined—without any gaps—before filling of the bags with filling material. In embodiments, first bag [ 114 ] may be sewn to second bag [ 101 ] in order to attach adjoining bags [ 114 ] and [ 101 ]. In other embodiments, each of bags [ 101 ], [ 108 ] and [ 114 ] may each be sewn to adjoining bags to attach multiple bags for the purpose of forming a multiple-bag barrier or wall.
[0017] Looking to FIG. 4 , shown are the exemplary configurations of FIG. 2 and FIG. 3 showing in additional detail the connection of multiple flood bags [ 101 ], [ 108 ], and [ 114 ] with the hook-and-loop attachments of adjoining bags engaged and the straps [ 103 ] and buckles [ 104 ], respectively of attached bags [ 101 ] and [ 108 ] engaged. In embodiments, every adjoining bag may be attached with hook-and-loop attachments, and every other bag may be adjoined with straps and buckles.
[0018] FIG. 5 and FIG. 6 depict perspective view of an individual flood bag [ 101 ] from the configurations of FIG. 1 , FIG. 2 , FIG. 3 and FIG. 4 showing the various side, bottom and neck panels and side and bottom dimensions of the bag [ 101 ]. With further reference to the examples illustrated in FIGS. 5-6 , bag [ 101 ] may be constructed of a woven material consisting of polypropylene or may be coated with a polyethylene or polypropylene coating to enhance its imperviousness to water or to strengthen the bottom [ 200 ] or sides [ 206 ], [ 207 ], and [ 208 ] of bag [ 101 ]. In embodiments, the bottom [ 200 ] of bag [ 101 ] is approximately 72 inches wide at side width [ 203 ], with front [ 204 ] and rear [ 205 ] side lengths of approximately 24 inches when filled, and front and rear “toes” [ 209 ] formed at a junction [ 211 ] of front wall panel [ 206 ] and bottom panel [ 200 ] and a junction [ 212 ] of back wall panel [ 207 ] and bottom panel [ 200 ] and measuring approximately 12 inches in height. In embodiments, the top of bag neck [ 107 ] is square-shaped, with each side[ 208 ] approximately 30 inches. In embodiments, the total height of bag [ 101 ] is approximately 48 inches when filled. In other embodiments, the height of bag [ 101 ] may vary up to approximately 72 inches when filled, with the same respective ratios of side widths [ 204 ] and [ 205 ], side lengths [ 203 ], front and rear “toe” heights [ 209 ], and bag neck sides [ 208 ]. Also in embodiments, bag [ 101 ] has four bag neck loops [ 210 ], one at each corner of the top of neck [ 105 ].
[0019] Referring next to FIG. 7 and FIG. 8 , shown are perspective views of another embodiment of an individual flood bag [ 101 ] from the configurations of FIG. 1 , FIG. 2 , FIG. 3 and FIG. 4 showing the optional closeable aperture [ 110 ] on the bottom [ 200 ] of bag [ 101 ]. Closeable aperture [ 110 ] allows for removal of bag [ 101 ] from its internal filling contents [ 118 ] without having to first remove the filling contents [ 118 ] from bag [ 101 ]. Aperture [ 110 ] is formed by two overlapping panels and [ 202 ] at bottom [ 200 ] of bag [ 101 ], with front bottom panel [ 201 ] overlapping rear panel [ 202 ] underneath rear bottom panel [ 202 ], such that flood water approaching front of bag [ 101 ] is deflected under aperture [ 110 ]. In embodiments, aperture [ 110 ] is closed and secured by hook-and-loop fasteners [ 220 ], such as Velcro®. In embodiments, width [ 221 ] of hook-and-loop fastener [ 220 ] is approximately one inch, and fastener [ 220 ] runs along entire width [ 222 ] of bottom [ 201 ] of bag [ 101 ]. In other embodiments, width [ 221 ] of hook-and-loop fasteners [ 220 ] is sufficient in width to keep the aperture closed when the bag is being filled. In embodiments, the ability to remove bag [ 101 ] from internal filling contents [ 118 ] allows for removal and storage of bag [ 101 ] and re-use of bag [ 101 ] for future applications.
[0020] With further reference to the examples illustrated in FIGS. 7-8 , bag [ 101 ] may be constructed of a woven material consisting of polypropylene or may be coated with a polyethylene or polypropylene coating to enhance its imperviousness to water or to strengthen the bottom [ 200 ] or sides of bag [ 101 ]. In embodiments, the bottom [ 200 ] of bag [ 101 ] is approximately 72 inches wide at side width [ 203 ], with front [ 204 ] and rear [ 205 ] side lengths of approximately 24 inches when filled, and front and rear “toes” [ 209 ] formed at the junction [ 211 ] of front wall panel [ 206 ] and bottom front panel [ 201 ] and the junction [ 212 ] of back wall panel [ 207 ] and rear bottom panel [ 202 ] and measuring approximately 12 inches in height. In embodiments, the top of bag neck [ 107 ] is square-shaped, with each side[ 208 ] approximately 30 inches. In embodiments, the total height of bag [ 101 ] is approximately 48 inches when filled. In other embodiments, the height of bag [ 101 ] may vary up to approximately 72 inches when filled, with the same respective ratios of side widths [ 204 ] and [ 205 ], side lengths [ 203 ], front and rear “toe” heights [ 209 ], and bag neck sides [ 208 ]. Also in embodiments, bag [ 101 ] has four bag neck loops [ 210 ], one at each corner of the top of neck [ 105 ].
[0021] With reference to FIG. 8 , in embodiments, when filled bag [ 101 ] is lifted at one or more of loops [ 210 ], the aperture [ 110 ] closures [ 221 ] release and allow the filling contents [ 118 ] of bag [ 101 ] to be released through aperture [ 110 ], causing bag [ 101 ] to empty and allowing for the removal, storage and re-use of bag [ 101 ].
[0022] Referring to FIG. 9 , shown is an optional serial connection of several sets of configurations [ 102 ] of bags [ 101 ] shown in FIGS. 1-8 . In embodiments, each cell set configuration [ 102 ] of bags [ 101 ] comprise a plurality of bags [ 101 ]. In embodiments, multiple cell sets [ 102 ] are conjoined to form an extended or protracted wall [ 310 ] of bags [ 101 ] of a desired or effective length. In embodiments, multiple cell sets [ 102 ] are conjoined to provide a protracted wall [ 310 ] of bags [ 101 ] of up to 110 feet in length.
[0023] FIG. 10 depicts another embodiment of a serial connection of a plurality of bags [ 101 ] shown in FIGS. 1-8 . In embodiments, bags [ 101 ] are conjoined to form a protracted wall of the plurality of bags [ 101 ] in a variably curved alignment in accordance with various embodiments of the present disclosure. In embodiments, the curvature of the wall is achieved by partially filling one or more bags [ 101 ] such that the front side[ 206 ] or back side[ 207 ] of the bags [ 101 ] may be folded or creased to achieve the desired degree of curvature.
[0024] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.
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An apparatus, system, and method for creating a flood barrier by use of an open-top fabric bag device or series of connected bag devices that can be filled with materials to create the barrier. Each bag has a bottom panel, a front panel, a back panel, a four-sided neck, an opening in the neck, and lifting loops at the neck for lifting the bag. The bottom panel may contain a closable aperture formed by a front bottom panel overlapping a back bottom panel underneath the back bottom panel and secured by a fastening device to releasably secure the aperture. When the bag is full of materials and is lifted at the neck loops, the aperture opens and the contents are released and remain in place as the bag is lifted and removed and is available for re-use.
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BACKGROUND OF THE INVENTION
This invention relates to the processing of photographic film. The invention particularly relates to a processing unit for processing photographic film which is portable.
There are several different ways in which the processing of photographic film can be achieved. A common way is to send the film to a processing laboratory where typically it will be processed in a large processing unit. On a smaller scale a photographic film can be wound on to elements such as spiral reels and processed in a small light tight tank. The chemicals used in the processing have to be mixed, raised to the correct temperature and the whole process operated with a timer and thermometer.
Also small processors are available, but again these need the chemicals to be mixed and they require connection to a water supply and have to be operated in a dark room for the loading of a film. Usually they also require a mains type electrical supply.
In a typical portable machine each film for processing is loaded onto a spiral in the dark usually in a dark room. Chemicals are supplied to the machine from external containers and typically the chemicals will be supplied as concentrates which are diluted to the correct concentration. As a rinse is used after every stage to overcome contamination the machines require connection to a water supply. This can make the process time consuming and large volumes of effluent have to be discharged. Finally the film requires removal for a drying step.
SUMMARY OF THE INVENTION
The present invention is concerned with a portable processing unit which attempts to alleviate some of these disadvantages.
According to the present invention there is provided a film processing unit comprising means for receiving a cassette containing undeveloped film, means for removing said film from said cassette and winding said film onto a spiral type holder located in a processing chamber, said loading means, said removal means and said processing chamber being housed in light tight conditions, receptacle means for containing processing fluid, means coupling the receptacle means to the processing chamber, valve means for selectively permitting flow of processing fluids between said receptacle means and said processing chamber, the arrangement being such that processing fluids can be dispensed from said receptacle to said processing chamber to perform a processing operation on said film and after said operation said fluid can be returned to its respective receptacle means or otherwise discharged.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be described now by way of example only, with particular reference to the accompanying drawings. In the drawings:
FIG. 1 is a perspective view of a portable processing unit in accordance with the present invention, and
FIG. 2 is a sectional view of the processing unit.
DETAILED DESCRIPTION OF THE INVENTION
Referring to the drawings the processing unit is in the form of a case like container having a base section (10) and a lid section (14) connected to the base by hinges (15). The base section (10) and the lid section (14) each define volumes within which are located elements which make up a self-contained photographic film processing unit. The case includes catches (16) for securing the lid to the base and a handle (17) for carrying the case.
The lid section (14) houses three containers (18, 19, 20) each provided to accommodate chemicals used in the developing process. Each container (18) can include a heating element (22) which when energised acts to heat the solution contained in it to a desired temperature. Also each container is connected at its lower end to a conduit (23) which extends from the lid section to a pump (24) disposed in the base section. The pump is coupled by a first valve (25) and a three-way valve (26) to a processing unit (30). As can be seen in FIG. 1 of the drawings four such processing units are located in the base section. The processing units (30) are arranged in spaced apart pairs, one adjacent each side wall of the base section.
Each processing unit (30) is defined by a light tight container having a lid (31). The container defines a chamber (35) in which is located a spiral type reel (32) which can be mounted so as to be rotatable about its axis. The case can include drive means for rotating the spiral (32) about its axis. The container (30) also defines a smaller chamber (33) within which can be disposed a cassette (34) containing film to be developed. Film extends from the cassette (34) to the spiral (32) by way of a loading shute (37). The loading shute (37) is designed to bow the film slightly as it is fed to the spiral (32) thereby facilitating passage of the film between and into the side walls of the spiral. The end of the film is connected to the spiral by clipping it to a belt (38).
Associated with each unit (30) is a manually operable knife (40) which can be used to cut the end of a film after it has been wound onto the spiral (32). A recess (41) is provided in the lid (31) above the knife. The cutting edge of the knife when it is moved upwardly can enter the recess (41) thereby facilitating the cutting operation.
Disposed between the spaced apart pairs of processing units (30) is a control section (45). This control section includes a microcomputer and associated memory. Instructions and data can be fed into the microcomputer by way of keys (48) and a display (49) is also provided. This can be a liquid crystal type display.
The computer is programmed to control developing process. It can output signals for controlling the valves (25, 26) and the pump (24) and also to control the heating of the chemicals in the containers (18, 19, and 20). The computer can also receive inputs from various sensors provided in the processing unit which can sense for example when the latching levers of the lid have been closed or when the drive to the spirals.
In use the unit is operated with lid (14) open. Appropriate chemicals are placed in the containers (18, 19, and 20) and are supplied in a form which requires no further additions of water. This means that once the solutions are in the containers no further contact from the operator is required. When required the solutions in the containers are heated by the 12 volt heater (22) whose operation is regulated by the temperature probe which feeds temperature data to the computer control. A cassette (34) containing the film to be processed is located in the compartment (33) provided for this purpose. A length of film is drawn out from the cassette and fed via the shute (37) and connected to the belt (38) on the spiral (32). The lid (31) is then closed on that processing unit. The spiral is then rotated by appropriate drive means and the film is drawn from the cassette (34) and wound onto the spiral. As has been explained the shute acts to assist this operation by bowing the film so that it can be fed correctly between the lands which are formed on the spiral. When the film has been completely drawn out from the cassette (34) this is sensed and the drive to the spiral is declutched. The film can then be cut by operating the knife (40). If necessary a further film can then be loaded in a simpler manner to one of the other processing units (30).
At this point in the operation the computer will by way of the display (49) inform the operator of its status and call for the operator to input the type of film and the type of process required. The machine can be arranged so that it is always ready to process film irrespective of the temperature of the chemicals in the containers (18, 19, and 20). The computer control can be programmed to automatically adjust the processing time to take account of temperature of the chemicals and their state of exhaustion. However in normal operation the machine should have been left on standby and the chemicals preheated to the optimum temperature. When the operator has inputted the type of film and process required the delivery of chemicals from the containers (18, 19 and 20) to the processing units (30) takes place. This occurs under the influence of gravity. The chemicals are fed by way of the valves (25 and 26) to the chamber (35). A level detector is provided to sense the level of liquid in the chamber and at an appropriate time causes the valve (25) to close so that no more liquid is fed to the processing unit. When the liquid has reached the desired level the process treatment starts with the spiral (32) rotating. After a predetermined time determined by the computer control the valve (15) is again opened and the pump (24) starts operating. This causes the chemical to be pumped back to the appropriate container (18, 19 or 20) following which the valve (25) is closed and the valve (26) is operated to select an outlet (50) through which any remaining chemicals can drain. Further chemicals can be fed into the unit (30) in a similar manner to complete the developing process, each container has its own valve and pump station.
The unit can be provided with a heater to supply hot air to the film held on the spiral in the processing unit (30). This air can be forced in by means of a fan heater (not shown) the air being fed into the chamber (35) by way of light traps behind an inlet (51). Air can exhaust via a vent with light traps in an opposite wall. Alternatively the film can be taken out wet if desired.
To remove the processed film the lids (31) are unlocked and the spiral removed and the film unwound from the spiral.
It should be noted that the pairs of units (30) can be arranged so that one part may be operating one process at the same time as the other part is operating another different process. One such process may be stopped without the other having to be interrupted.
It will be appreciated that after use the case lid can be closed and latched and the whole unit taken to another location if necessary. Bottles containing used chemicals can be removed by inverting and unplugging them and new chemicals located therein.
The apparatus described above has a number of features which are considered to be significant inventive both singly and in combination. These include the following:
The provision of a self-contained photographic film processing unit which does not require a dark room for its operation. The unit can be operated from a 12 volt supply such as a car battery.
The provision of such a processing unit in which the chemicals are supplied ready mixed.
A portable processing unit having automatic processor control. The use of processor control allows the unit to adopt a low temperature start up process which may be necessary if film is required quickly before the developing chemicals have reached an optimum temperature.
The unit can be used at low power and low voltage and the computer can be designed to carry out a power sharing function to conserve power.
The unit can have two film processing stations running in parallel. It is possible to stop one processing station and remove the film from that station while film is still being developed in the other station.
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Described herein is a portable film processing arrangement which is housed in a case-like receptacle comprising a base portion and a lid portion. Base portion 10 houses a plurality of processing units 30 which accommodate spiral holders onto which film to be processed can be wound automatically. Lid portion 14 houses a plurality of containers 18,19,20 which contain processing chemicals for processing the film. The chemicals are fed to the processing units 30 from the containers 18,19,20 as required by valves which are controlled by an on-board computer in a control section 45 located in the base portion 10 between the processing units 30.
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BACKGROUND OF THE INVENTION
1. Field of Invention
This invention relates to a fluid pump having a rotary swash plate and several axially arranged pumping pistons mounted in a fixed cylinder in which the swash plate strokes the pumping pistons through an intermediate bearing unit which rotationally isolates the swash plate from the pumping pistons to permit the use of check type fluid intake and exhaust valves to control flow to and from the pumping chambers.
2. Description of Related Art
A direct injection fuel system for an internal combustion engine may be designed to inject a fine mist of fuel in a desired shaped pattern directly into a combustion chamber. This is in contrast to indirect injection into an intake manifold and through an intake port as is presently the norm. With this direct injection of fuel, the mean size of fuel particles needs to be of sufficiently small dimension to achieve fast evaporation and quicker and more complete ignition, particularly, as compared to a more conventional port injector. Generally however, with direct fuel injection, there is less time to inject a desirable and required quantity of fuel for each given cycle as compared to port fuel injection. Accordingly, small gas particle size and a relatively great fuel velocity are important. Therefore, the fuel pressure in the fuel conduit or rail leading to the injector must be greater than the pressures normally needed for port type fuel injections. Additionally, the pressure of fuel injected into the cylinder or combustion chamber must be greater than the cylinder pressure during the time of injection to assure the opening operation of the injector and a desirable full forward flow of the fuel charge from the injectors into the combustion chamber.
Prior to the present invention various types of fuel pumps have been designed for injecting gasoline into internal combustion engines for vehicles. Included among these designs are axial pumping piston and swash plate units incorporating rotary slide valves with resultant sliding interfaces for porting fuel into and out of the pumping chambers of the pistons. The use of such rotary valves results in high frictional heat and resultant boiling of the fuel in the pump, particularly at the inlet of a pumping chamber. This frictional heat tends to vaporize fuel. Since vaporized fuel is compressible as compared to incompressible liquid fuel, a pressure loss in the fuel rail will undesirably decrease the effectiveness and service life of such pumps, but primarily and more importantly will cause the associated engine to stall.
Additionally, the prior pumps having sliding rotary valves and resultant friction at the pump inlet results in an increased torque characteristic for the pump which imposes an additional load on the engine and reduces its net horse power output. Also, the sliding interface of rotary valves is susceptible to damage from a wide variety of particulate matter and other foreign material that may possibly find its way in the fuel system. Such matter may scratch or abrade the sealing surface and cause a loss of pressure which can cause the engine to stall. If sufficiently severe, such scratches and abrasions will detract from the subsequent build-up of pressure in the system.
Generally, a fuel such as gasoline is a poor lubricant. Accordingly, a fuel pump for gasoline which has relatively rotating, porting or valving mechanisms which relies on a formation of a hydrodynamic film of gasoline as a lubricant between moving surfaces will experience high friction and perhaps reduced service life.
SUMMARY OF THE INVENTION
With the above in mind, the present invention is drawn to a new and improved fuel pump that has a special load transmitting bearing unit to effectively isolate the rotary input to the pump from the axial stroking of a plurality of pistons so that intake and exhaust valves of the fuel pump have no sliding porting surfaces. In one preferred embodiment of the present invention, the fuel inlet to each pumping piston is through an one-way check valve and the outlet is through an one-way reed valve. These inlet and outlet valves are sufficiently large to permit passage of foreign particles that may be present in the fuel flow. With the stroking pistons and valves of this invention, friction is reduced so that significant heat to cause fuel boiling or vaporization is not generated and a resultant loss of fuel pressure does not occur. In view of the fact that there is no relative turning and sliding valve structure, the intake and exhaust valves in this invention seal well at all fuel pump speeds and pressures required by the engine. With the fuel pump of this invention, there is a higher volumetric efficiency over a wide range of engine speeds and fuel pressures.
In the present invention, the pumping elements including the axially-moving pistons and their cylinder assembly are maintained in a non-rotational posture relative to the rotatable swash plate. A new and improved bearing assembly is employed to isolate the non-rotating pistons and barrel assembly from the rotating input shaft and swash plate assembly while at the same time effectively transmitting significant thrust loads from the pumping pistons to the swash plate. It is the relatively great fluid pressure inside the cylinders creating a force on the pistons that creates the substantial thrust load which is transmitted to the swash plate. To this end, a creeper plate is provided in abutting association with the bearing assembly. Pockets are formed in a side face of the creeper plate and a slipper member is inserted into each of the pockets. Each slipper is connected to one end of a pumping piston by means of a ball-type universal joint. The ball joint includes a spherically shaped socket in the slipper and a conforming spherically shaped head or end portion of the associated pumping piston. This connection generates a very smooth pumping operation and decreases wear.
In the present invention, the bearing assembly transfers loads between the swash plate and the pumping pistons and has a generally annular configuration. The central axis of the annular bearing assembly is not parallel to the input shaft but is perpendicular to the angled surface of the swash plate. The bearing assembly in the preferred embodiment is a cylindrical roller thrust type bearing. This bearing assembly has a rotating race member abutting the angled surface of the swash plate which is operationally acted upon by this angled surface in a manner which permits some sliding contact therebetween. The bearing assembly also includes a non-rotating race member abutting a creeper plate and is spaced from the rotating counterpart. A plurality of roller bearing units or elements are captured between the two races. Specifically, the non-rotating race member and the creeper plate do not rotate about the input shaft but oscillate axially. The piston ends are operatively attached to members which reside in slots formed in the non-rotating creeper plate. This arragement effectively transfers forces or loads between the swash plate and the pumping pistons. The arrangement shown in the preferred embodiment eliminates any sliding contact between the non-rotating race member off the bearing unit and the creeper plate and therefore wear is greatly reduced.
This arrangement is only useful for a fuel pump with at least three pistons. Since a minimum of three points determine a plane or surface, the preferred pump embodiment of this invention has three pumping pistons each mounted within a cylinder or chamber of a stationary barrel member. The pistons are equally spaced both circumferentially and radially. A spring urges each piston into engagement with the bearing assembly at all times. The piston's even circumferential spacing produces a desired sequential cycling of each pumping piston as a different thickness of the swash plate moves into alignment with the piston. A creeper plate is positioned in abutting relationship with the roller bearing assembly's non-rotating race member and is adapted to move with the pistons as they reciprocate in the pumping chambers. The creeper plate has radially directed slots in which small slipper members reside. Each slipper member is attached to one of the pistons by means of a rotatable joint.
As the swash plate rotates, the contact path defined by the intersection of the piston's axis and the creeper plate is elliptical. In other words, the creeper orbits about the shaft centerline slightly as well as moving axially back and forth. As the creeper orbits, the slippers slide radially in the slots formed in the creeper plate. The slots in the creeper plate permit the slippers to maintain their same circumferential positioning as dictated by the piston mounted in the cylinders of the barrel. Thus, as the creeper plate oscillates both radially inward and outward and axially back and forth, the pistons are subjected to an axially oriented force with little sideways thrust which would tend to promote wear.
The connection between the slippers and the pistons allows angulation therebetween to inhibit wear. One end of the piston is formed with a substantially spherical head and the associated slipper has a semi-spherical cavity to receive the piston end. This effectively acts as a ball joint to distribute loads produced by pressure developed within the piston pumping chambers.
This invention provides a new and improved method of distributing axial loads created by pistons actuated by a swash plate. It employs a special slotted creeper plate that has slots formed on one side face and has a shoulder to operably join it to the non-rotating race member of the bearing assembly. Preferably, the non-rotating race member moves with creeper plate, that is, moves axially and slightly radially but does not rotate. However, the creeper plate is capable of slowly rotating relative to the creeper without significant wear resulting. Importantly, the axial thrust loads are applied and distributed evenly over the whole surface of the non-rotating race member by this slow rotation.
These and other features, advantages and objects of the present invention will be more apparent from the following detailed description and drawing:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a longitudinal cross-sectional view of a swash plate actuated axial piston pump and diagrammatically illustrated fuel injection system;
FIG. 2 is an enlarged view of a portion FIG. 1;
FIG. 3 is a pictorial view showing a rotatable isolator and bearing unit separating the swash plate from the pumping barrel of the pump of FIG. 1;
FIG. 4 is a front view of a creeper plate element parts used in the pump of FIG. 1;
FIG. 5 is a cross-sectional view of the creeper plate element of FIG. 4 taken generally along sight line 5--5 of FIG. 4;
FIG. 6 is a pictorial view of a swash plate used in the pump of FIG. 1;
FIG. 7 is a front view reduced in scale of a valve plate element used in the pump of FIG. 1; and
FIGS. 8 and 9 are enlarged pictorial views of one-way valve components used in the pumping pistons of the pump of FIGS. 1 and 2.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now in greater detail to the drawings, there is shown in FIG. 1 a fuel pump 10 for pumping gasoline or other fuel at high pressure to the combustion chambers 12 or the cylinders of an internal combustion engine 14 through a common fuel rail 16 and separate fuel injectors 18. These injectors 18 open in accordance to a predetermined sequence for injecting a fine mist of fuel directly into the respective combustion chamber 12.
The fuel pump 10 is rotated or driven through a cylindrical input shaft 22 which is mounted for rotation within a stepped cylindrical pump housing 24 by ball bearing unit 26. A pump housing 24 is supported by a support structure 28 of the engine which forms a generally cylindrical cavity into which the housing 24 partially extends. Housing 24 is attached to structure 28 by threaded fasteners 30 (only one illustrated). A pulley 32 is mounted on the leftward end portion of the input shaft 22 externally of housing 24 so the pulley 32 can be engaged by a drive belt 36 whose movement causes rotation of the pulley and shaft by operation of an associated internal combustion engine 14. A gear train or other suitable drive mechanism could also be utilized.
As shown in FIG. 1, the rightward end of input shaft 22 has a stepped smaller diameter end portion which forms an extended nose portion 38. Portion 38 extends through the inner diameter of an annular fluid seal 40 which is disposed within the housing 24. The nose portion 38 further has an annular swash plate member 44 mounted thereto by an axially extending threaded fastener 46. More specifically, a fastener 46 has a threaded end which extends into a similarly threaded bore formed in the extended nose portion 38 of the input shaft 22. The fastener 46 has a cylindrical midportion 48 which closely resides within a bore in the central hub portion of the swash plate member 44. The fastener 46 secures the swash plate 44 to the nose portion 38 of input shaft 22 so that the shaft 22 and swash plate 44 rotate together as pulley 32 is driven or rotated by movement of the belt 36.
The rotatable swash plate 44 produces axial directed forces for pumping fuel by means of an annular working face or surface 50 which is disposed in an plane inclined from a plane normal to the rotational axis 52 of the shaft 22. The surface 50 is in a plane which is at a predetermined angle or axis of inclination with respect to the rotational axis 52. Swash plate 44 is also formed with an extending cylindrical bearing support shoulder portion 54 adjacent surface 50. The longitudinal axis of the cylindrical portion 54 is perpendicular to the plane of the working face or surface 50 of swash plate 44.
The support shoulder 54 of swash plate 44 operatively mounts a substantially flat, annular-shaped race member 56 of an associated roller bearing unit 58. The race member 56 engages the inclined or angled surface 50 of the swash plate in a manner thereby permiting sliding movement therebetween so that race member 56 rotates with the swash plate 44 but may not rotate at the same rotational rate as the swash plate. The roller bearing unit 58 transmits axially directed thrust forces as created by rotation of the inclined surface 50 of the swash plate 44.
In FIG. 3, a plurality of pumping pistons 60, 62 and 64 are shown in axial alignment with the pump's rotation axis 52 established by shaft 22. The roller bearing unit 58 isolates three pistons 60, 62, and 64 from the rotation movement of input shaft 22 and swash plate 44. As best shown in FIGS. 1 and 2, using piston 60 as an example, each piston is operatively mounted for axial reciprocation and resultant pumping motion in a cylinder or pumping chamber 66. Each chamber 66 is formed in an associated cylindrical barrel member 67 which is held stationary within the housing 24 of pump 10.
Referring again to FIG. 2, attention is directed to a thrust-load transmitting second race member 68 of the roller bearing unit 58. This second race member 68 is spaced axially away from the corresponding first rotating race member 56 by a plurality of cylindrical rollers 74 which are sandwiched between the race members 56 and 68. Note that second race member 68 is spaced axially away from the edge of support shoulder 54. The positioning of the individual rollers 74 primarily in the radial direction is maintained by a cage assembly 72 while the rollers themselves maintain the axial spacing between race members 56 and 68. Resultatly, each of the rollers 74 is free to rotate about its individual axis when there is relative rotational movement between the first and second race members 56 and 68. This is caused by the rotation of the first race member 56 along with the swash plate 44 and the substantial non-rotation of the second race member 68 which is restrained as more fully explained hereinafter.
As best seen in FIG. 1, an generally annular-shaped creeper plate 75 is positioned in abutting relationship to the second race member 68. The exact configuration of the creeper plate 75 is best shown in FIGS. 4 and 5. Creeper plate 75 consists of a relatively thick, substantially flat body which also includes a protruding face shoulder portion 73. As best shown in FIG. 2, this face shoulder 73 extends into the inner diameter of the second race member 68 and serves to pilot or position it.
As best seen in FIG. 4, the creeper plate 75 has three equally spaced pockets 76 formed in one face. Each of the three pockets 76 receives or retains a slipper member 80 therein, as illustrated in FIG. 2. A semi-spherical cavity 82 is formed in an end of each of the slippers 80 which is adapted to receive a spherical head portion 83 of one of the pumping pistons 60, 62, or 64. The connection provided by the cavity 82 and head portion 83 creates a ball-type universal joint between the creeper plate 75 and a respective piston. The cavities 82 are configured to receive the head portions 83 by a forceful insertion so that the members 80 and 83 are thereafter retained together. To accomplish this assembly, it might be desirable to elevate the temperature of the slipper member and lower the temperature of the piston to better accomplish the tight insertion therebetween. It is thought that with some pumps operating in some particular situations, the slipper members may not be necessary and that the head portions of the pistons might be sucessfully mounted directly into slots or pockets formed in the creeper plate.
As previously stated, the pumping pistons 60, 62, 64 are reciprocally mounted in cylindrical pumping chambers formed in the barrel member 67. Chamber 66 shown in FIG. 2 is an example of the piston/chamber arrangement. The chambers 66 are formed in bores which extend completely through the body of the barrel member 67. The ends of each of these chambers 66 furthest from the swash plate 44 is normally covered by reed valves 86, 88, 90 which are formed in a flattened annular valve plate 92 as shown in FIG. 7. This plate has three semi-circular and radially spaced cutouts 95 which define the three reed valves 86, 88, 90. The valves 86, 88, and 90 normally register with and cover the outer ends of the three associated pumping chambers 66. As seen in FIG. 1, the valve plate 92 is held to the left against the rightward end of the barrel 67 by a fuel outlet fitting 96. Fitting 96 is fluidly connected to the fuel rail 16 by a line or conduit 98 as schematically shown in FIG. 1.
The end interface 99 of fitting 96 has a plurality of concavities placed adjacent the valve portions 86, 88, and 90 to allow flexure of the normally closed valves during a pumping stroke of the associated piston so that the pumping chambers are serially opened to allow the pistons to move fuel at high pressure to the fuel rail 16.
As can be best understood by reference to FIGS. 1 and 2, the configuration of each pumping piston 60, 62 and 64 is the same. Each piston consists of a cylindrical body 100 formed with an interior bore 102 which forms an interior passage which communicates with the interior 106 of the pump housing 24 through an axial connector passage 104 and a cross passage 105. The pump interior 106 receives a supply of low pressure fuel by flow through an inlet passage 108 in the housing 24 which is overlaid by a screen.
As best shown in FIG. 2, the piston's connector passage 104 is normally blocked by a one-way valve element 112 which is yieldably held in its closed blocking position by a light helical spring 114. The other end of the spring 114 seats against a spring seat member 116 which is secured within the interior 102 of the piston. Member 116 has outer fuel passages 118 formed within its outer surface as best seen in FIG. 8. The member 116 is held in an intermediate position within the interior of the piston against an annular shoulder 120 by a relatively heavy coil spring 122. The rightward end of spring 122 is secured in the pumping chamber 66 by a retaining ring member 126 which has a fluid passage 127 extending therethrough. The retaining ring member 126 is in turn fixed at an outer edge portion in the pumping chamber by a shoulder or its equivalent formed in the barrel 67.
The force of spring 122 urges the associated piston axially to the left in FIG. 2. to urge the associated slipper member 80 against the creeper plate 75. This in turn urges the creeper plate 75 against the second race member 68 of bearing assembly 58. The resultant leftward axial force maintains the slipper member 80 within a corresponding pocket 76 in the creeper plate 75. The reciprocal mounting of the pistons in the stationary barrel 67 also prevents rotation of the operatively connected slippers 80 and creeper plate 75 about the axis of the input shaft 22. Likewise, the second race member 68 is inhibited from substantial rotation by its contact with the non-rotating creeper plate 75 although some slippage between race member 68 and creeper plate 75 is possible.
Pump Operation
Operation of the engine drives or moves belt 36 to cause rotation of the pulley 32 which is attached to the input shaft 22. This rotates the swash plate 44 which produces a corresponding back and forth axial oscillation of the swash plate's angled or inclined face 50. More specifically, the angle or inclination between surface 50 and a plane normal to the input shaft's axis causes the distance between the surface 50 and a particular piston head to vary at any circumferential position. This of course produces a desired pumping action of an associated piston. Thus, one rotation of the swash plate 44 produces one complete pumping action of the piston causing it to move first to the right and then back to the leftward starting position.
In FIGS. 1 and 2, the pumping piston 60 is shown at the completion of a full compression stroke for full displacement of a particular pumping chamber. Note the alignment of the thickest portion of the swash plate with the piston 60. Simultaneously, the other two pistons are at a midposition of their cycle, one piston part way into its compression stroke and the other piston moving back from a pumping position and thus drawing fuel into the pumping chamber. During this operation, the roller bearing assembly 58 isolates the non-rotating creeper plate 75, slippers 80, and pistons 60 from rotation of the swash plate 44 while transmitting axial loads from the pistons 60, 62, and 64.
In the completed compression or pumping stroke of piston 60 shown in FIGS. 1 and 2, the high fuel pressure and the force of spring 114 maintains the one-way fuel intake valve 112 in its illustrated closed operational position so that fuel in the pumping chamber can only be directed outward past the outlet reed valve 86. Valve 86 responds to the increase in fuel pressure by deflecting to the right so that fuel flows therepast into the fuel rail 16 and to the injectors 18.
Continued rotation of the swash plate 44 from the above described position moves the thickest portion of the swash plate toward another piston. During this period, the arrival of a continuously thinner portion of the swash plate 44 permits spring 122 to urge piston 60 leftward, thus expanding the pumping chamber. During this expansion phase, the outlet reed valve 86 returns to its normal closed operative position to block flow back into the pumping chamber. The decrease of pressure in the pumping chamber relative to the pressure in chamber 106 causes the intake valve 112 to compress spring 114 and draw fuel into the pumping chamber for recharging to prepare that pumping chamber for a subsequent pumping stroke.
An important aspect of this invention is the isolation of the non-rotating pumping components such as the creeper plate 75, the slippers 80 and the pistons 60-66 from the rotating components such as the input shaft 22, the swash plate 44, and the first rotating race member 56. The aforedescribed creeper plate and slipper arrangement creates only a slow rotation of the second non-rotating race 68 relative to the creeper. Thus, wear and friction are minimized while the pumping loads are transmitted from the pumping pistons to the swash plate. Also, the ball joint configuration of the slippers and pistons transmits axial loads with minimal transmission of side loads.
With this invention, any sliding frictions are minimized using the above identified one-way fuel inlet valves and reed type outlet valves, each of which have no sliding interface to create friction or heat. More particularly, this invention with its improved fuel porting system, which does not rely on hydrodynamic film as a lubricant can be advantageously useful with poor lubricant fluids such as gasoline.
The fuel inlet and outlet openings in the preferred embodiment are large and greater than one 1 mm so that they are able to pass a wide range of debris that may find its way in to the system.
While a preferred embodiment of the invention has been shown and described, other embodiments will now become apparent to those skilled in the art. Accordingly, this invention is not to be limited to that which is shown and described but by the following claims.
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A fuel injection system for injecting gasoline or other fuel directly into the combustion chambers of an internal combustion engine including a pump that incorporates a rotary driven swash plate, a plurality of fuel pumping pistons radially separated from one another and operatively mounted for axial fuel pumping movement in a fixed barrel. A special bearing assembly and creeper plate is operatively interposed in the pump housing to transmit pumping forces of the swash plate to the pumping pistons while isolating the pumping pistons from rotation so that they stroke axially in the barrel. With this arrangement, check type valves are effectively used to control the inlet and discharge of fuel to and from the pumping chambers of the pistons eliminating rotary sliding valves with attendant heat build-up and undesirable fuel vaporization.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This patent application is a continuation of U.S. patent application Ser. No. 10/478,973 filed on May 27, 2004 now U.S. Pat. No. 7,432,772. This application incorporates by reference the entire disclosure of U.S. patent application Ser. No. 10/478,973.
This patent application claims the benefit of priority from U.S. Provisional Patent Application Ser. No. 60/298,408 filed on Jun. 18, 2001. This application incorporates by reference the entire disclosure of U.S. Provisional Patent Application Ser. No. 60/298,408.
TECHNICAL FIELD OF THE INVENTION
This invention relates to an electrical oscillator circuit comprising: a first subcircuit and a second subcircuit with a signal ground reference; a resonator unit comprised in the first subcircuit; an active device comprised in the second subcircuit connected to energize the resonator to provide an oscillating electrical signal transmitted as a differential signal via electrical conductors to the second subcircuit.
Moreover, the invention relates to an integrated circuit.
BACKGROUND OF THE INVENTION
Electrical oscillators are used in various types of electronic equipment for instance in equipment where microprocessors and/or communications means are involved.
Especially in communications means the oscillator is a very central device for obtaining timing and modulation/demodulation. In order to obtain modem high speed communication, a stable and precise oscillator is required. Further, since small size and long duration battery operation is typically in demand the oscillator consequently has to be small sized and consume a minimum of electrical power.
An oscillator for the above devices fulfilling the demands is typically implemented by means of a crystal mounted on printed circuit board, connected to an active device, e.g. a CMOS transistor in an integrated circuit providing an oscillator signal to components or subcircuits in the integrated circuit by energizing the crystal to make the crystal generate the oscillator signal. This may provide for an accurate oscillator signal.
Ideally the whole oscillator should be placed in the chip, but this would require too much substrate area on in the integrated circuit. Preferably, the active device is within the integrated circuit where it can be implemented easily along with other active devices in subcircuits using the oscillator signal. Moreover, the least possible number of active devices should be used i.a. in order to minimize power consumption as indicated above.
However, those facts, in combination with design rules and physical limitations impose very strict limitations on a circuit designer in creating the geometrical layout of the electrical connections between the resonator and the active device. Thus it cannot be ensured that the electrical connections are designed to follow a path not subjected to noise induction on the connections. As a matter of fact noise induction is a problem due to often heavy use of digital/logic gates and subcircuits in the integrated circuits, especially for those arranged for communications purposes.
A first known oscillator is implemented by means of a crystal mounted on a printed circuit board, connected to an active device e.g. a CMOS transistor in an integrated circuit providing an oscillator signal to components or subcircuits in the integrated circuit by energizing the crystal to make the crystal generate the oscillator signal. The oscillator signal is provided as the output of an inverter with its input connected to a terminal of the crystal by means of an electrical connection.
However, such an oscillator will be very sensitive to noise induced on the electrical connection. This in turn will ruin extraction of exact timing and oscillation information from the oscillator signal.
SUMMARY OF THE INVENTION
Consequently, the prior art involves the problem that oscillators arranged to consume low power are sensitive to noise induced on the electrical conductors extending between the resonator and the active device.
This problem is overcome when the device mentioned in the opening paragraph is characterized in that the second subcircuit comprises means for receiving the differential signal transmitted via the electrical conductors and converting the differential signal to a single-ended signal with reference to the signal ground reference of the second subcircuit.
Consequently, the oscillating electrical signal is provided as a single-ended signal with diminished noise sensitivity. The oscillation information, provided by the resonator, in the single-ended signal can thus be extracted and used by components in the second subcircuit for obtaining very exact timing information with the use of a minimum of components.
In a preferred embodiment of the electrical oscillator circuit the first subcircuit is arranged on a printed circuit board, PCB.
In a further preferred embodiment of the electrical oscillator circuit, the second subcircuit is arranged in an integrated circuit component, IC.
In still a further preferred embodiment the resonator is arranged to provide an oscillating signal across two terminals, each connected to one of two electrical connectors for transmitting the oscillating signal to the second subcircuit. Typically, it will be possible to layout the two electrical connectors close to each other in order to obtain a common mode noise induction, which in turn is suppressed in the means for receiving the differential signal.
When the resonator unit is a crystal, very precise and stable oscillating information is obtainable.
When the first subcircuit comprises a ground reference electrically connected to the ground reference of the second subcircuit, a common ground reference is obtained.
In a preferred embodiment the first subcircuit comprises a capacitor connected between a resonator terminal and the ground reference of the first subcircuit; said capacitor having a relatively low impedance at frequencies above the oscillating frequency and a relatively high impedance at the oscillating frequency. Thereby high frequency noise signals will be diminished by short circuiting them to the ground reference.
In a preferred embodiment the active device is a CMOS type transistor.
When the CMOS type transistor is coupled with its source terminal to the ground reference of the second subcircuit, with its drain terminal to a current or voltage supply and to one of the electrical conductors and with its gate connected to the other of the electrical conductors, a single-element active device is provided. This can further reduce the power consumption.
In a preferred embodiment the means is a differential amplifier.
When the means is connected to supply the single-ended signal to components comprised in the second subcircuit, a simple system for distributing a low noise oscillator signal to the components comprised in the second subcircuit is provided.
The oscillator can be powered by a capacitor. It is possible to supply the oscillator with power from a capacitor with small capacity during exchange of e. g. a battery pack. This is possible due to the small power consumption.
BRIEF DESCRIPTION OF DRAWINGS
The invention will be explained more fully below in connection with a preferred embodiment and with reference to the drawing, in which:
FIG. 1 shows an electrical oscillator circuit;
FIG. 2 shows an inverter;
FIG. 3 shows an electrical oscillator circuit coupled to an amplifier with differential inputs and a single-ended output; and
FIG. 4 shows a block diagram of an apparatus utilizing the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows an electrical oscillator circuit. The oscillator circuit is illustrated to comprise a first and a second subcircuit. The first subcircuit 101 is typically implemented by means of passive components mounted on a printed circuit board (PCB), whereas the second subcircuit 102 is implemented on a substrate in an integrated circuit (IC) component that is mounted on the PCB.
The first subcircuit 101 comprises an oscillating device in the form of a crystal (Xtal) 103 for instance with a nominal oscillating frequency of 32 Kilo Hertz. The crystal is electrically connected to the second subcircuit 102 by means of two connectors 106 and 107 .
At frequencies about the nominal series resonance frequency the crystal has a relatively low impedance. However, at frequencies below and above the series resonance frequency the crystal has a relatively high impedance. Thus, below and especially above the nominal frequency an oscillating signal across the crystal will be sensitive to electromagnetic interference, that is, noise induced on the connectors 106 and 107 . Capacitors 104 and 105 are connected to the crystal to provide a defined load and resonance frequency—and to couple high frequency signal components to a ground reference G 1 .
The second subcircuit 102 comprises an active device 109 in the form of a CMOS transistor biased by a current source (IQ) 110 . The CMOS transistor and the current source are connected to a ground reference G 2 . The ground reference G 2 is electrically connected to the ground reference G 1 by means of a conductor 108 .
Thus it is possible to detect an oscillating signal with reference to the ground reference G 2 at point A in the second circuit.
A bias resistor 111 is applied between the drain and gate terminal of transistor 109 to provide proper working conditions for the transistor.
An oscillator of the above described type typically provides timing signals extracted from the oscillator signal by means of a two-transistor CMOS inverter to be provided to other subcircuits on the substrate in the above mentioned integrated circuit.
FIG. 2 shows an inverter. The converter comprises two CMOS transistors M 2 201 and M 3 202 with their gate terminals connected to form an input terminal A. The drain terminal of transistor M 2 202 is connected to a voltage supply V and the drain terminal of transistor M 3 is connected to the ground reference. An output terminal B of the inverter is formed as a connection of the source terminals of the transistors M 2 and M 3 . Thereby the inverter works as hard limiting inverter.
The inverter is connected to form a part of the subcircuit 102 by connecting point A of subcircuit 102 to point A of the inverter. The ground reference of the inverter is connected to the ground reference of the subcircuit 102 . Thereby a square-wave oscillating signal is provided on the output B of the inverter.
The above described way of implementing an oscillator circuit is almost mandatory due to the following facts:
1. a crystal is preferred as resonator since it can generate a very precise oscillating signal;
2. the crystal is a relatively large component that would occupy too much substrate area in the integrated circuit and is not compatible with standard integrated circuit processing technology;
3. the crystal needs to be energized by an active device in order to generate an oscillating signal;
4. the active device is preferably within the integrated circuit where it can be implemented easily along with subcircuits using the oscillator signal; and
5. the least possible number of active devices should be used i.a. in order to minimize power consumption.
However, those facts, design rules and physical limitations impose very strict limitations on a circuit designer in creating the geometrical layout of the electrical connections between the resonator and the active device. Thus it cannot be ensured that the electrical connections are designed to follow a path not subjected to noise induction on the connections.
FIG. 3 shows an electrical oscillator circuit comprising an amplifier with differential inputs and a single-ended output. As above, the oscillator circuit is illustrated to comprise a first and a second subcircuit.
The first subcircuit 301 comprises an oscillating device in the form of a crystal (Xtal) 303 electrically connected to the second subcircuit 102 by means of two connectors 306 and 307 . To diminish high frequency noise the crystal is coupled to the ground reference G 1 by means of two capacitors C 1 304 and C 2 305 .
The second subcircuit 302 comprises an active device 309 in the form of a CMOS transistor biased by a current source (IQ) 110 . The CMOS transistor and the current source are connected to a ground reference G 2 . The signal ground reference G 2 is electrically connected to the ground reference G 1 by means of a conductor 108 . A bias resistor 309 is applied between the drain and gate terminal of transistor 309 to provide proper working conditions for the transistor.
Furthermore, and according to the invention, the oscillating signal provided by the crystal 303 which is energized by the active device Ml is connected to the differential inputs of the amplifier. The amplifier is connected to the gate and drain terminal of the active device M 1 to receive a differential signal at the gate terminals of CMOS transistors M 2 311 and M 3 312 , respectively. The CMOS transistors M 2 and M 3 are connected to transistors M 4 313 and M 5 314 forming a current-mirror. The output of the amplifier is provided at point C as the junction between the drain terminals of M 5 and M 3 . The amplifier is powered by a voltage supply Vdd 316 with reference to the ground reference G 2 in the second subcircuit 302 .
Thus an oscillating signal with reference to the ground reference G 2 at point C in the second circuit can be detected and used by other subcircuits connected to the ground reference G 2 .
Thereby, the oscillating signal can be detected as a single-mode signal with a low noise level since common mode noise signals induced on the connectors 306 and 307 are suppressed effectively. This result releases the designer of the oscillator from the important design criterion of ensuring low noise induction on the oscillator-to-active-device connection. Now it only has to be ensured that the two-wire-connection between the active device and crystal will be exposed to similar noise signals. This is typically ensured when the wires of the two-wire-connection follow almost the same path on a PCB and/or inside an integrated circuit.
Generally, the term ‘signal ground’ shall be interpreted broadly to cover any DC stable potential/terminal e.g. a ground potential/terminal or a voltage supply potential/terminal.
FIG. 4 shows a block diagram of an apparatus utilizing the invention. The block diagram depicts a circuit 401 with a resonator unit 402 and an integrated circuit 403 .
The resonator 402 is connected to the integrated circuit 403 by means of a two-wire connection 404 . Further, the resonator is coupled to a ground reference 405 . In a preferred embodiment, the resonator is a crystal coupled to the ground reference 405 by means of capacitors.
However, other types of resonators may be preferred, e.g., in the form of an LC-circuit. An LC-circuit may be preferred when a less accurate, but less expensive resonator is desired. Additionally or alternatively—an LC oscillator may be used if a high frequency resonator is desired.
The integrated circuit 403 comprises an amplifier subcircuit 407 arranged to convert a differential input signal to a single-mode output signal. The output signal is delivered to a subcircuit 408 . Further, the integrated circuit 403 comprises an additional subcircuit 409 . The subcircuits 408 , 409 and the amplifier 407 are connected to a common ground reference 410 . The ground references 405 , 410 are connected to each other via a single terminal 406 . The amplifier subcircuit 407 and the subcircuits 408 and 409 are connected to a voltage supply terminal Vc for supplying voltage power to the subcircuits. This voltage is more generally denoted a power supply reference Vc.
It would be possible to reduce the noise interference by providing additional terminals 406 connected to interconnect the ground references 405 , 410 and thereby maintain more stable ground reference voltage potentials. However, this would be infeasible because it will often be necessary to use the limited number of terminals of an integrated circuit for other circuit connections.
Generally, ground references with a low ohmic resistance are preferred since the signal level of the induced noise will be lower, other things being equal. Typically, ground references in printed circuit boards (PCBs) are implemented as a conductive layer in the PCB, thus making it possible to obtain a ground reference with a relatively low ohmic resistance. However, within integrated circuit designs thin electrical connections are used. Consequently, the ohmic resistance of the connector increases and thus involves the problem that the noise level will increase. Therefore especially within integrated circuits it is necessary to workaround the problem of having a ground reference that is more sensitive to electromagnetic noise influx. However, the invention may be utilized for circuit embodiments other than integrated circuits.
In a preferred embodiment the oscillator according to the invention is used in a mobile communications device e.g. a mobile telephone. In such an appliance the oscillator may run constantly in order to maintain a correct timing for the device to stay synchronized with a base-station. Therefore the oscillator is not switched into a sleep-mode like several other components in a mobile communications device. Sometimes, e.g. during exchange of battery supply packs of the device, the device is powered by a capacitor. This fact, in particular creates a demand for an oscillator with very low power consumption.
In the above, the term ‘active device’ is used as a generic term for transistors or transistor circuits of any type capable of amplifying an electrical signal. The transistors can be Bipolar transistors, CMOS transistors, FET transistors, JFET transistors etc. Moreover, substrates similar to PCB's can be used e. g. ceramic substrates. It should be noted that alternative types of differential-to-single-ended amplifiers can be used according to the invention, e.g. an amplifier as disclosed in U.S. Pat. No. 5,517,148.
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An electrical oscillator circuit comprising: a resonator comprised in the first subcircuit; and an active device comprised in the second subcircuit connected to energize the resonator to provide an oscillating electrical signal transmitted as a differential signal via electrical conductors to the second subcircuit. The oscillator is characterized in that the second subcircuit comprises means for receiving the differential signal transmitted via the electrical conductors and converting the differential signal to a single-ended signal with reference to the signal ground reference of the second subcircuit. Thereby a noise robust oscillator signal is provided with the use of very few components. Particularly suitable for oscillators embodied in an integrated circuit with the resonator mounted on a printed circuit board, PCB. And an integrated circuit.
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CLAIMING FOREIGN PRIORITY
[0001] The applicant claims and requests a foreign priority, through the Paris Convention for the Protection of Industry Property, based on a patent application filed in the Republic of Korea (South Korea) with the filing date of Apr. 2, 2004, with the patent application number 10-2004-0023104, by the applicant. (See the attached Declaration)
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an ozone sterilization method and device for water supply drainage, and in particular to an ozone sterilization method and device for water supply drainage that do not produce residual ozone for thereby omitting a process facility of residual ozone in such a manner that a fluid cavitation phenomenon is repeatedly adapted.
[0004] 2. Description of the Background Art
[0005] Ozone is known to have strong oxidation force compared to chlorine. Ozone has advantages that oxidation speed is high, and residual substances are not made after deodorization and sterilization. It is very important to effectively contact ozone generated by an ozone generator with treated process water. When contacting ozone with treated process water, the efficiency of the whole processes may be decreased when the contacting efficiency is decreased. At this time, since ozone that is not absorbed by water is discharged into the air, it is not properly processed in the air for thereby causing various environmental problems. Therefore, the optimum contact method is needed by carefully discharged into the air, it is not properly processed in the air for thereby causing various environmental problems. Therefore, the optimum contact method is needed by carefully reviewing contact time, process purpose, energy consumption amount, etc. More advanced analyzing research is needed. In a contacting method between ozone and water, there are known scattering method, pressurized injector method, Venturi injector method, etc.
[0006] The scattering method is achieved in such a manner that ozone is contacted with water through porous scattering tube made of a zone-based material like ceramic or stainless in ozone gas. In the above method, when foams are moved up to the surface of water, ozone is dissolved in water, and residual ozone discharged to the upper side is reused. In the pressurized injector method, water to be treated and ozone are concurrently pressurized for thereby achieving high-speed process. In this case, since remaining effect of ozone is high, the above method is used for water purification or water treatment for swimming pool, etc. In the Venturi injector method, in a state that pressure is applied by a pump, a treated water is passed through a Venturi tube, generating a negative pressure. Ozone gas is sucked using the above negative pressure. Ozone is transferred to a contact tank in a state that it is mixed with gas and liquid, so that ozone gas having a lower pressure is contacted. This method is directed to thermally cracking surplus ozone gas or surplus ozone is passed through active carbon.
[0007] In the above-described methods, aeration method is adapted for inputting ozone into water. Here, the amount of ozone generated during excitation is very small. Namely, a large amount of ozone is not used but discharged into the air. In the case of the aeration method, about 30% through 60% of ozone is mixed with water. A surplus ozone treatment apparatus is needed after generation of ozone water. In addition, the above-described methods are not well adapted to the places where need a large amount of ozone water.
[0008] In the Korean registered patent No. 0135460 (fabrication method of ozone water, and method of using ozone water) invented by the applicant of the present invention, a new method has been developed for thereby largely enhancing dissolution efficiency of ozone. In the above method, a pressurizing tank is adapted and achieved in such a manner that gaseous particles are agitated based on gas and liquid and are treated to have a super critical state in which bubbles are not seen. The above method can be easily used with a certain concentration that a customer wants at home or in business field. However, a power source is separately needed for a water analysis agitating apparatus, and dissolved gases are unstable due to turbulence by the agitating apparatus. In the case that the pressure condition is not satisfied, ozone gas may be easily separated from ozone water.
[0009] In addition, in the Korean registered patent No. 0242413 (ozone water fabrication method and apparatus) invented by the applicant of the present invention, a very advanced method has been developed for fabricating ozone water in such a manner that water is sprayed onto ozone gas, differently from the conventional method in which ozone is inputted into water.
[0010] Furthermore, in the Korean registered patent No. 0294793 (method for fabricating gas dissolved water in pressurized spraying method) invented by the applicant of the present invention, the dissolution is further promoted by installing a nozzle at a lower side of a mixing dissolution machine. The ozone is pressurized and stabilized in the pressure tank for thereby enhancing a dissolution ratio. Residual ozone gas is analyzed through an ozone thermal analysis apparatus or an ozone activation analysis tank for thereby processing residual ozone. However, in the above-described methods, ozone is mixed with water, the water mixed with ozone is passed through a mixing dissolution device and is reacted in the pressurizing tank for thereby producing ozone water. Non-reacted ozone should be separated from gas, and residual ozone should be separately processed. In addition, the above method is directed to processing polluted water itself. Namely, the ozone treatment is performed with respect to all polluted water, and then the following work is performed. Therefore, a large amount of power is consumed for treating all polluted water, and an apparatus cost, and maintenance cost are increased.
SUMMARY OF THE INVENTION
[0011] Accordingly, it is an object of the present invention to provide an ozone sterilization method and device for water supply drainage in which a dissolution efficiency of ozone and excellent, and no residual ozone is produced in such a manner that cavitation of fluid is repeatedly adapted in a method of dissolving liquid and gas (ozone) in an environmental field.
[0012] It is another object of the present invention to provide an ozone sterilization method and device for water supply drainage capable of achieving an environment friendly system as compared to a sterilization using fluorine or chloride, and the cost problem in a conventional process method using ozone is overcome.
[0013] It is further another object of the present invention to provide an ozone sterilization method and device for water supply drainage capable of accurately adjusting the amount of inputted ozone by adjusting the input amount of ozone based on pollutant such as oxidized material, organic material, etc., and decreasing ozone process time from minute unit to second unit. In addition, residual ozone treatment facility is not needed based on full process of ozone for thereby preventing pollution.
[0014] It is still further another object of the present invention to provide an ozone sterilization method and device for water supply drainage that do not need a compressor for supplying ozone as compared to a conventional art in such a manner that ozone is sucked using vacuum phenomenon occurring due to a strong flow speed of source water.
[0015] To achieve the above objects, the present invention is implemented by fully mixing ozone based on cavitation phenomenon that occurs in such a manner that when source water flows in water supply drainage pipe or waste water pipe, the source water is pressurized with a constant pressure using a pump and is passed through a small size part in a state that ozone is sucked for thereby achieving high speed flow.
[0016] Here, the cavitation phenomenon will be described in more detail. In evaporation of liquid, as the temperature of liquid is increased, the liquid is boiled, and the cavitation occurs or as the pressure in liquid is decreased below vapor pressure, the cavitation occurs. In the present invention, the later phenomenon is adapted. Namely, when the flowing speed of fluid is increased, the pressure of the fluid is decreased below a saturation vapor pressure of the liquid in part. At this time, a cavitation bubble group formed of water molecular and non-condensed gas molecular are generated in liquid. When the flowing speed is decreased, and the pressure is recovered, each cavitation bubble forms a large impact pressure and a high temperature environment near the bubbles through a contraction, re-expansion and destruction, and at the same time a micro-jet occurs in the destroying bubbles. Various reactors are formed near the destroying bubbles. Each reactor operates as a micro-reactor, so that it is well reacted with surrounding reaction materials. In the above state, the reaction with ozone is very new. When reactors are sprayed to ozone, so that the dissolution ratio of ozone is significantly enhanced. The ozone agitated with reaction substance contained in source water is concurrently decreased at 1:1. As a high value of ozone is decreased, and the reaction substance contained in source water is decreased.
[0017] To achieve the above objects, there is provided an ozone sterilization apparatus for water supply drainage, comprising a first suction unit for sucking source water; a first source supply unit formed of a first pump and a first pipe way in order for the first suction unit to effectively suck source water; a first vacuum pipe of which one side sucks ozone, and the other side discharges the sucked ozone; a first ejector connected with the first source water unit and the first vacuum pipe for spraying source water onto ozone; a first critical pipe for spraying ozone water mixed by the first ejector onto the pipe way; a first aeration tank of which an upper side and lateral side surround an outer side of the first critical pipe, and a lower side is extended in the direction of water flow way; a first gas staying tank installed on an upper side of the first aeration tank for gathering ozone that is not dissolved when passing the first critical pipe; a second suction unit for sucking source water; a second source supply unit formed of a second pump and a second pipe way in order for the second suction unit to effectively suck source water; a second vacuum pipe of which one side connected with the first gas staying tank sucks ozone, and the other side discharges the sucked ozone; a second ejector connected with the second source water unit and the second vacuum pipe for spraying source water onto ozone; a second critical pipe for spraying ozone water mixed by the second ejector onto the pipe way; a second aeration tank of which an upper side and lateral side surround an outer side of the second critical pipe, and a lower side is extended in the direction of water flow way; and a second gas staying tank installed on an upper side of the second aeration tank for gathering ozone that is not dissolved when passing the second critical pipe.
[0018] Preferably, there is further provided an ozone analysis apparatus that has active carbon in the interior of the same, wherein one side of the same is extended from the second gas staying tank, and the residual gas collected by the second gas staying tank is passes through the active carbon and is removed.
[0019] Preferably, first and second water pressure gauges are installed at one side of the first and second pipe ways, and a sensor is installed at one side of the first water pressure gauge for stopping an operation of the system when the pressure exceeds a certain set range of the water pressure gauge.
[0020] Preferably, the first ejector includes an ejector reduction pipe in which a diameter of an upper side connected with the discharge unit of the first pipe way is gradually decreased, and an ejector expansion pipe in which a diameter of a lower side connected with the inlet unit of the first critical pipe is gradually increased, and a suction pipe is installed between the ejector reduction pipe and the ejector expansion pipe for sucking ozone from the first vacuum pipe.
[0021] Preferably, first and second negative and positive pressure gauges are installed at one side of the first ejector for measuring the positive pressure of the ozone inputted through the first and second vacuum pipes and the negative pressure of the source water inputted through the first and second pipe ways.
[0022] Preferably, a second water block is installed at one side of the discharge unit for discharging the discharge water when it reaches a certain amount wherein the discharge water is discharged to the first critical pipe.
[0023] Preferably, a sensor is installed at one side of each of the first, second and third vacuum pipes for measuring the concentration of ozone gas.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The present invention will become better understood with reference to the accompanying drawings which are given only by way of illustration and thus are not limitative of the present invention, wherein;
[0025] FIG. 1 is a perspective view illustrating an ozone sterilization apparatus for water supply drainage according to the present invention;
[0026] FIG. 2 is a partial horizontal cross sectional view taken along line A-A of FIG. 1 according to the present invention;
[0027] FIG. 3 is a perspective view of a first ozone process based on the construction of FIG. 1 ;
[0028] FIG. 4 is an inner cross sectional view illustrating first and second ejectors according to the present invention;
[0029] FIG. 5 is a perspective view of a second ozone process based on the construction of FIG. 1 ;
[0030] FIG. 6 is a perspective view illustrating an ozone sterilization apparatus for water supply drainage according to another embodiment of the present invention;
[0031] FIG. 7 is a partial horizontal cross sectional view of line B-B' of FIG. 6 ;
[0032] FIG. 8 is a perspective view of a first ozone process based on the construction of FIG. 6 ;
[0033] FIG. 9 is a cross sectional view for describing an operation of a critical pipe and an aeration tank according to the present invention; and
[0034] FIG. 10 is a perspective view of a second ozone process based on the construction of FIG. 6 according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0035] The preferred embodiments of the present invention will be described with reference to the accompanying drawings.
[0036] FIG. 1 is a perspective view illustrating an ozone sterilization apparatus for water supply drainage according to the present invention, FIG. 2 is a partial horizontal cross sectional view taken along line A-A of FIG. 1 according to the present invention, FIG. 3 is a perspective view of a first ozone process based on the construction of FIG. 1 , FIG. 4 is an inner cross sectional view illustrating first and second ejectors according to the present invention, FIG. 5 is a perspective view of a second ozone process based on the construction of FIG. 1 , FIG. 6 is a perspective view illustrating an ozone sterilization apparatus for water supply drainage according to another embodiment of the present invention, FIG. 7 is a partial horizontal cross sectional view of line B-B' of FIG. 6 , FIG. 8 is a perspective view of a first ozone process based on the construction of FIG. 6 , FIG. 9 is a cross sectional view for describing an operation of a critical pipe and an aeration tank according to the present invention, and FIG. 10 is a perspective view of a second ozone process based on the construction of FIG. 6 according to the present invention. Here, when describing the present invention, the related known art and construction of the same will be omitted for a clear understanding of the present invention.
[0037] The ozone treatment apparatus according to an embodiment of the present invention will be described with reference to FIGS. 1 through 5 .
[0038] As shown in FIGS. 1 through 3 , a first ozone treatment will be described. When source water is inputted into a water supply drainage pipe or a waste water pipe 1 , a first pump 4 is operated, and the source water is first sucked into a first suction unit 3 . The sucked source water is inputted into a first ejector 6 through a first pipe way 5 with a pumping pressure of 23 M through 25 M. At this time, a first water pressure gauge 7 installed in one side of the first pipe way checks the pressure of source water. When the pressure of the checked source water exceeds a certain range, a sensor 8 installed in one side of the first water pressure gauge 7 operates, so that the operation of the ozone sterilization is automatically stopped.
[0039] The ozone mixed with the source water is inputted into the first ejector 6 through a first vacuum pipe 12 . At this time, the concentration of ozone inputted through the first vacuum pipe is preferably 3% (30,000 ppm) through 12% (120,000 ppm).
[0040] A vacuum phenomenon (hereinafter referred to as a critical phenomenon) occurs in the source water inputted into the interior of the first ejector 6 based on a strong pressure and high speed of the source water. The critical phenomenon operates with the pressure and speed of ozone inputted into the interior of the first critical pipe 9 and is increased. Here, the critical phenomenon has a pressure of ozone (hereinafter referred to positive pressure) supplied to the first ejector 6 and a pressure of ozone (hereinafter referred to as negative pressure) sucked by the source water inputted into the first ejector 6 and represents the operations that the source water passing through the interior is exploded as the interior of the first critical pipe has a vacuum phenomenon. Namely, the above explosion may be referred to as cavitation. The above phenomenon is repeatedly performed.
[0041] As shown in FIG. 4 , the first ejector 6 includes an ejector reduction pipe 43 of which the diameter of its upper side connected to the first pipe way 5 is gradually decreased, an ejector expansion pipe 44 of which the diameter of its lower side connected with the first critical pipe is gradually increased, and a suction pipe 45 into which ozone from the first vacuum pipe 12 between the ejector reduction pipe 43 and the ejector expansion pipe 44 is inputted. Therefore, the flow speed of the source water inputted into the first ejector through the first pipe way is increased when it passes through the reduced diameter portion of the ejector reduction pipe 43 for thereby strongly sucking and mixing the ozone inputted into the suction pipe 45 , so that the cavitation phenomenon occurs. Thereafter, the ozone water passing through the ejector expansion pipe 44 has a strong flow speed, passing through the portion in which the diameter is gradually increased, so that the mixed ozone get pressurized and dissolved. The dissolved ozone reacts with oxidation substance and organic substance contained in the source water for thereby achieving sterilization.
[0042] Here, it is possible to control the pressure and speed of the source water and ozone for thereby generating cavitation phenomenon in such a manner that the positive pressure of the ozone inputted into a first negative and positive pressure gauge 12 installed in one side of the first ejector 6 through the first vacuum pipe 12 is measured, and the negative pressure capable of sucking the source water inputted through the first pipe way is measured. In addition, it is possible to adjust the amount of ozone based on the amount of oxidation substance and organic substance included in the source water.
[0043] The ozone water mixed with ozone in the interior of the first ejector 6 is discharged to the water supply drainage pipe or the waster water pipe through the first critical pipe 9 .
[0044] The ozone water from the first critical pipe 9 flows into the pipe through the lower side of a first aeration tank surrounding the first critical pipe, and the ozone that is not dissolved by source water is gathered at a first gas staying tank 11 installed on an upper side of the first aeration tank 10 . More than about 95% ozone inputted into the first ejector 6 through the above procedures is dissolved.
[0045] An ozone check sensor and monitors 15 , 15 ′ may be installed in one side of each of the first vacuum pipe 12 and the first gas staying tank 11 in order to check a result of the process in which ozone is dissolved.
[0046] The second ozone treatment procedures of the ozone treatment apparatus according to an embodiment of the present invention will be described with reference to FIG. 5 .
[0047] In order to process ozone gathered at the first gas staying tank 11 , the second pump 24 is operated, and the source water of the water supply drainage pipe or the waste water pipe 1 is sucked using the second suction unit 23 . The sucked source water is inputted into the second ejector 26 through the second pipe way 25 . At this time, the pressure of the source water inputted into the second ejector 26 is checked by the second water pressure gauge 27 installed in one side of the second pipe way.
[0048] The ozone gathered at the first gas staying tank 11 is inputted into the second ejector 26 through the second vacuum pipe 32 . The ozone is sucked based on the vacuum phenomenon occurring due to the strong pressure and high speed of the source water passing through the second critical pipe 29 and is mixed with the source water. The second ejector 26 has the same shape as the first ejector 6 . A pump may be installed at the second vacuum pipe for adjusting the pressure of the ozone.
[0049] In the second ejector 26 , the vacuum phenomenon occurs due to the strong pressure and high speed of the source water inputted into the second ejector 26 based on the same operation as the first ejector. The source water is sprayed to the ozone inputted based on the above vacuum phenomenon, namely, the cavitation phenomenon. It is possible to adjust the speed and pressure of the source water, so that the cavitation phenomenon occurs well by measuring the positive pressure of the ozone inputted through the second vacuum pipe 32 and the negative pressure of the ozone inputted through the first pipe way using the second negative and positive pressure gauge 33 .
[0050] The ozone water having the critical phenomenon based on the above operation passes through the second critical pipe 29 and is discharged to the water supply drainage pipe or waste water pipe 1 and is mixed with the source water that does not pass through the above apparatus, so that the sterilization is achieved by the source water by ozone dissolved in the ozone water.
[0051] At this time, the ozone water discharged from the second critical pipe 29 is discharged along the pipes through the lower side of the second aeration tank 30 surrounding the second critical pipe 29 . The gas that is not dissolved in the ozone water is gathered at the second gas staying tank 31 positioned at the upper side of the second aeration tank 30 . The ozone components included in the second ejector 6 is fully dissolved and disappears through the above procedures.
[0052] In order to achieve a satisfied process of ozone that is not mixed in the second ejector 26 , the gas gathered at the second gas staying tank 31 is inputted into an ozone analysis apparatus 35 having active carbon (not shown) through a third vacuum pipe extended from the upper side of the second gas staying tank 31 and is fully removed and discharged as purified oxygen. At this time, an ozone check sensor (not shown) and a monitor ( 15 ″) may be installed in one side of the second gas staying tank 31 , so that it is possible to check the concentration of the ozone contained in the gas inputted into the ozone analysis apparatus.
[0053] In addition, a static mixer 41 may be installed in flowing water at crossing positions for thereby achieving a desired mixing of ozone. The static mixer 41 capable of well mixing ozone does not need power. Namely, it is directed to forming turbulence in water using natural physical phenomenon for thereby achieving a desired mixing.
[0054] In the waste water treatment apparatus according to the present invention, the ozone is sucked based on the vacuum phenomenon occurring based on the strong pressure and high speed of the source water even when the ozone is not provided by the compressor in the conventional art. The ozone that is not dissolved through the first ozone dissolution is fully processed through the second ozone dissolution procedures.
[0055] The ozone treatment apparatus according to another embodiment of the present invention will be described with reference to FIGS. 6 through 10 .
[0056] As shown in FIG. 6 , a first water block 2 is formed at one side of the water supply drainage pipe or waste water pipe 1 , so that the pipe 1 is divided into an inlet part into which source water is inputted, and a discharge part from which processed water is discharged. At this time, the first water block 2 is basically capable of blocking the flow of source water inputted, but is designed in such a manner that the upper side of the pipe 1 is not fully blocked so that the source water flows beyond the upper side of the first water block 2 when a certain amount of source water flows.
[0057] The first ozone treatment procedures of the ozone treatment apparatus according to another embodiment of the present invention will be described with reference to FIGS. 6 through 8 . When the source water is inputted into the inlet part blocked by the first water block 2 , the source water is sucked into the first suction unit 3 installed at one side of the inlet part by operating the first pump 4 , and the sucked source water is inputted into the first ejector 6 through the first pipe way 5 with a pumping power of 23 M through 25 M. At this time, the pressure of the source water is checked by the first water pressure gauge 7 installed at one side of the first pipe way. When the pressure of the source water checked by the first water pressure gauge 7 exceeds a certain reference range, the operation of the ozone sterilization apparatus is automatically stopped based on an operation of a sensor 8 .
[0058] The ozone mixed in the source water is inputted into the first ejector 6 through the first vacuum pipe 12 . At this time, the concentration of the ozone inputted through the first vacuum pipe is 3% (30,000 ppm) through 12% (120,000 ppm).
[0059] A vacuum phenomenon occurs in the source water inputted into the interior of the first ejector 6 by the strong pressure and high speed of the source water. The vacuum phenomenon helps the ozone inputted into the interior of the first critical pipe 9 to be faster inputted. The source water is explosively sprayed to ozone based on the cavitation phenomenon, and the ozone is sucked and mixed. At this time, the first negative and positive pressure gauge 13 installed at one side of the first ejector 6 measures the positive pressure of the ozone inputted through the first vacuum pipe 123 and the negative pressure occurring based on the operation of the source water for thereby adjusting the pressure and speed of the source water and ozone.
[0060] The ozone water mixed with ozone based on the critical phenomenon by the first ejector 6 through the above procedures is discharged through a discharge part of the water supply drainage pipe or waste water pipe 1 blocked by the first water block through the lower side of the first critical pipe 9 .
[0061] At this time, as shown in FIG. 9 , the ozone water from the first critical pipe 9 collides with a U-shaped first water collector 14 installed in a lower side of the first critical pipe 9 and is analyzed into micro water molecular of which a part of the same is reverse-flown in the upper direction of the first critical pipe 9 and is fully mixed with the ozone water discharged from the first ejector 6 to the first critical pipe. At this time, the height of the first critical pipe 9 is preferably about 1.2 through 1.5 times with respect to the height of water flowing in the discharge part.
[0062] The discharged water of the first critical pipe 9 collided with the water block is discharged to the discharge part through a space between the U-shaped first water collector 14 and the first aeration tank 10 . The ozone that is not dissolved into source water is gathered at the first gas staying tank 11 positioned at the top of the first aeration tank 10 . The ozone inputted into the first ejector 6 through the above procedures is decreased from ten thousands unit to hundreds units, and more than 95% of the ozone is dissolved.
[0063] The second ozone treatment of the ozone treatment apparatus according to another embodiment of the present invention will be described with reference to FIG. 10 .
[0064] As shown therein, in order to process the ozone gathered at the first gas staying tank 11 , the second pump 24 is operated. The source water is sucked by the second suction unit 23 installed at one side of the inlet unit and is inputted into the second ejector 26 through the second pipe way 25 .
[0065] The ozone gathered at the first gas staying tank 11 is inputted into the second ejector 26 through the second vacuum pipe 32 and is sucked by the vacuum phenomenon occurring based on the strong pressure and high speed of the source water passing through the second critical pipe 29 and is mixed with the source water. The second ejector 26 has the same shape as the first ejector 6 . A pump may be installed in the second vacuum pipe in order to adjust the pressure of the ozone. At this time, the second negative and positive pressure gauge 33 may be installed for measuring the pressure of the source water inputted into the second ejector 26 and the pressure of the ozone.
[0066] The ozone water having the critical phenomenon through the above procedures is inputted into the inlet unit of the water supply drainage pipe or waste water pipe 1 blocked by the first water block through the second critical pipe 29 . At this time, the ozone water collides with the U-shaped second water collector 14 installed at the lower side of the second critical pipe 29 and is analyzed into micro water molecular of which a part of the same is reverse-flown in the upper direction of the second critical pipe 29 and is mixed with the ozone water flowing from the upper side for thereby achieving an easier mixing with ozone.
[0067] The discharge water from the second critical pipe through the above procedures is discharged through the discharge unit through the space between the U-shaped second water collector and the second aeration tank 30 , and the gas that is not dissolved into source water is collected at the second gas staying tank 31 installed at the upper side of the second aeration tank 30 . The ozone inputted into the second ejector 26 through the above procedure is fully dissolved.
[0068] The gas gathered at the second gas staying tank 31 flows through a third vacuum pipe 36 extended from the upper side of the second gas staying tank 31 and is inputted into the ozone analysis apparatus 35 having active carbon (not shown) and is fully purified and changed into oxygen.
[0069] In addition, the ozone water from the second critical pipe 9 is well diluted with the source water passing through the upper side of the first water block 42 and passes through the static mixer 41 for thereby achieving a desired sterilization based on ozone dissolved therein.
[0070] After a certain amount of discharge water is inputted into the discharge unit, it is discharged beyond the second water block 42 .
[0071] As described above, in the present invention, the source water passing through the water supply drainage pipe is explosively analyzed based on the cavitation phenomenon, so that the pollutant is oxidized and analyzed, and is sprayed onto ozone. Therefore, the dissolution of ozone is enhanced, and the amount of the residual ozone is significantly decreased, and the source water is effectively sterilized using the ozone.
[0072] In addition, the source water is retreated using a small amount of residual ozone, so that it is not needed to install the residual ozone facility for thereby preventing environment pollution by residual ozone. The facility and maintenance cost is significantly decreased.
[0073] The ozone is sucked based on a vacuum phenomenon occurring due to the strong pressure and high speed of the source water, so that it is not needed to use the compressor for supplying ozone as compared to the conventional art.
[0074] The ozone sterilization apparatus for water supply drainage according to the present invention may be well adapted when dissolving gas such as oxygen, etc. into liquid except for waste water.
[0075] As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described examples are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.
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The present invention relates to an ozone sterilization device and method for sterilizing source water of water supply drainage using ozone generated in an ozone generator. The method includes a first process in which source water inputted to a first water block is sucked and discharged; a second process in which source water is sprayed onto ozone through the first ejector, wherein the above routine is repeatedly performed for thereby generating ozone water; a third process in which the ozone water which source water and ozone is mixed is discharged to the discharge unit separated by the first water block, and the ozone not dissolved is collected by a first gas staying tank; and a fourth process in which the source water of the inlet unit is sucked and passed through a second ejector, and the ozone from the first gas staying tank is sucked by a second vacuum pipe.
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BACKGROUND AND SUMMARY OF THE INVENTION
This application claims the priority of German Application 10 2004 058 606.3, filed Dec. 3, 2004, the disclosure of which is expressly incorporated by reference herein.
This invention is concerned with a process for testing the tightness of a container. Additionally, the invention provides for a process for sealing a container after a test of its tightness has been made, as well as a device for sealing the container.
The lack of tightness of fuel tanks and other containers in aircraft is a problem with far reaching effects on flight safety and operational safety on the ground. This problem also affects work safety and environmental protection. If aircraft fuel tanks are lacking in tightness, substantial repair costs can result, and the operational readiness of an aircraft fleet could be impaired. During a delivery of a new or overhauled aircraft to a customer, all systems are given a final testing. Tightnesses of the tank installations are also tested. During the operation of the aircraft on the ground, as well as during air operations, leaks may occur over the aircraft life-cycle, typically more than 25 years. The leaks may be the result of mechanical damage of the tank walls due to improper handling of the aircraft or due to unplanned stresses caused by flight operations such as overloads or vibrations. In military aircraft especially, such leaks may occur when the aircraft is being fired upon.
It is in the interest of an airline operator to restore flight worthiness of the aircraft at as little expense in time and personnel as possible without having the aircraft spend time in the repair hangar of the manufacturer. Especially in integral tanks, that is to say tanks which are fitted in their spatial design to the external contour of the aircraft and/or to the internal contour of the aircraft, the tank inner walls have multiple joint locations at which leakages can occur, even though the state of the art of sealing technology is very high both with respect to manufacture and testing quality.
In spite of all the measures taken, leaks that must be located and sealed can spring up in the tank walls during operation of an aircraft.
It is one object this invention to provide a process for testing the tightnesses of containers which can be carried out without a great expense even when the containers have complex internal and/or external contours, such as, for example, in the case of integral aircraft tanks, and to permit rapid determination of leak locations. Furthermore, it must be possible to seal leaks quickly and without great cost.
Testing for leakage of a container according to the invention includes separating a first fluid in an interior space of the container from a second fluid surrounding the container, producing a negative pressure in the interior space, testing interior surfaces of container walls for traces of second fluid penetration, and localizing any points of entry of the second fluid.
According to the invention, a partial vacuum is created in the tank and subsequently tested to determine whether a fluid has penetrated the internal space of the container. This makes it possible to locate in a simple way the exact entry point of the fluid entering the inner space of the container. This reversal of the principle, known as such, of creating high pressure in the interior space of a container and observing at which point fluid exits the container, avoids disadvantages of this known solution, since the fluid escaping from the container frequently is not visible at its point of exit but rather at some distance from it.
The localization of the entry point can also be observed through a window provided in the container, and it can be observed, from the outside, where the second fluid enters the interior space of the container. Nevertheless, it is especially advantageous when a probe is or several probes are brought into the interior space of the container. Such probes can be designed so as to be stationary within the internal container space or movable along the container internal wall.
Advantageous additional improvements are additionally provided.
After completion of the process of testing the containers for leakage, that is to say, after the localization of the entry point, a sealing compound can be applied with the help of a probe from the inside of the container at the point of leakage. This probe can be either independent of the camera or a combined probe which, in addition to the camera and, as the case may be, a gas supply, can also include at least one suitable repair tool such as, for example, an injector or an extruder for the sealing compound.
A device according to the invention for testing for container leakage and for repair of leaks allows for a fast repair immediately after identification of a leakage point.
BRIEF DESCRIPTION OF THE DRAWINGS
An example of the invention will be explained in greater detail with reference to the drawings.
FIG. 1 shows a cross-section of an integrated aircraft tank,
FIG. 2 is a cross-sectional representation of an integrated tank showing locations of the joints,
FIG. 3 shows sealing of an integrated tank at a joint location, and
FIG. 4 shows inspection of an integrated tank with a camera probe.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a schematic view of a cross-section of a jet aircraft fuselage 1 . The wings 2 and 3 , of which only the wing roots are shown, are attached sideways in the lower area of the fuselage 1 . As shown in the upper internal section of the fuselage 1 , two air conduction channels 4 and 5 through which ram air is conducted to the engines are provided.
An integrated tank 10 , which has several chambers, is shown within the fuselage. The chambers include an upper chamber 12 , a left chamber 14 , a right chamber 16 , and a lower chamber 18 . The fluid in the chambers can either be cross-connected or they each can have a separate refueling opening.
The upper chamber 12 of the integral tank 10 is limited by (not shown here) front and rear face walls, a section of the fuselage external skin 20 , a section of the wall 22 of the left air conduction channel 4 , a section of the wall 24 of the right air conduction channel 5 , a left upper vertical bulkhead wall 26 , a right upper vertical bulkhead wall 28 , and a middle horizontal bulkhead wall 30 .
The left chamber 14 of the integrated tank 10 is limited by a section of the fuselage external skin 20 , a section of the wall 22 of the left air conduction channel 4 , the upper left vertical bulkhead wall 26 , as well as a left horizontal bulkhead wall 32 and the (not shown here) front and rear face walls.
The right chamber 16 of the integrated tank 10 is limited by a section of the fuselage external skin 20 , a section of the wall 24 of the right air conduction channel 5 , the upper right vertical bulkhead wall 28 , as well as a right horizontal bulkhead wall 34 and the (not shown here) front and rear face walls.
The lower chamber 18 of the integrated tank 10 is limited by the middle horizontal bulkhead wall 30 , a section of the wall 22 of the left air conduction channel 4 , a section of the wall 24 of the right air conduction channel 5 , a lower left bulkhead wall 36 , a lower right bulkhead wall 38 ,as well as a lower horizontal bulkhead wall 40 and (not shown here) front and rear face walls.
The interior of the integrated tanks is accessible through a tank lid 11 lockable in or over an opening in the fuselage external skin 20 .
Corresponding sealing measures must be undertaken in order to seal reliably the integrated tank 10 everywhere the previously mentioned bulkhead walls or face walls push against the fuselage skin 20 and each of the walls 22 and 24 of the air conduction channels 4 and 5 . FIG. 2 shows an example of such attachment of a bulkhead wall 50 on the corresponding side walls 52 and 54 .
The bulkhead wall 50 is composed of multiple types of profiles or profile sections, which are fastened together by rivets 56 . One of these profile sections is fastened by rivets 57 to the left wall 52 , and others of these profile sections are fastened with rivets 58 to the right wall 54 . Shown above the bulkhead wall 50 and between the left side wall 52 and the right side wall 54 is a chamber 60 of the integrated tanks. The individual profile sections of the bulkhead wall 50 are sealed together with a track sealant 62 on the side facing the chamber 60 . In the area in which the profile sections of the bulkhead wall 50 are secured to the left side wall 52 , a track sealant 64 is provided on the side of the chamber 60 . Similarly, in the area in which the profile sections of the bulkhead 50 are secured to the right side wall 54 , a track sealant 66 is also provided on the side of the chamber 60 .
Spray sealants 68 and 69 overlying the securing area are additionally provided on the side of the chamber 60 of the integrated tanks where the bulkhead 50 is pushed against the left side wall 52 and against the right side wall 54 .
The mounting and sealing of one bulkhead wall against another wall is represented in FIG. 3 .
A bulkhead wall 70 , which has a cross-section in the form of an “I,” pushes with its bottom surface against the interior surface of a side wall 72 . The lower section of the bulkhead 70 has a left horizontal leg 70 ′ and a right horizontal leg 70 ″. A surface seal 74 is disposed between the bottom surface of the left horizontal leg 70 ′ and the bottom surface of the right horizontal leg 70 ″ of the bulkhead wall 70 as well as the interior surface of the side wall 72 . The surface seal 74 , for example, may consist of a polytetrafluoroethylene.
In its lower area at the side facing the side wall 72 , the bulkhead wall 70 is provided with a groove 71 at a location where the left horizontal leg 70 ′ and the right horizontal leg 70 ″ push against each other. The groove 71 is also filled with sealant 75 .
The bulkhead wall 70 and the side wall 72 are connected by rivets 73 , 73 ′, which also penetrate the side wall 72 , the left horizontal leg 70 ′, and the right horizontal leg 70 ″.
Track sealants 76 and 77 are preferably provided, on the free rims of the left horizontal legs 70 ′ as well as the right horizontal leg 70 ″, between the legs 70 ′, 70 ″ and the side wall 72 .
The entire connection arrangement between the bulkhead wall 70 and the side wall 72 described above is additionally sealed on each side of the bulkhead wall 70 by sealant coatings 78 and 79 which, at the least, overlap a surface section of the bulkhead wall 70 , the interior head of the respective rivets 73 , 73 ′, each of the track sealants 76 , 77 , and at least one area of the internal side wall 72 .
In this way, a seal with three barriers between the bulkhead wall 70 and the side wall 72 is achieved. This sealing of the joint locations provides for reliable sealing of the interior spaces 80 and 82 from the external surroundings 84 .
During manufacture, each of these barriers is individually tested, during the assembly of the structure, in order to find any leaks as early as during the formation process. Here a differentiation is made between the dry tests in which gaseous test substances are used and the wet tests which take place with liquids such as, for example, water, fuel, or fuel substitute liquids. Customarily, these tests are carried out using high pressure in the tank space while simultaneously looking for leakage. In the process according to this invention, however, the interior space of the container or integral tank 10 is put under pressure lower than the prevalent pressure of the external environment. This causes leakage, in contrast to a process according to the state of the art, to proceed in the reverse direction along a track which terminates at the source of leakage, and thus the point of entry. Using this process, leakage can be both reliably located and perfectly pinpointed.
When a tank has a simple geometry, a transparent tank cover can be used in order to observe and locate the entry of the leakage through the transparent tank lid. When a more complicated tank geometry with especially difficult access to individual chambers of a tank or, as in the example of FIG. 1 , an integral tank is present, it is preferable to insert controllable camera probes through the special sealable openings provided for such purpose in the tank covers of the individual chambers.
FIG. 4 shows an example of such a camera probe inserted into an integral tank.
The tank cover 11 of FIG. 1 has been replaced in the example of FIG. 4 by a tank cover 11 ′. A swiveling and axially adjustable probe 90 can be guided through a guiding tube 91 into the integral tank 10 . The guiding tube 91 is provided at its external end with a handle 92 , with the help of which the guiding tube 91 swivels about the transition point through the tank cover 11 ′ and can then be axially shifted. The guiding tube 91 is inserted through an opening 31 in the middle horizontal bulkhead wall 30 into the lower chamber 18 of the integrated tank 10 . A camera head 93 is provided at the lower end of the guiding tube 91 , which is linked by outside controlled optical or electrical wiring 94 through the guiding tube 91 to an image reproduction device (not shown here).
In addition to the camera head 93 , a device 95 , such as a spray nozzle, for emission of a sealant is located at the end of the guiding tube 91 . This device is also linked by a tube 96 extending through the conducting tube 91 outside to a feed line (not shown here) for a sealing compound. Sealant can be transported through the tube 96 into the nozzle 95 and then delivered under pressure through the nozzle 95 .
In place of a camera head 93 , or in addition thereto, a different type of sensor, for example a gas sensor, can also be used. This makes it possible to detect and recognize a point of entry of a gas entering into the chamber 18 of the integrated tank 10 from the outside.
With the shown probe 90 , it is possible to test the interior of a container, especially the shown integral tank 10 , for leakage when the container interior space is under lower pressure than the surrounding environment. It is thus possible to locate and identify the points of leakage and, using the nozzle 95 , to bring up sealing compound from the inside to the corresponding points of leakage of the chamber 18 and thus seal off and eliminate the leakage. If necessary, lighting (not shown here) can Also be planned to be added to the camera head 93 . As a probe 90 , for example, a conventional commercial borescope can be used.
The invention is not limited to the aforementioned examples, which have only been used for a general description of the invention. Within the scope of legal protection, a device according to this invention can take on other than the above-described forms. In this connection, the device can also include features which constitute a combination of the individual characteristics of the claims.
The reference characters in the claims and the drawings serve only for better understanding of the invention and are not to be considered to limit the scope of protection.
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A process for testing the tightness of containers includes making available a first fluid in the container interior space that is different from a second fluid surrounding the container, creating a negative pressure in the container interior space, testing the interior surfaces of the container side wall for traces of second fluid penetration, and possibly localizing any entry points.
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BACKGROUND
[0001] This invention relates to a system and method of developing a drilling fluid in an efficient and environmentally-friendly manner. This invention further relates to recycling a drilling fluid.
[0002] Drilling fluids are used downhole in well-drilling operations in treating subterranean wells. In offshore drilling operations, these drilling fluids are usually mixed onshore in large full scale production volumes and are delivered to the offshore platform by trucks and barges and stored for later use. However, this can be time-consuming, and the equipment needed to transport and store the drilling fluids is costly. Therefore what is needed is a system and method of developing drilling fluids which eliminates these problems.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] [0003]FIG. 1 is a schematic view depicting an embodiment of the invention.
[0004] [0004]FIG. 2 is a schematic view depicting an alternative embodiment of the invention.
DETAILED DESCRIPTION
[0005] An embodiment of the system and method of the present invention will be described in connection with the drilling of a subterranean well in an offshore location with a water-based fluid in FIG. 1.
[0006] Water, such as seawater, is recovered in any conventional manner and passes, via a conduit 10 , to a vessel 12 in which chemicals are added to the water to discourage bacteria growth. The treated water then passes through a conduit 14 under the action of a pump 16 and into a blender 20 .
[0007] Specialty drilling additives from a container 22 are added to the water in the blender 20 to mix with the water to develop an initial water-based drilling fluid (hereinafter referred to as “drilling fluid”). The specialty drilling additives may include fluid controlling additives such as starches, encapsulating polymers, or other dry material such as caustic soda, sodium chloride, and silicic acid, and/or concentrated liqueurs.
[0008] The drilling fluid then passes from the blender 20 through a conduit 24 under the action of a high shear pump 26 , which pumps the drilling fluid into a blender 30 and maximizes the efficiency of materials introduction. Various bulk materials, such as bentonite and barite, from a container 32 , mix with the drilling fluid in the blender 30 to further develop the drilling fluid. It will be understood that drilling additives and materials are drilling fluid components.
[0009] The drilling fluid then passes from the blender 30 through a conduit 34 into an analyzer 36 which includes one or more of a number of specialty instruments such as a volume meter, a three-phase meter, a PH meter, and a mud analyzer for measuring rheology and other fluid properties. The analyzer 36 , including the above instruments, analyzes the drilling fluid and provides information as to the suitability of the drilling fluid for use downhole.
[0010] If the analyzer 36 determines that the drilling fluid is suitable for use downhole, the drilling fluid from the analyzer is directed into a conduit 38 for passage to a downhole pump system 40 . If the analyzer 36 determines that the drilling fluid is unsuitable for use downhole, the drilling fluid is directed into a conduit 42 which is connected to the conduit 14 for recycling and therefore reconditioning the unsuitable drilling fluid.
[0011] After entering and passing through the downhole pump system 40 , the drilling fluid passes through a conduit 44 to and through a hose system 50 and a kelly 51 to a downhole location for assisting in the further drilling of the well.
[0012] After use, the drilling fluid is returned from the downhole location, via a conduit 52 , to a shale shaker 54 with vibrating screens to separate out larger drill cuttings (solids) for disposal. The drilling fluid then passes through a conduit 56 and into a degasser 58 to remove unwanted gas from the drilling fluid. For further cleaning, the drilling fluid then passes through a conduit 60 to a mud cleaner 62 that includes hydrocyclones positioned over small mesh screens to remove smaller drill cuttings for disposal.
[0013] From the mud cleaner 62 , the majority of the drilling fluid is recycled through a conduit 64 . A smaller amount of drilling fluid passes through a conduit 66 to a centrifuge 68 wherein barite is separated out and recycled through a conduit 70 . The drilling fluid from the centrifuge 68 passes through a conduit 72 to another centrifuge 74 that separates out the smallest drill cuttings for disposal. The drilling fluid from the centrifuge 74 is then recycled through a conduit 76 . During the passage of the drilling fluid through the conduit 76 , the recycled barite from the conduit 70 and the drilling fluid from the conduit 64 are added and mixed with the drilling fluid in the conduit 76 to prepare the drilling fluid for entry into the analyzer 36 . The analyzer 36 again determines the suitability of the drilling fluid for reuse downhole. Alternatively, the recycled water-based drilling fluid may be passed, via the conduit 76 , to the sea or ocean in a safe manner adhering to environmental regulations or used to develop a new drilling fluid system for a new hole section.
[0014] The separated drill cuttings from the shale shaker 54 , the mud cleaner 62 , and the second centrifuge 74 are extracted via conduits 80 , 82 , and 84 , respectively, and sent back to shore for an environmentally safe disposal or disposed of on location if regulations allow.
Alternates and Equivalents
[0015] [0015]FIG. 2 depicts an alternative embodiment of the system and method of the present invention that will be described in connection with the drilling of a subterranean well in an offshore location with a hydrocarbon-based fluid. The embodiment of FIG. 2 is similar to that of FIG. 1, and includes substantially similar components which are given the same reference numerals.
[0016] A hydrocarbon-base fluid is delivered in any conventional manner to the conduit 10 for introduction into the vessel 12 . The hydrocarbon-base fluid is developed into a hydrocarbon-based drilling fluid (hereinafter referred to as “drilling fluid”) for use downhole in substantially the same manner as the water-based fluid in the previous embodiment. Thus, it passes through the system in the manner described above before it passes through the hose system 50 and the kelly 51 to a downhole location. The drilling fluid returns from the downhole location in a conventional manner and is passed through the shale shaker 54 , the mud cleaner 62 and the additional centrifuge 74 in the manner described above in connection with the embodiment of FIG. 1. Drill cuttings (solids) are removed from the shaker 54 , the mud cleaner 62 and the additional centrifuge 74 via conduits 80 , 82 , and 84 , respectively and pass into a solvent extraction unit 86 to recover the hydrocarbon-base fluid.
[0017] The solvent extraction unit 86 contains a lower pressure liquid recovery section, wherein the hydrocarbon-base fluid is recovered from the hydrocarbon-based drilling fluid still on the drill cuttings. In particular, the solvent extraction unit 86 contains lower boiling point hydrocarbon-based solvent fluids, or alternatively carbon dioxide, to extract the higher boiling point hydrocarbon-base fluid from the drill cuttings. The drill cuttings may then be disposed of in a safe manner adhering to environmental regulations through conduit 88 .
[0018] After recovery of the hydrocarbon-base fluid, the solvent fluids undergo a recompression cycle so that they may be recycled for later use. The hydrocarbon-base fluid is then recycled to a storage container 92 via a conduit 94 . The storage container 92 stores the hydrocarbon-base fluid for reuse and is connected to the conduit 10 via a conduit 96 for recycling the hydrocarbon-base fluid back to the vessel 12 for reintroduction into the drilling fluid system.
[0019] The benefits of this system are twofold. First, well construction costs can be reduced by minimizing the volume of drilling fluids used, maximizing the recycling of well-drilling fluids and cuttings, and reducing transportation costs associated with drilling fluids. Secondly, the drilling fluids and components of this system are environmentally friendly in that they are dramatically reduced in volume and can be reused for other well-drilling operations.
[0020] Although only a few exemplary embodiments of this invention have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to cover the structures described herein as performing the recited function. In the claims, means-plus-function clauses are intended to cover the structures described herein as performing the recited function and not only structural equivalents, but also equivalent structures.
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A system and method for developing and recycling drilling fluids at the site of a subterranean well is described, thus eliminating the need for transporting the fluids to the site.
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FIELD OF THE INVENTION
This invention relates to the use of identification means in cooperation with the computer system aboard a vehicle to track service and maintenance activities relating to the vehicle when the vehicle is operated under severe conditions.
BACKGROUND OF THE INVENTION
It is common knowledge that a properly maintained motor vehicle is more dependable, safer, lasts longer, and increases the satisfaction of its owner as compared to a vehicle that is poorly maintained. Furthermore, following a good maintenance schedule helps to preserve the integrity of any warranty that the owner might have on the vehicle. In addition, the residual value of the vehicle is higher at the time of sale or trade-in.
The manufacturer of a vehicle typically provides a maintenance schedule that includes a recommended timetable or mileage schedule for tire rotation, engine tune-ups, lubrication, oil changes, front end alignments, radiator flushing, and the like. Failure to follow prescribed maintenance can seriously shorten the operative lifetime of the vehicle, and can adversely affect any applicable warranties on the vehicle itself or on the specific components. The maintenance schedule generally provides an accelerated timetable for oil changes and other maintenance items if the vehicle has been operated under less than favorable conditions.
The purchasing of a used vehicle is an inherently risky transaction. The buyer suffers from what economists term “an imbalance of information”, wherein the seller, or previous sellers, know vastly more about the vehicle being exchanged than the potential buyer.
SUMMARY OF THE INVENTION
The invention relates to systems and methods to detect and record if and when a vehicle is being operated under adverse conditions. Furthermore, the invention notes the specific nature of the adverse condition(s) and the date(s) on which the adverse operating conditions existed. Additionally, it recalculates and adjusts prorated maintenance schedules to accommodate for the operation of the vehicle under adverse or less than ideal conditions.
The system for monitoring the operation of a vehicle under adverse conditions includes a detection sensor, a transmitter and a circuit module. The detection sensor is installed on or in association with a vehicle component or an operating fluid that may be subject to use or abuse under an adverse operating condition. The transmitter comprises means for transmitting a signal from said sensor to a receiver upon detection of such use or abuse. The circuit module determines whether the adverse operating condition is outside of an acceptable range.
The invention also relates to a method for monitoring the operation of a vehicle under adverse conditions. The method comprises the following. An identification sensor is installed on or in a vehicle component or an operating fluid that may be subject to use or abuse under adverse operating conditions. An antenna or other device is installed for transmitting a signal from the identification sensor. An integrated circuit module is installed for receiving a signal from the sensor that reports the adverse operating conditions that are outside of an acceptable range. The signal is transmitted to a device such as an on-board computer for subsequent handling of the information relating to the operation of the vehicle.
The invention also relates to a method comprising producing computer executable program code. The code is stored in a computer readable medium installed on or associated with a motor vehicle. A program code is provided for deployment and execution on a computer system. The program code comprises instructions that are executed on the computer system. The execution of these instructions causes the computer system to read input obtained from a detector associated with the motor vehicle relative to the occurrence of a condition determined to be a potential adverse operating condition of the vehicle. Data from said detector is transferred to the computer system after which adjustments are made in the maintenance schedule with respect to said condition. The updated schedule is then stored in database storage.
In another embodiment, the invention also relates to a method for deploying an application for detecting and tracking information relating to the operation of a motor vehicle under adverse conditions. The method comprises providing a computer infrastructure being operable to a) receive information indicative of an adverse operating condition; b) generate a signal indicative of the nature and extent of the adverse condition; and c) store the indicia in a non-volatile memory.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features of this invention will be more readily understood from the following detailed description of the various aspects of the invention taken in conjunction with the accompanying drawings in which:
FIG. 1 illustrates the effect of water contamination in brake fluid;
FIG. 2 shows a flowchart of the logic of a computer module;
FIG. 3 exemplifies a computer implementation of the system of the present invention; and
FIG. 4 is a block illustration of embodiments of sensors and modules according to the present invention.
The drawings are not necessarily to scale but instead are merely schematic representations, not intended to portray specific parameters of the invention. The drawings are intended to depict only typical embodiments of the invention, and therefore should not be considered as limiting the scope of the invention. In the drawings, like numbering represents like elements.
DETAILED DESCRIPTION OF THE INVENTION
The present invention utilizes active and passive detection sensors in a system coupled by serial communication with vehicle computers in order to track and record driving patterns under adverse conditions. The system and method combines technologies whereby adverse driving conditions are detected, and data relating thereto is automatically recorded.
Among the adverse operating conditions are the following: high levels of air; fluid and gas contaminants; vehicle operation in extreme temperatures (hot or cold); strenuous driving patterns, such as mountain driving, off-road driving, or city driving; towing and hauling loads, such as a trailer or a boat; hard braking and rapid acceleration, under or over inflated tires, and driving at high altitudes with reduced atmospheric pressures.
The present invention includes the following components and systems, each of which will be described in detail:
1. Adverse condition detection systems 2. Adverse condition computer module 3. Prorated scheduler module 4. Operator notification module 5. Part replacement detection 6. Maintenance record storage module
Adverse Condition Detection Systems
The detectable adverse conditions described hereinabove are a small subset of possible detectable conditions. Numerous other conditions can be detected without deviating from the scope of the present invention. Therefore, the present invention is disclosed by way of illustration and the examples provided do not limit the invention. Several of these examples are disclosed as follows.
a) Air Contaminant Detection Module
FIG. 4 is a block illustration of an embodiment according to the present invention wherein a contaminant detection system module 110 is installed on a vehicle 101 in communication with an adverse condition computer module 116 . The usable lifetime of an air filter is impacted by the quality of air that it filters. If the air contains high levels of contaminants, such as dust, dirt, or other airborne particulates, the filter should be changed more frequently than required under normal operating conditions. Failure to change an air filter at proper intervals results in performance degradation and increased strain on the engine. The technology needed to detect particulate matter in a sample of air is well known technology. The contaminant detection system module 110 repeatedly samples the air before it is filtered to detect the level of air contamination. A diverter 102 is installed into the vehicle's “air-box” 104 prior to the filtration stage air filter 108 . At preset intervals, the diverter 102 is activated and a sample of air is directed to the contaminant detection chamber 106 . The contaminant detection system module 110 samples the air in the chamber 106 to determine the parts per million of contaminates. If the containment level exceeds a preset threshold, the adverse condition computer module 116 is notified and the event is recorded.
Air sampling equipment of the type that is useful in practicing the teachings of the present invention is available from such sources as Airmetrics in Eugene, Oreg. and SKC, Inc. in Eighty Four, Pa.
b) Oil and Transmission Fluid Modules
Vehicle and oil manufacturers recommend oil change schedules for both ideal and severe driving conditions. Manufacturers consider the following conditions to be severe: temperature extremes: ‘stop and go’ driving patterns, excessive idling, hauling heavy loads, and towing. Severe conditions that affect the breakdown of oil generally also have the same effect on the transmission fluid. The same set of guidelines may be used to determine harsh conditions jointly, or additional logic can address and monitor the fluid in the transmission separately.
FIG. 4 also shows one or more sets of additional sensors 122 and associated sensor modules 120 that are installed on the vehicle 101 in communication with the adverse condition computer module 116 . (For simplicity and clarity of illustration only one each of the sensors 122 and sensor modules 120 are shown in the present view, though it will be understood by one skilled in the art that a plurality of different ones of the sensors 122 and sensor modules 120 may be deployed). Thus, fluid sensor module(s) 120 via the sensor(s) 122 may thus determine parameters, such as viscosity or changes in viscosity, reserve alkalinity, fluid oxidation, and volatility of these fluids, thereby determining if these fluids are undergoing appreciable degradation. This information is then reported to the adverse condition computer module 116 .
c) Temperature Sensor Module
Vehicles often include temperature sensors or thermometers 122 to detect and report (display) the outside temperature. These temperature sensors 122 are monitored by temperature sensor modules 120 to ascertain when the vehicle is being operated at temperatures that constitute adverse conditions. If a temperature sensor 122 reports that the temperature is outside of preset thresholds, the temperature sensor module 120 will notify the adverse condition computer module 116 .
d) Driving Pattern Recognition Module
Several types of driving patterns are classified as severe driving, including but not limited to: stop and go driving, short trips, and excessive idling. A driving pattern recognition module 120 is employed to detect when the vehicle's operation matches any of these patterns.
e) Stop and Go Driving
The module recognizes stop and go driving by monitoring the speed of the vehicle over a given time span. If the vehicle accelerates to a certain speed and then decelerates to almost a full stop multiple times in a short period of time, the driving pattern may be categorized as “stop and go” driving. If the acceleration and deceleration exceed a preset threshold, using sensors, such as inertial accelerometers or decelerometers 122 , the drive pattern recognition module 120 will notify the adverse condition computer module 116 . The same sensor module 120 can be used to detect and report “fast acceleration” and “hard stop” patterns. Another type of brake sensor 122 that can be used for determining “hard stop” driving patterns is the one that is associated with the ABS braking system of most vehicles. Still another is one that comprises a magnetic field producing element and a Hall Effect sensor with one of the elements supported for movement relative to the other.
f) Short Trips
A short trip sensor module 120 recognizes short trip patterns by monitoring the length of time or the number of miles traveled from engine start to engine stop. If the vehicle 101 is started and stopped within a short period of time (generally recognized as 10 minutes), or short distance (such as 10 miles), this pattern constitutes adverse driving conditions. If this condition recurs x number of times over a preset threshold of time, the adverse condition computer module is notified.
g) Excessive Idling
An idling module 120 recognizes excessive idling by monitoring the vehicle's 101 speed when the engine is running. If the engine has been running for a fixed time period and vehicle movement has not occurred for a moderate percentage of that time period, the adverse condition computer module 116 is notified. Additional logic in the adverse condition computer module 116 tracks the number of times this condition is reported over a time period, and if the occurrences exceed a preset threshold, the module 116 records the incident as an adverse driving condition.
h) Towing and Load Sensor Module
Towing and hauling heavy loads exert additional strain on an engine and transmission as well as other vehicle components, such as the suspension system and tires. Manufacturers, therefore, consider towing and heavy load hauling to be a severe driving condition. Several methods are available to detect if the vehicle is towing an object. The following are two example methods to monitor if the vehicle is currently towing.
If the vehicle is equipped with a trailer wiring package, a wiring package sensor 122 included in the package is used to detect when the trailer wiring package circuit is closed. If the circuit is closed and the vehicle 101 is moving, the wiring package has been attached to a trailer and is currently towing an object behind it. If the wiring package sensor module 120 detects the closed circuit, it will notify the adverse condition computer module 116 .
The trailer hitch may be modified to detect when it is engaged in towing activity. Sensors, such as strain gauges 122 , are included on the trailer hitch to determine the forces exerted on the hitch. If an associated trailer hitch sensor module 120 detects a tow force, the adverse condition computer module 116 is notified.
The hauling of heavy loads can be monitored with the use of well known devices, such as strain gauges 122 . Again, if such hauling exceeds preset limits so as to constitute an adverse condition, such a condition is reported to the adverse condition computer module 116 .
i) Transmission Stress and Down-Shift Patterns
When traveling in environments with steep grades (mountains and hilly urban areas, such as San Francisco, Calif.), additional stress is placed on the engine and transmission. Often this is accompanied by automatic or manual down-shifting of the transmission. Shifting and speed are controlled and/or monitored by the vehicle computer. This data can be used to determine adverse driving conditions. As an example, on a flat grade, less power is required to maintain a constant speed of, for example, 55 MPH than on a 20% grade, or a 30% grade. Power required to achieve or maintain vehicle speed can be used to detect strenuous driving conditions. Detection of such conditions then evokes notification to the adverse condition computer module 116 . These methods may be used separately or combined to detect if the vehicle is engaged in towing. This condition can also be identified (along with other harsh driving patterns or incidents) by detecting the engine's RPM, looking for a preset threshold for a preset time span. This would also be effective for determining travel up a steep grade, or a driver who does not shift appropriately (like driving 55 MPH in the third gear) as well as revving of the engine while in idle before a drag or street race.
j) Brake Fluid Temperature Sensor Module
Conventional brake fluids are hygroscopic. Over time, brake fluid begins to absorb moisture, and as moisture is absorbed into brake fluid, the boiling temperature of the fluid is lowered. The boiling point may be reduced to such a degree that the normal operation of the brake can cause the fluid to boil, thereby causing vapor to form in the brake system. This may result in the brakes becoming ‘spongy’ or may even cause a complete loss of braking ability.
FIG. 1 depicts the effects of water contamination in brake fluid over a period of several years. While braking, heat builds up in the brake system and is partially dissipated by the brake fluid. If the brake fluid boils, the braking system may be rendered incapacitated and brakes cannot be used to slow the vehicle. In ideal conditions, brake fluid is not heated to temperatures that would cause newer brake fluid, less than three years of age, to boil. However, if the vehicle is routinely subjected to patterns that cause the brake fluid temperature to be higher than a threshold, this qualifies as adverse driving conditions. When this occurs, it is imperative that the service schedule for brake fluid replacement be accelerated.
In order to determine if the brake system is consistently used in adverse conditions, a brake fluid temperature sensor 122 or module 120 is required at each of the four brake cylinders at the wheels as well as the master cylinder. These sensors 122 /modules 120 measure the temperature of the brake fluid while the vehicle 101 is in use. If the temperature exceeds a preset threshold, the adverse condition computer module 116 is notified. Additional logic in the computer module 116 tracks the number, time, and frequency of such notifications. If enough notifications occur in a given time period, the system recognizes that the brake fluid replacement schedule should be altered.
Adverse Condition Computer Module
The adverse condition computer module 116 receives notifications from one or more adverse condition detection sensors 122 or sensor modules 120 that are installed throughout the vehicle 101 . These sensors 122 may be positioned in locations that are suitable for detecting such factors as air contamination, extreme operating temperatures, driving patterns such as rapid acceleration and hard braking, heavy loads, and under or over inflation of tires. An antenna or other transmitting system may be installed sufficiently near to each sensor 122 to relay a detected signal to an integrated circuit module 120 or 116 installed within range of the transmitted signal. The IC module 116 or 120 contains the logic to interpret the notifications from the sensors 122 and to determine if the car is engaging in severe driving conditions. Additionally, the adverse condition computer module 116 is able to determine which systems and corresponding maintenance schedules are impacted by the multitude of sensor 122 notifications. Additionally, the adverse condition computer module 116 may be coupled to an operator notification module (not shown) to notify the vehicle's operator that the vehicle 101 is being operated under severe conditions. Notification can also be transmitted wirelessly to other parties, such as the dealer, the provider of a vehicle or parts warranty, or a service provider, of the severe operation status. The adverse condition computer module 116 may be an independent device or integrated into an existing on-board computer device, and it may be protected from tampering such as using a “black box” architecture.
FIG. 2 is a flowchart showing the logic of an adverse condition computer module useful in the present invention, for example with respect to the. sensors 122 , sensor modules 110 / 120 and adverse condition computer module 116 installed on the vehicle 101 as illustrated in FIG. 4 . These may be installed during the production of the vehicle, or may be acquired and installed as an after-market system. The logic commences at 10 when the vehicle ignition is turned on and the operator starts up the engine. If an adverse condition is detected by one of the sensors, a sensor notification is received at 12 and the relevant data concerning a possible adverse condition executes a sensor dependant adverse condition logic 16 . If the logic indicates at 18 that no adverse condition exists, a message is returned to the sensor notification 12 . If, however, the logic recognizes the presence of an adverse condition, an updated maintenance schedule 22 is prepared and is sent to the operator notification module 24 , which in turn updates the sensor dependent adverse condition logic 16 .
Prorating Vehicle Maintenance Schedules
There is currently no automated method to prorate a vehicle service schedule based on adverse usage. The algorithm shown below can be used for such prorating purposes, using as an example the oil change schedule for a vehicle. The oil in the vehicle under ideal conditions should be replaced every 7500 miles. Under severe conditions, the oil should be replaced every 3000 miles. Immediately after an oil change, the vehicle towed an object for 500 miles. The following calculation will determine the prorated maintenance schedule, indicating when the oil must be changed next:
7500
-
(
500
3000
*
7500
)
=
6250
In general terms, the formula for mile based schedules can be expressed as:
Normal_Schedule
-
(
Advesrse_Miles
Adverse_Schedule
*
Normal_Schedule
)
=
Pro_Rated
_Schedule
In a preferred embodiment, a weighting mechanism can also be used based on the severity of driving conditions and the likely relative vehicle wear. As an example, operating the vehicle in an ambient temperature of 110° F. would carry a higher weight than the same operation at 95° F. Additionally, towing a heavy object would have a higher weight than towing a lighter object and a higher weight than operating at 95° F. Finally, if multiple adverse conditions exist, the individual calculations could be aggregated prior to executing the generic prorating logic.
Operator Notification Module
When a vehicle is operating under adverse conditions, it is necessary to inform the driver and perhaps others of such conditions. Several known methods can be used to inform the driver of severe conditions. One method is to use a standard dashboard light possibly in conjunction with an audible notification. More advanced vehicles may be capable of displaying added detailed information about the severe conditions using vehicle information displays. Such displays can accurately describe the severe conditions the vehicle is currently operating under and may additionally display the updated prorated maintenance schedule. Among these displays are meters, gauges and other similar visual warnings. In an extreme measure, the notification may take the form of an ignition interrupt, a speed governor, a temporary modification to performance settings, or other similar device.
While shown and described herein as a method and system for tracking maintenance services that have been performed on a vehicle, it is understood that the invention further provides various alternative embodiments. For example, in one embodiment, the invention provides a computer-readable/useable medium that includes computer program code to enable a computer infrastructure to send any one of a number of prerecorded telephone messages to a service provider, dealer, or even alert the driver of the adverse condition. To this extent, the computer-readable/useable medium includes program code that implements each of the various process steps of the invention.
It is understood that the terms “computer-readable medium” or “computer useable medium” comprise one or more of any type of physical embodiment of the program code. In particular, and referring to FIG. 3 , the computer-readable/useable medium can comprise program code embodied on one or more portable storage articles of manufacture (e.g., a compact disc, a magnetic disk, a tape, etc.), on one or more data storage portions of a computing device, such as the memory 52 and/or the storage system 62 (e.g., a fixed disk, a read-only memory, a random access memory, a cache memory, etc.).
Communication throughout the vehicle can occur via any combination of various types of communication links. For example, the communication links can comprise addressable connections that may utilize any combination of wired and/or wireless transmission methods.
As shown in FIG. 3 , a vehicle 70 includes a computer system 50 . The system comprises a processing unit (CPU) 40 , a memory 56 , a bus 60 , and input/output (I/O) interfaces 64 . Within the memory 56 may be installed the vehicle adverse driving system 54 including an adverse condition detector 66 , a notification module 26 , and other components as needed or desired. Further, the computer system 50 is shown in communication with external I/O devices/resources 58 and storage system 62 . In general, the processing unit of the computer system 50 executes computer program code, such as the code to implement the parts detection system, which is stored in the external memory 56 and/or database storage system 62 . The adverse condition detector 66 can be, for example, a pressure or temperature gauge, a high or low fluid level detector, accelerometer, or strain gauge, depending on the condition or conditions being monitored.
While executing computer program code, the computer system 50 can read and/or write data to/from the memory 56 , the storage system 62 , and/or the I/O interfaces 64 . The bus 60 provides a communication link between each of the components in computer system 50 . The external devices 58 can comprise any of the previously mentioned components, such as the sensor or detector, the reader, the data stream converter and the user notification module.
Further, I/O interfaces 64 can comprise any system for exchanging information with one or more of the external devices 58 . Still further, it is understood that one or more additional components (e.g., system software, math co-processing unit, etc.) not shown in FIG. 4 can be included in computer system 50 . However, if computer system 50 comprises a handheld device or the like, it is understood that one or more of the external devices 58 (e.g., a display) and/or the storage system 62 could be contained within computer system 50 , not externally as shown. The computer system can further include a wired or wireless connection 78 and bus 80 to allow it to communicate outside of the vehicle to, for example, an owner 82 or a dealer 84 . This capability allows the transfer of updated information for any of the purposes heretofore described.
The storage system 62 can be any type of system (e.g., a database) capable of providing storage for information under the present invention. To this extent, the storage system 62 could include one or more storage devices, such as a magnetic disk drive or an optical disk drive. In another embodiment, the storage system 62 includes data distributed across, for example, a local area network (LAN), wide area network (WAN), or a storage area network (SAN) (not shown). Also, although not shown, additional components, such as cache memory, communication systems, system software, etc., may be incorporated into computer system 50 .
The invention provides a business method that performs the process steps of the invention on a subscription, advertising, and/or fee basis. That is, a service provider could offer to manage the monitoring or reporting of the data. In this case, the service provider can create, maintain, support, etc., a computer system 50 on-board a vehicle 70 . The computer system 50 performs the process steps of the invention for one or more customers, such as the owner or dealer. In return, the service provider can receive payment from the customer(s) under a subscription and/or fee agreement and/or the service provider can receive payment from the sale of advertising content to one or more third parties.
As used herein, it is understood that the terms “program code” and “computer program code” are synonymous and mean any expression, in any language, code or notation, of a set of instructions intended to cause a computing device having an information processing capability to perform a particular function either directly or after either or both of the following: (a) conversion to another language, code or notation; and/or (b) reproduction in a different material form. To this extent, program code can be embodied as one or more of an application/software program, component software/a library of functions, an operating system, a basic I/O system/driver for a particular computing and/or I/O device, and the like.
The computer system 50 is only illustrative of various types of computer infrastructures for implementing the invention. For example, in one embodiment, computer system 50 comprises two or more computing devices (e.g., a server cluster) that communicate over a network to perform the various process steps of the invention. Moreover, computer system 50 is only representative of various possible computer systems that can include numerous combinations of hardware.
To this extent, in other embodiments, computer system 50 can comprise any specific purpose computing article of manufacture comprising hardware and/or computer program code for performing specific functions, any computing article of manufacture that comprises a combination of specific purpose and general purpose hardware/software, or the like. In each case, the program code and hardware can be created using standard programming and engineering techniques, respectively.
Moreover, the processing unit or CPU 40 may comprise a single processing unit, or be distributed across one or more processing units in one or more locations, e.g., on a client and server. Similarly, the memory 56 and/or the storage system 62 can comprise any combination of various types of data storage and/or transmission media that reside at one or more physical locations.
In one non-limiting implementation, the invention contemplates the use of one or more radio frequency identification (RFID) readers or the like variously located throughout the vehicle. The readers may be positioned in the vehicle so that the aggregate coverage by the one or more RFID readers covers the component parts of the vehicle that are likely to contain sensors. The use of RFID can be two-fold: 1) to relay information from the sensors to the computer module to avoid the use of wires, and 2) for the computer module to report information to the dashboard or consumer of the information, such as the dealership or potential buyer of the vehicle. The RFID tag could take on many forms. The RFID tag can be a passive tag, an active tag, or a semi-passive tag. With a passive tag, the reader(s) emits an electromagnetic field that induces an electrical current in an antenna of the tag. The electrical current provides power for the tag, for example, for powering an integrated circuit in the tag, which invokes the tag to emit or transmit the information stored in the tag (e.g., in Electrically Erasable Programmable Read-Only Memory, or EEPROM, etc.) via the antenna.
With an active tag, the RFID tag includes an internal power source such as a battery, a solar cell, etc., that powers the integrated circuit, which broadcasts the sensor information for reception by an authorized reader tuned to a broadcast frequency. Alternatively or additionally, the RFID tag may be powered from the battery of the vehicle. The RFID tag may also be semi-passive in that an internal battery or the vehicle's battery may provide power to activate the tag, but the field provided by the reader invokes the broadcast of the sensor information.
It should be understood that the invention is not limited solely to the use of RFID tags as sensors. Other similar devices such as RuBee (registered trademark of Visible Assets, Inc.) long wavelength tags, VLIS visible light identification tags and H-P Memory Spot tags can likewise be utilized as sensors in the practice of this invention.
While shown and described herein as a method and system for detecting adverse operating conditions relating to the operation of a vehicle, it is understood that the invention further provides various alternative embodiments. For example, in one embodiment, the invention provides a computer-readable/useable medium that includes computer program code to enable a computer infrastructure to monitor all systems in the vehicle. To this extent, the computer-readable/useable medium includes program code that implements each of the various process steps of the invention.
The foregoing description of various aspects of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed and, obviously, many modifications and variations are possible. Such modifications and variations that may be apparent to a person skilled in the art are intended to be included within the scope of the invention as defined by the accompanying claims.
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Details relating to the operation of a vehicle under adverse conditions are recorded and collected. This data is particularly useful to forestall catastrophic failures, and to provide valuable information for potential buyers of used vehicles. Among the operating conditions that are considered are high levels of air contaminants, operation in extreme hot or cold temperatures, hauling heavy loads, as well as hard braking, turning and acceleration. In addition to the detection and recording of data, prorated maintenance schedules are recalculated and adjusted to accommodate for the operation of the vehicle under these adverse or less than ideal conditions. Typically, the data is stored in the on-board computers present in most vehicles. Periodic off loading of the data to the dealer and service providers is also provided.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation-in-part of U.S. application Ser. No. 12/591,612 filed on Nov. 25, 2009, now pending.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The instant disclosure relates to a vacuum glass structure. In particular, the instant disclosure relates to a flat vacuum glass structure that achieves internal vacuum by means of air extraction through a pumping tube.
[0004] 2. Description of Related Art
[0005] Vacuum in a glass structure can be achieved by first using two glass substrates separated at a suitable distance in between, bonding them with adhesives at the periphery, and then exhausting/extracting air molecules from the internal cavity with a vacuum pump, and further placing the getter material in the cavity. The internal vacuum pressure may range approximately from 10 −2 to 10 −7 torr. This conventional technique can be applied to vacuum glass components in the Field Emission Display (FED), Vacuum Fluorescent Display (VFD), Plasma Display Panel (PDP), and so forth.
[0006] There are several ways for making the vacuum glass. For example, one common approach is to extract gas molecules out of the cavity through a glass pumping tube, and then hermetically seal and truncate the tube. The truncation of the hermetic seal is accomplished by melting the glass pumping tube with a local heating process upon completion of vacuum extraction system. However, because the working temperature required to melt glass is relatively high, the heating point for melting the glass pumping tube can not be too close to the glass substrate, thus to prevent cracking in the glass substrate due to the effect of high thermal gradient. As a result, a small piece of the glass pumping tube will unavoidably remain on the outside of the glass substrate after the fusion and cut-off processes. This type of glass pumping tube would leave a remaining protrusion from the surface of the glass substrate. In applications, although this problem may be reduced through suitable mechanical designs, the conventional design still can not achieve total planarization on the surface of the vacuum glass substrate. Furthermore, basing on numerous relevant experiments, it is shown that the protrusion of the glass pumping tube from the glass substrate is a necessary result from the conventional manufacturing technique, and is inevitable.
[0007] In order to resolve the aforementioned issue concerning the protrusion of the glass pumping tube from the glass substrate, a structural design of vacuum glass substrate has been developed. The improved design introduces a recessive gap respectively at the edges of two glass substrates, with the internal end of the pumping tube located inside of the cavity formed by the two glass substrates and the seal, and the axle of the pumping tube being parallel to the surface of the glass substrate, thereby allowing that the external end of the pumping tube after hermetic seal can be located within the geometric space constituting the gap so as to prevent the hermetically sealed pumping tube from protruding out of the two glass substrates.
[0008] However, during manufacturing processes, the internal end of the pumping tube is directly installed between the two glass substrates. This may lead to the existence of lower air transferring efficiency, or result in connection blockage in the pumping tube by the seal of the glass frit. Therefore, improvements for the aforementioned vacuum glass substrate structure remains to be desired.
[0009] Accordingly, in view of the amendable defects found in prior art as previously described, the inventors of the instant disclosure have proposed the instant disclosure featuring reasonable design and effectiveness in improving the aforementioned drawbacks.
SUMMARY OF THE INVENTION
[0010] The objective of the instant disclosure is to provide a vacuum glass substrate structure having enhanced of air transferring efficiency and eliminating pumping tube blockage. Besides, it can successfully achieve the planarization of glass surface without additional mechanism designs.
[0011] To accomplish the objective above, the instant disclosure provides a vacuum glass substrate structure comprising at least two glass substrates arranged parallel to each other with a constant distance in between and the glass frit applied to join the peripheries of the glass substrates and seal the glass structure.
[0012] The glass substrates and the glass frit jointly constitute a hermetically sealed vacuum room. A receiving gap is installed at the periphery of the glass substrate toward the inward direction, and the internal surface of the glass substrate is further installed with an air chamber formed to be in communication with the vacuum room, as well as a glass tube groove for receiving a pumping tube. The air chamber is adjacent to the receiving gap, with the air chamber, the glass tube groove and the receiving gap being connected in series. The pumping tube is located within the receiving gap with the internal end of the pumping tube extending from the receiving gap into the air chamber through the glass tube groove, and is in communication with the air chamber. Glass fit adheres to the external edge of the pumping tube extending into the glass tube groove in order to hermetically seal the glass tube groove, while the external end of the pumping tube does not surpass the geometric space forming the receiving gap and is also sealed.
[0013] Preferably, the periphery of the air chamber, G, and the capacity of the air chamber, C, essentially follow the relationship equations as below:
[0000] G≧ 2 ×Pi×R and
[0000] C≧Pi×R 2 ×h,
[0014] where Pi indicates the ratio of the circumference of a circle to the diameter (π), R the radius of the external circumference of the pumping tube, and h the interval between the two glass substrates.
[0015] The beneficial effects that the instant disclosure can provide include: a structure of air chamber is added to the location where the pumping tube couples to the internal vacuum room, such that during the aforementioned manufacture processes it facilitates to improve air transferring efficiency and eliminate concerns about such as accidental blockage in the pumping tube caused by the adherence of glass frit and the like, thus enhancing the product yield through the design of such an air chamber structure.
[0016] Besides, by means of the installation of such a receiving gap structure, the sealed and truncated pumping tube will not protrude out of the rim or surface of the two glass substrates, but accommodated inside of the receiving gap, so as to achieve the objective of planarization in the two glass substrates without any additional mechanism designs to overcome the defects in non-planarization.
[0017] In order to further appreciate the features and technical contents of the instant disclosure, references are made to the detailed descriptions and appended drawings as below; however, the appended drawings shown herein are simply referential and illustrative, rather than for limiting the scope of the instant disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a disassembly stereogram of the instant disclosure.
[0019] FIG. 2 is an assembly stereogram of the instant disclosure.
[0020] FIG. 3 is a top view ( 1 ) of the instant disclosure.
[0021] FIG. 4 is a top view ( 2 ) of the instant disclosure showing that the pumping tube is accommodated in the receiving gap after being hermetically sealed.
[0022] FIG. 5 is a plane side view of the instant disclosure showing that the air chamber is formed in the lower glass substrate.
[0023] FIG. 6 is another plane side view of the instant disclosure showing that the air chamber is conjunctively formed by the upper and lower glass substrates.
[0024] FIG. 7 is a top view ( 3 ) of the instant disclosure showing an embodiment of variation on the placement of the receiving gap.
[0025] FIG. 8 is a top view ( 4 ) of the instant disclosure showing an embodiment of variation on the placement of the receiving gap.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] Refer now to FIGS. 1 to 3 , wherein the instant disclosure provides a vacuum glass substrate structure comprising two glass substrates 2 , a pumping tube 4 and a glass frit 3 .
[0027] The two glass substrates 2 are arranged parallel to each other and maintained a constant distance in between. A corresponding receiving gap 21 is disposed at the periphery thereof toward an inward direction. A glass tube groove 22 is further recessively disposed on the internal surface of the adjacent sides of the two glass substrates 2 . The air chamber 5 is close to the receiving gap 21 , and the glass tube groove 22 is connected in series with the air chamber 5 and the receiving gap 21 . In addition, a supporter 4 is installed between the two glass substrates 2 thereby separating and supporting the two glass substrates 2 maintaining a constant interval in between.
[0028] The pumping tube 4 is placed at the receiving gap 21 in the glass substrate 1 , with the internal end of the pumping tube 4 extends from the receiving gap 21 into the air chamber 12 through the glass tube groove 22 so that pumping tube 4 is allowed to communicate with the air chamber 12 .
[0029] The glass frit 3 may be a glass paste, and is applied to the periphery of the two glass substrates 2 sealing the two glass substrates 2 hermetically (under a solidification condition of 460° C. for 30 minutes). Thus, the glass frit 3 and the two glass substrates 2 jointly form a vacuum room 14 . Also, the glass fit 3 sticks to the outer rim of the pumping tube 4 and extends into the glass tube groove 22 to provide a hermetic seal between the edge of the glass tube groove 22 and the air chamber 12 . Accordingly, the air chamber 12 can be in gas communication with the vacuum room 14 .
[0030] To further illustrate the operations of vacuum extraction, a vacuum pump (not shown) is used to extract gas molecules from inside of the vacuum room 14 via the pumping tube 4 , placing the vacuum room 14 under a highly vacuum state (10 −2 ˜10 −7 torr). During extractions, the internal end of the pumping tube 4 extends into the air chamber 12 and gradually pumps gas molecules out of the vacuum room 14 , the inside of vacuum room 14 can thus reach the desired vacuum condition through extractions. Upon reaching the desired vacuum conditions, an appropriate heating devices, e.g., a heating coil 5 , is employed to locally heat up the external end of the pumping tube 4 (at a preferred temperature ranging between 600° C. and 700° C.). The location where the pumping tube 4 is locally heated will melt and form a fusion bump thereby enabling completion of hermetic sealing to the pumping tube 4 , resulting in evacuation of the vacuum room 14 . Finally, as shown in FIG. 4 , the pumping tube 4 is truncated at the fusion bump and hermetically sealed to form an external end 22 . Thus, the external end 22 can be kept within the geometric boundary of the receiving gap 21 without protruding. The planarization of structural surface of the glass substrates 2 can therefore be retained.
[0031] In the instant disclosure, as shown in FIG. 5 , the air chamber 12 can be installed recessively on the inner surface of any one of the two glass substrates 2 . That is, either the upper or the lower glass substrate alone can provide the space for constructing the air chamber; or alternatively, as shown in FIG. 6 , the air chamber 12 is installed in recess jointly on the inner surface of the two glass substrates 2 . In other words, the air chamber is provided by both the upper and the lower glass substrates at the same time. The profile of the air chamber 12 may be cylindrical, rectangular or of any other geometries, and the size thereof can be also designated based on the requirements of practical implementations.
[0032] Preferably, the periphery of the air chamber 12 , G, and the capacity of the air chamber 12 , G, essentially follow the relationship equations as below:
[0000] G≧ 2× Pi×R and
[0000] C≧Pi×R 2 ×h,
[0033] where Pi indicates the ratio of the circumference of a circle to the diameter (π), R the radius of the external circumference of the pumping tube, and h the interval between the two glass substrates.
[0034] In accordance with the equations illustrated as above, it is possible to effectively reduce the bottleneck existing in the air transferring flow and prevent the occurrence of pumping tube blockages. In the design of the instant disclosure, since the air chamber 12 and the pumping tube 4 respectively belong to two different geometrical blocks, due to the required communication between them, the external edge of the pumping tube 4 is therefore taken to define the minima of the volume and circumference in the air chamber 12 without imposing any limits on the geometry thereof. Thus, the air chamber 12 can be of cubic, elliptical, cylindrical, spherical or even irregular shapes, and the geometry of the air chamber 12 is only restricted by the minima of the volume and circumference thereof. However, the profile of the air chamber 12 is by no means limited to the cylinder-like shape shown in the diagram of the instant disclosure and the cross-section of the pumping tube 4 is not limited to be circular, either. The relationships regarding to geometry sizes between the air chamber 12 and the pumping tube 4 can be approximated based on the aforementioned equations or other suitable mathematic formula for further designing geometry sizes of the air chamber and the pumping tube.
[0035] In addition, the air chamber 12 can be further used for the placement of the getter material in order to provide and preserve the desired vacuum condition.
[0036] Also, in the embodiments shown as FIGS. 1 to 4 , the receiving gap 21 is installed at the center on one side of the two glass substrates 2 . For example, in case that a pumping tube 4 having an external diameter of 5 mm is used, the depth of the receiving gap 21 inwardly recessed can be 4 mm, which is sufficient for accommodating the protruding pumping tube 4 after sealing. However, the location where the receiving gap is installed is by no means limited thereto. As shown in FIGS. 7 and 8 , the receiving gap 21 and 21 a may be also installed at a peripheral location on a lateral side or a corner of the two glass substrates 2 . Alternatively, the receiving gap may be formed by inwardly excavated from one of the common outer top side and outer bottom side on the periphery of the two glass substrates 2 (not shown). Take another example, as shown in FIG. 7 , wherein the receiving gap 21 a is constructed by cutting in slant one of the four lateral corners of the two glass substrates 2 ; that is, the geometric space of the receiving gap 21 a is triangular, while the external end 22 of the pumping tube 4 should not surpass the apex of the triangular receiving gap 21 a . For further illustrations, in the present embodiment, two glass substrates with each having a thickness of 3 mm can be selected, a pumping tube of 3 mm in the external diameter can be used, and the safe design value for the protrusion length of the pumping tube after sealing is 4 mm. Therefore, based on the mathematic formula for the three sides of a right triangle, truncating 5.6 mm in both lateral and longitudinal lengths at the corner of the glass substrates allows for accommodating and “burying” the 4 mm protrusion of the pumping tube within the geometric space of the gap.
[0037] From the illustrations set forth as above, it can be seen that the instant disclosure adds an air chamber structure at the location where the pumping tube links to the internal vacuum room, such that, during the aforementioned manufacture processes, the air transferring efficiency can be enhanced and the concerns about accidental blockage in the pumping tube by the glass frit and the like can be effectively prevented, thus achieving the improvement in product yields by means of the air chamber structure according to the instant disclosure.
[0038] Meanwhile, through the design of a receiving gap structure, the truncated pumping tube does not protrude out of the edge or surface of the two glass substrates. Rather, but the truncated end of the tube is contained inside of the receiving gap, such that the objective of surface planarization in the two glass substrates can be successfully achieved without having to install extra mechanism designs to eliminate such a non-planarization defects. Therefore, the instant disclosure advantageously enables applications in products like construction glasses, Field Emission Display (FED), Vacuum Fluorescent Display (VFD), Plasma Display Panel (PDP) etc. requiring both the features of heat isolation and light transmission.
[0039] The texts illustrated hereinbefore simply set forth the preferred embodiments of the instant disclosure, rather than limiting the scope of the instant disclosure. All effectively and structurally equivalent changes, modifications and alternations made thereto in accordance with the disclosures and appended drawings of the instant disclosure are therefore deemed as being included in the scope of the instant disclosure defined in the following claims.
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A vacuum glass structure comprising two glass substrates maintained at an substantially constant interval by a glass frit paste sealingly adhering to the peripheries thereof, forming a hermetically sealed vacuum room. A receiving gap is formed at the periphery of the glass substrate. The internal surface of the glass structure further includes an air chamber and a glass tube groove for receiving a pumping tube. The pumping tube can be placed inside the receiving gap with the internal end of the pumping tube extending from the receiving gap through the glass tube groove into the air chamber. The external end of the pumping tube constitutes a hermetic seal retained within the geometric boundary of the receiving gap. The air chamber structure may improve air transferring efficiency and prevents problems such as blockage in the pumping tube, thus enabling an increase in production yield.
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CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is related to U.S. application Ser. No. 09/426,870, filed Oct. 26, 1999, by Robert M. Guidash, and entitled, CMOS IMAGE SENSOR WITH EXTENDED DYNAMIC RANGE.
FIELD OF THE INVENTION
The present invention pertains to semiconductor based image sensors and more particularly to Active Pixel image sensors (APS) or Passive Pixel image sensors (PPS) having increased dynamic range.
BACKGROUND OF THE INVENTION
APS are solid state imagers wherein each pixel contains both a photo-sensing means and at least one other active component, creating a charge that is converted to a signal (either a voltage or current signal). The signal represents the amount of light incident upon a pixel photosite. The dynamic range (DR) of an image sensing device is defined as the ratio of the effective maximum detectable signal level, typically referred to as the saturation signal, (V sat ), with respect to the rms. noise level of the sensor, (σ noise ). This is shown in Equation 1.
Dynamic Range= V sat /σ noise Equation 1
Image sensor devices such as charge coupled devices (CCD) that integrate charge created by incident photons have dynamic range limited by the amount of charge that can be collected and held in a given photosite, (V sat ). For example, for any given CCD, the amount of charge that can be collected and detected in a pixel is proportional to the pixel area. Thus for a commercial device used in a megapixel digital still camera (DSC), the number of electrons representing Vsat is on the order of 13,000 to 20,000 electrons. If the incident light is very bright and creates more electrons that can be held in the pixel or photodetector, these excess electrons are extracted by the anti-blooming means in the pixel and do not contribute to an increased saturation signal. Hence, the maximum detectable signal level is limited to the amount of charge that can be held in the photodetector or pixel. The DR is also limited by the sensor noise level, σ noise . Due to the limitations on Vsat, much work has been done in CCD's to decrease σ noise to very low levels. Typically, commercial megapixel DSC devices have a DR of 1000:1 or less.
The same limitations on DR exist for APS devices. The V sat is limited by the amount of charge that can be held and isolated in the photodetector. Excess charge is lost. This can become even more problematic with APS compared to CCD due to the active components within the pixel in the APS, limiting the area available for the photodetector, and due to the low voltage supply and clocks used in APS devices. In addition, since APS devices have been used to provide image sensor systems on a chip, the digital and analog circuits used on APS devices such as timing and control and analog to digital conversion, that are not present on CCD's, provide a much higher noise floor on APS devices compared to CCD. This is due to higher temporal noise as well as possibly quantization noise from the on-chip analog to digital converter.
Within the art of semiconductor based image sensors there are numerous disclosures that provide extended dynamic range for both APS and PPS devices. These include (1) measurement of number of clock periods to reach a threshold as taught by Konuma in U.S. Pat. No. 5,650,643; (2) capture of 2 or more correlated images with varying integration times as described by Orly Yadid-Pecht et al. in “Wide Intrascene Dynamic Range CMOS APS Using Dual Sampling” published in the 1997 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors; paper #R15; (3) logarithmic transfer function pixel architectures as described by Sypros Kavadias et al. in “On-chip Offset Calibrated Logarithmic Response Image Sensor”, 1999 IEEE Workshop on Charge-Coupled Devices, and Advanced Image Sensors, pp. 68-71, M. Loose et al., “Self-Calibrating Logarithmic CMOS Image Sensor with Single Chip Camera Functionality”, 1999 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, pp. 191-194, N. Ricquier, et al., “Active Pixel CMOS Image Sensor with On-Chip Non-Uniformity Correction”, 1995 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, J. Huppertz et al., “Fast CMOS Imaging with High Dynamic Range”, 1997 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, pp. 1-4; and (4) varying the level of the reset gate during integration as described in prior art references by S. Decker et al., “Comparison of CCD and CMOS Pixels for a Wide Dynamic Range Area Imager”, 1995 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, and “A 256×256 CMOS Imaging Array with Wide Dynamic Range Pixels and Column-Parallel Digital Output”, IEEE Journal of Solid State Circuits, Vol 33, No. 12, December 1998.
U.S. Pat. No. 5,650,643 issued to Konuma (Konuma) teaches a device that can be used to increase the dynamic range of solid state image sensing devices. Konuma shows a means to increase the effective V sat level by incorporating a comparator and a counter associated with a photodetector to measure the time required to reach an integrated signal threshold level, and provide this as the only sensor output. The counter is used in conjunction with the comparator to determine the number of counter clock periods that it took the photodetector to reach the signal level of that supplied to the comparator input. The device then provides only the number of counter clock periods as an output or signal value associated with the photodetector.
While the disclosure of Konuma does provide increased dynamic range through effectively increasing V sat , this approach has several problems.
First, if one were to have a counter and comparator in each pixel, the number of components in each pixel is very large leading to a pixel with a very small fill factor or a very large pixel. This approach is not practical given the present minimum feature sizes of state of the art semiconductor technology, and the need for small pixel, low cost image sensors.
Second, the output for each pixel is a counter value for the time required to reach a given threshold, and does not contain an analog output value for the actual amount of charge integrated in the photodetector. With this approach, although the effective V sat level is increased, the effective DR will be limited by the time period or accuracy of the counter clock, and the size of the counter. For example, if the counter has 10 bits or 1024 counts, the dynamic range is extended to 10 bits provided that the 1024 master clock periods can fit into the desired exposure time. If the desired exposure time were 100 msec., then the counter clock period must be ≦97.6 usec. If one were try to extend the DR to 20 bits, a 20 bit counter would be required, and a counter clock frequency of >10.5 MHz for an exposure time of 100 msec. In this example, the extension of the DR from 10 to bits results in a clock frequency requirement that is 1000 times faster. As the exposure time decreases a commensurately faster master clock is required. For example, if an exposure time of {fraction (1/60)} th of a second were desired or required in the case of capturing an image in outdoors in bright sunlight, a master clock of 63 MHz would be required to quantize 20 bits. It is evident that very fast counter clocks are required to provide high dynamic range in typical exposure conditions. Also, as the number of bits in the counter gets larger, more area required to integrate this into the pixel, producing a larger and larger pixel Typical counters require 4-8 transistors per bit. Thus a 20 bit counter would require 80-160 transistors, yielding pixel sizes of >40 um in a 0.35 um CMOS process. Additionally this approach requires that all pixels within the image sensor reach the programmed threshold level in order to have an output value for each pixel. This would require very long exposure times to allow dark regions of the scene to reach the threshold level if the threshold level is near V sat . The exposure times could be decreased by programming the threshold level to a very low value, but this would reduce the accuracy of information in very bright regions of the scene since they will reach the threshold value in extremely short time periods.
Thirdly, with the approach of Konuma, at the brightest light levels the data is more quantized. This is shown is Equation 2 by looking at how the effective light measurement is calculated from the time to threshold.
If one knows the amount of time (t T ) required to reach a threshold (V T ) and assume that the source is constant over the time being measured, then one can calculate the amount of light at any arbitrary time, (t M ). The expression for the extended effective voltage (V ext ) is given by Equation 2 below.
In a discrete system the time variable, t T , would be measured by a quantized unit as indicated in Equation 3.
Where cv is the quantized integer code value and MaxCv is the code value that corresponds to the cv value at t M . Substituting values we arrive at Equation 4.
Referring to FIG. 2, a code value (cv) of zero implies infinite light. The first measurable quantization, which is also the largest, is between cv=1 and cv=2. The quantization for an 8 bit linear system is 0.0039, which is less than the smallest quantization in a time to threshold method described by Konuma.
Fourthly, if one were to have a single counter and comparator used outside of the pixel array to keep track of the time to threshold, each pixel would then have to be measured at an extremely high rate in order to have a small enough sampling frequency per pixel to provide fine enough quantization for extension of the dynamic range. For example, assume that 10 bits of quantization over the desired exposure time is required, and that there are 1 million pixels in the image sensor. Given a desired exposure time of 100 msec., each pixel would have to be accessed and measured against the programmed threshold level every 97.65 usec. This means that 1 million pixels need to be sampled every 97.65 usec. This would require a pixel sampling rate of 1 pixel per 97.65 psec, or 10.24 GHz. A means for doing this is not disclosed by Konuma or elsewhere in the field of APS devices or other image sensor devices.
Finally, the output value provided is a time. In order to reconstruct the incident image from this output, ( i.e. determine the signal level), one must extrapolate by multiplication from the time value. This can degrade the effective noise level of the sensor. The value t is used to measure the time for a voltage v(t) to reach to a threshold. The signal VPD(t) represents the accumulation of photons over time with some Gaussian additive noise with a standard deviation of σ v . One experienced in the art can show that the noise in the extended voltage domain (σ Ext ) is related to the additive noise as indicated by Equation 5.
Given that t M is always greater than t T one can see that the value of σ Ext is always greater than σ v . From the foregoing discussion it should be apparent that there remains a need within the prior art for a device that provides extended V sat and dynamic range while retaining low noise, small pixel, simple and low frequency readout, and means to manage the quantization of extended voltage signals.
With the method of capturing 2 or more frames as disclosed by prior art references: Orly Yadid-Pecht et al. in “Wide Intrascene Dynamic Range CMOS APS Using Dual Sampling”; 1997 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors; paper #R15; O. Pecht et al., “CMOS APS with Autoscaling and Customized Wide Dynamic Range”, 1999 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors; and M. Schantz et al., “256×256 CMOS Imager with Linear Readout and 120 dB Dynamic Range”, 1999 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, two or more frames of the same image or scene with different integration times are captured, multiple readouts are required and the integration times for each readout must be chosen in accordance with the scene illuminance in order to get an accurate interpolation. This adds complexity to the imaging auto-exposure system to facilitate rapid choice of integration times and has not been shown in the art. Also, additional frame memory is required to perform the multiple frame output comparison and calculation of effective signal level. Additionally, if there is any motion or change in scene illuminance between the 2 frames, this method of extending dynamic range will not work.
With the methods of extending dynamic range described by: Sypros Kavadias et al., “On-chip Offset Calibrated Logarithmic Response Image Sensor”, 1999 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, pp. 68-71; M. Loose et al., “Self-Calibrating Logarithmic CMOS Image Sensor with Single Chip Camera Functionality”, 1999 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, pp. 191-194; and N. Ricquier, et al., “Active Pixel CMOS Image Sensor with On-Chip Non-Uniformity Correction”, 1995 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, a pixel with a logarithmic transfer function is provided. This approach of using a MOSFET sub-threshold exhibits behavior having very high fixed pattern noise. Approaches to correct this require extra system memory, individual threshold trimming of each pixel, or extra transistors per pixel. This increases chip size as well as system cost and complexity.
With the methods of extending dynamic described by J. Huppertz et al., “Fast CMOS Imaging with High Dynamic Range”, 1997 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, pp. 1-4; and S. Decker et al., “Comparison of CCD and CMOS Pixels for a Wide Dynamic Range Area Imager”, 1995 IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, the reset gate voltage level is changed from an on-state to an off-state with a specified time response during integration. With this method the dynamic range is extended by skimming off charge to the reset drain for bright pixels so that the pixel does not saturate. This method has the disadvantages of requiring complicated timing to operate in an electronic shutter mode, and difficulty in discerning whether or not a particular signal level is due to skimming of charge or is simply the total integrated signal level.
From the foregoing discussion it should be apparent that there remains a need within the prior art for a device that retains provides extended dynamic range while retaining low noise, small pixel, single frame readout, and flexible transfer function.
SUMMARY OF THE INVENTION
According to the present invention, there is provided a solution to problems of the prior art. In the present invention, blooming behavior of CMOS based image sensors is used to provide extended intrascene dynamic range.
A first embodiment of the present invention utilizes the charge that blooms from the photodetector during integration. In prior art devices the signal level of the photodetector is limited in bright regions by removing and discarding the blooming charge. In the present invention the charge that blooms from the photodetector is integrated for a period that is controlled independently from the photodetector integration time, and this collected blooming charge is added to the photodetector signal charge in the readout of the pixel.
A second embodiment of the present invention provides extended dynamic range by utilizing the behavior of diminishing signal with increasing light level associated with the readout of CMOS APS under high illumination levels. This is done by performing 2 samples of the reset level that have different elapsed times between reset and measurement of the reset level, thus providing 2 different effective reset level integration times. By comparing the 2 measured reset levels, one can determine the effective signal level of the photodetector beyond the physical saturation signal of the photodetector. The difference determined in the two reset measured levels is used to if the pixel is operating in the diminishing high light signal region, or in low light standard linear signal region. Depending on the result, a different transfer function is applied to voltage output from the from readout of the photodetector of that pixel to provide an effective signal level for that pixel. If the light that is incident on that pixel is bright, and a difference in the 2 measured reset levels exceeds a predetermined threshold, a transfer function associated with the diminishing signal region will be used to calculate the photodetector value. If a difference in the 2 measured reset levels does not exceed a predetermined threshold value, then the standard linear transfer function will be used to identify that photodetector value. Additionally, the value of the measured difference can be used independently to calculate or determine the effective signal level or incident illumination level for that pixel.
According to the present invention, an active pixel sensor device that significantly increases the dynamic range of the device and can be used in current system designs is provided by a method and apparatus of employing an X-Y addressable MOS imager to obtain increased dynamic range wherein the X-Y addressable imager as a semiconductor based sensor having an array of pixels formed in rows and column, with a plurality of the pixels formed such that each pixel within the plurality of pixels has a photodetector, a sense node and a transfer mechanism for transferring charge from the photodetector to the sense node, and with a reset mechanism for resetting the sense node to a predetermined potential. An integration period for the photodetector is initiated through operation of the transfer mechanism followed by initiating an integration period for the sense node through operation of the reset mechanism and reading charge from both sense node and photodetector accumulated during their respective integration periods.
ADVANTAGEOUS EFFECT OF THE INVENTION
The invention has the following advantages. It provides for extending the dynamic range of a sensor that can easily be employed within current pixel and sensor architectures with little or no modification. Small pixel with high fill factor can detect signal level out to 40,000×V sat single frame capture standard read-out.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram of a first embodiment of the present invention that extends the dynamic range by collecting charge that bloomed from the photodetector;
FIGS. 2 a and 2 c are diagrams illustrating the operation of the pixel shown in FIG. 1 on a column basis where photodetector charge is added, and an associated timing diagram;
FIGS. 2 b and 2 d are diagrams illustrating the operation of the pixel shown in FIG. 1 on a column basis where photodetector voltage is added, and an associated timing diagram;
FIG. 3 a illustrates a pair of transfer functions for the pixel in FIG. 1 operated by the timing diagrams shown in FIGS. 2 ( a-d ) having a short floating diffusion integration time leading to a small slope for linear region 2 ;
FIG. 3 b illustrates a pair of transfer functions for the pixel in FIG. 1 operated by the timing diagrams shown in FIGS. 2 ( a-d ) having a relatively longer floating diffusion integration time leading to a larger slope for linear region 2;
FIG. 4 is a timing diagram used to illustrate the diminishing signal behavior shown in FIGS. 5 ( a-d );
FIGS. 5 ( a-d ) are an electrostatic diagrams illustrating the effect of diminishing signal behavior for the pixel as illustrated;
FIG. 6 is a timing diagram used to illustrate the diminishing signal behavior shown in FIGS. 7 ( a-d );
FIGS. 7 ( a-d ) are an electrostatic diagrams illustrating the effect of diminishing signal behavior for the pixel as illustrated;
FIGS. 8 ( a-b ) are diagrams illustrating the diminishing signal region; and
FIGS. 9 ( a-b ) are diagrams illustrating the output of a sampled and held pixel.
DETAILED DESCRIPTION OF THE INVENTION
The first embodiment of the present invention utilizes collection of charge that blooms from the photodetector during integration. This is accomplished using the pixel shown in FIG. 1 . This is a similar pixel design to that disclosed by Guidash et al in U.S. patent application 08/800,947. This pixel 10 comprises a photodetector 12 (preferably a pinned photodiode PD), a transfer gate TG 16, a floating diffusion FD 18 , a light shield 8 over at least the floating diffusion 18 , an input signal transistor and a reset transistor comprised of source floating diffusion 18 , reset gate 17 and reset drain 19 . A microlens 6 is provided to focus light onto the photodetector 12 . Operation of the first embodiment of the present invention is shown in timing diagram of FIG. 2 for the pixel 10 of FIG. 1 resulting in the output signal transfer function shown in FIG. 3 .
Referring to FIG. 2 a , which is diagram illustrating the operation of the pixel 10 shown in FIG. 1 on a column basis wherein charge from photodetector 12 , and floating diffusion 18 , is added by in the charge domain on the floating diffusion, with the combined charge from the photodetector and floating diffusion read out through amplifier 22 , and an associated timing diagram. The pixel 10 is reset or initialized by transferring charge from the photodetector 12 to the floating diffusion 18 by activation of the transfer gate 16 (shown as signal TG) and the subsequent resetting of the floating diffusion 18 by the activation of reset gate 17 , which resets the floating diffusion 18 to a predetermined potential. The photodetector integration time (t intpd ) commences when the transfer gate 16 is turned off after the initialization or reset sequence, at time τ 1 . The electrostatic potential of the transfer gate in its off state is set at a level deeper than 0 volts so that excess charge in the photodetector will bloom through the transfer gate region and into the floating diffusion 18 . As photodetector integration time (t intpd ) proceeds, the photodetector 12 will fill up with photoelectrons. If the incident light is bright, the number of photoelectrons generated in that pixel will exceed the capacity of the photodetector 12 . At this point the excess charge will spill into the floating diffusion 18 . If the reset gate 17 is on when charge begins to spill onto the floating diffusion 18 , this charge will be swept through the reset gate 17 region to reset drain 19 leaving the floating diffusion at the same predetermined potential, typically a threshold voltage below that of the reset drain 19 (VDD). If the reset gate 17 is off when charge begins to spill into the floating diffusion 18 , then this charge will be collected in the floating diffusion 18 . The amount of time that RG is turned off during the photodetector integration period is referred to as the floating diffusion integration time t intfd .
At the end of desired photodetector integration time t intpd , the signal charge in the photodetector 12 is transferred to the floating diffusion 18 by pulsing the transfer gate 16 on and off at time τ 2 . The signal level of the floating diffusion 18 is then sampled by SHS and held on capacitor C 1 . If no blooming charge has been collected on the floating diffusion 18 during the floating diffusion integration time t intfd ,(i.e. a dark region of the image), then the signal charge on capacitor C 1 from the floating diffusion 18 comprises the charge collected in the photodetector 12 during integration. If blooming charge has been collected on the floating diffusion 18 , then the signal charge on the capacitor C 1 from floating diffusion 18 comprises the charge collected in the photodetector 12 during photodetector integration time (t intpd ), plus the charge collected in the floating diffusion during the floating diffusion integration time. This floating diffusion integration time t intfd , is the time elapsed from when reset gate 17 is turned off to when the signal charge is transferred from the photodetector 12 at time τ 2 . The floating diffusion integration time t intfd is controlled separately and independently from the photodetector integration time t intpd .
As a result of the operation described for FIG. 2 a the sensor output response will be as shown in FIGS. 3 a and 3 b . The output response comprises 2 regions. For low light levels the output response will follow linear region 1 . As the number of photoelectrons exceeds the capacity of the photodetector, this charge will be collected on the floating diffusion and added to the photodetector signal charge. In this case the pixel output response will follow region 2 . The preferred embodiment provides a linear response in region 2 , by the timing shown in FIG. 2 a . A non-linear response could be generated by having a time varying reset gate potential level as described in the prior art reference by S. Decker et al., “A 256×256 CMOS Imaging Array with Wide Dynamic Range Pixels and Column-Parallel Digital Output”, IEEE Journal of Solid State Circuits, Vol 33, No. 12, December 1998. In the preferred embodiment, the output response in region 2 is linear, and the slope is dependent on and directly proportional to the floating diffusion integration time t intfd . The two FIGS. ( 3 a and 3 b ) illustrate the 2 different slopes for region 2 . The floating diffusion integration time in FIG. 3 a is shorter than that for FIG. 3 b . Consequently, the slope of region 2 in FIG. 3 b . is greater than that for FIG. 3 a.
Since the floating diffusion integration time t intfd is known, the effective signal level of the pixel can be determined by Equation 6.
Veff=Vout for Vout<Vpdsat Veff=Vpdsat +( Vout−Vpdsat )( t pdint /t fdint ) for Vout/Vpdsat Equation 6
Since the ratio of the photodetector integration time t intpd to the floating diffusion integration time t intfd can be made large, Veff can be increased substantially over the signal limited by the photodetector capacity. Hence, the dynamic range is extended. Additionally, the maximum voltage level, Vmax, which is determined by the floating diffusion charge capacity can be larger than that of the photodetector capacity by controlling the capacitance of the floating diffusion. It is also possible to display the sensor output signal directly without determining the effective signal level from region 2 . This still provides extended intrascene dynamic range by mapping and directly displaying a larger incident illuminant range into the directly detectable signal voltage range. Also, the level of Vpdsat can be programmed by setting the off level of the transfer gate 16 to the desired level.
The timing shown in FIG. 2 a shows a single readout of the total combined charge on the floating diffusion that comprises the photodetector signal and the collected blooming charge. The signal is read first followed by a reset and then a measurement of the reset level. This is an uncorrelated double sample readout, which adds temporal reset noise to the signal. It is possible to accomplish readout of the photodetector signal level and floating diffusion blooming charge level by performing 2 readouts. This is shown in FIG. 2 b . In this manner the level of blooming charge collected on the floating diffusion 18 is sampled and held by pulsing SHS fd which places the blooming charge on Capacitor C 4 , followed by a reset of the floating diffusion 18 by RG and a sample and hold of the reset level by SHR which places the reset level on Capacitor C 5 . Charge is then transferred from the photodetector 12 to the floating diffusion 18 and that signal level is then sampled and held by SHS pd and placed on Capacitor C 6 . The present invention envisions a differential readout for the stored blooming charge on capacitor C 4 and the reset level on capacitor C 5 via differential amplifier 31 , and a second differential readout for the stored signal charge on capacitor C 6 and the reset level on capacitor C 5 via differential amplifier 32 , thus providing true correlated double sampling for the photodetector signal level. The final output signal can then be determined by several means. One is reading the signals from the 2 differential amplifiers 31 and 32 separately providing 2 signal values per pixel that can be added off-chip. A second embodiment is accomplished by providing the signals as inputs to a 3 rd differential amplifier and reading the signal out as a single level per pixel. This readout method of combining the signal in the voltage domain also provides a larger Vmax than combining the signals in the charge domain. This is because the floating diffusion does not have to hold the photodetector signal and blooming signal simultaneously. Hence the Vmax is extended to be the full floating diffusion capacity plus the photodetector capacity.
Since this method utilizes differential readout of the pixel with respect to a reference reset level, the pixel offset noise is cancelled. Additionally the dynamic range is extended without any additional components in the pixel, so that it can be accomplished with small pixels that are practical for low cost consumer digital imaging applications. With this approach pixel read noise will be increased by KTC due to the reset level being uncorrelated to the signal level. This will be typically less than 30 electrons and is small compared to the gain in effective signal level.
The second embodiment of the present invention also utilizes blooming behavior to extend dynamic range. In CMOS APS and PPS devices it is pointed out that as the incident light level becomes extremely bright, the output signal determined from the difference between the signal level and a reset level is perceived to decrease with increasing light levels, eventually reaching a “black” level. This diminishing signal behavior is due to the effect of the reset level decreasing as a result of charge accumulating on the charge to voltage conversion node, typically referred to as a sense node, during the time between reset and when the reset level is sampled and held. This occurs either by blooming charge from a separate photodetector being collected during on the sense node in the case of a 4 transistor APS, or by accumulation of electrons in the photodetector that also functions as the sense node in the case of 3 transistor APS pixels, or in the case of PPS pixels. If uncorrected, this diminishing signal effect with increasing incident light levels may be undesirable.
Cross sectional diagrams of the relevant region of pixels envisioned to operate under the second embodiment of the present invention are shown schematically in FIGS. 5 a-d and 7 a-d with corresponding timing diagrams of FIGS. 4 and 6. The pixel 20 shown in FIGS. 5 a-d and the corresponding timing diagram of FIGS. 4 are for the case of either a 3 transistor APS device where the photodetector serves as the charge to voltage conversion node, and also or for the case of a PPS device. The pixel 30 shown in FIGS. 7 a-d and the corresponding timing diagram of FIGS. 6 are for the case of an APS where the charge to voltage conversion node (floating diffusion 38 ) is separate and isolated from the photodetector 32 .
Referring to FIGS. 4 and 5 a-d , which is the case of 3 transistor APS devices and PPS devices, the pixel 20 is initialized by resetting the photodetector 22 when RG 27 is pulsed on and off. Integration of signal in the photodetector now commences. As integration proceeds the electrostatic potential of the photodetector VPD decreases until the photodetector 22 has completely filled up with photoelectrons. At this point the VPD is approximately 0 volts. The signal level of the photodetector 22 is then sampled and held by strobing SHS. Next the photodetector is reset by strobing RG 27 in order to provided a reference level differential readout of the signal from photodetector 22 . The time elapsed between the reset and sample and hold of the reset level is typically a few μsec. If the incident light level during this elapsed time is low, the reset level will not change appreciably and will be extremely close to the nominal reset level RL 0 . If this incident light is very bright, the reset level can change during this elapsed time if the sensor is not shielded from the incident light. The example seen in FIGS. 5 a-d is for a very bright incident light level that causes the photodetector voltage VPD to go to reset level RLA. Since the readout of the output signal level is determined by the difference between the signal level and the reset level, the perceived output signal level will decrease because the full photodetector level is compared against RLA rather than RL 0 . If the incident light level is bright enough to completely fill the photodetector in the time between reset and sample and hold of the rest level, the photodetector will reach a reset level RLB. In this case the difference between the sampled and held signal level and the sampled and held reset level is zero, producing a black or dark image. This produces a diminishing signal region with increasing incident light intensity as shown in FIGS. 8 a and 8 b.
Referring to FIGS. 6 and 7 a-d , which is for the case of 4 transistor APS devices, the same effect occurs. As the incident light level becomes bright enough the photodetector 32 fills up and excess electrons spill into the floating diffusion 38 , consequently decreasing the reset level and the differentially read out signal level in a manner similar to that described for FIGS. 4 and 5 a-d.
However, measurements of this diminishing signal level effect show that the transfer function is very linear and reaches a black level at incident light levels that are 20,000× to 50,000× the normal saturation exposure, Isat, as shown in FIG. 8 b . In FIG. 8 a , the x-axis scale extends from no illumination to 3× times the saturation exposure. With this x-axis scale it is possible to discern the linear region output response of the pixel prior to saturation. This is the region between no illumination and Isat. The x-axis scale is changed in FIG. 3 b to extend from no illumination to 50,000 times Isat. With this scale it is easier to discern the output response of the sensor in the saturated region, but difficult to discern the region prior to saturation shown in FIG. 3 a . In the output response of the sensor in the saturated region, the output signal diminishes linearly, or by some other characterized and empirically known transfer function, until reaching ˜50,000 times Isat, where the output signal reaches 0 volts and appears as a black or dark signal.
The new concept presented with the present invention is to use this diminishing signal region to determine the “effective signal level” to extend dynamic range. The “effective reset integration time” for this behavior is simply elapsed time between the falling edge of the reset of the charge to voltage conversion node and the falling edge of the sample and hold of the reset level, as shown in FIG. 4 and FIG. 6 . The signal change in this small integration time can be ascertained by having two reset sequences that are sampled and held with different effective integration times. If there is a difference between the 2 reset levels that exceed a predetermined threshold, then it is known that pixel is in the diminishing signal region of the response curve. This could also be done by comparing a single reset level to a reference reset level that is generated from a dark reset. Once it is determined that the pixel is in the diminishing region of the response curve, the incident illumination level can be determined from the specific measured transfer function provided by the diminishing signal region of the sensor. Thus incident illumination levels from no illumination up to 50,000× the saturation exposure can be detected by the sensor, providing extended dynamic range. Additionally, the effective signal level could be determined from the measured difference in the two reset level by using equation (7) V eff = Δ V reset ( t exp t int r ) + V sat where Δ V reset = V reset dark - V reset illum . Equation 7
where t exp =exposure time and t int r =effective reset integration time.
Application of the saturated region transfer function, or calculation of the effective signal level as described in equation 7, could be accomplished outside of the image sensor via system software or hardware, or on the sensor in the analog or digital domain. One embodiment of this concept is shown in FIGS. 9 a-b . Referring to FIGS. 9 a-b , a comparator with a programmable threshold is used to determine if there is a difference between the 2 reset levels with different elapsed times between reset and sample and hold of the reset level. The pixel output signal level is read in a manner similar to that described in prior art; the sampled and held photodetector signal level is read out differentially with respect to reset 1 , and digitized to N bits, (8 shown in this example). The output of this comparator with reset 1 and reset 2 as inputs is then used as a transfer function bit. A “zero” transfer function bit indicates that the 8 bit photodetector signal level should be used as is. A “one” transfer function bit indicates that the 8 bit photodetector signal level should be calculated using the 8 bit output using the saturated region transfer function. The timing for this readout operation is also shown in FIGS. 9 a-b for the pixel shown in FIGS. 5 a-d . After the photodetector integration time has elapsed the floating diffusion is reset and the reset level is sampled and held. This is reset 1 and has an elapsed reset integration time 1 . Next the charge in the PD is transferred to the floating diffusion and the signal level is sampled and held. Next, the FD is reset and the reset level is sampled and held provided reset 2 , with an elapsed reset integration time 2 that is different than that for reset 1 .
The operation occurs in a similar manner for APS pixels where the PD functions as the sense node or for PPS pixels, except that the readouts occur in the sequence of read signal level, reset, read reset 1 , wait for an desired elapsed time, read reset 2 .
Additionally, rather than using a comparator to determine if there is a predetermined difference between reset 1 and reset 2 , the actual value of the differences in reset levels could be read out in a similar manner to that used to determine the value of (signal−reset 1 ). This value of (reset 2 −reset 1 ) could then be used to determine the effective signal level using equation 7. A comparison could be done to provide a flag bit to determine which value, either signal−reset 1 , or reset 2 −reset 1 to read out through the 8 bit ADC.
PARTS LIST
10 pixel
12 photodetector
14 substrate
16 transfer gate
17 reset gate
18 floating diffusion
19 reset drain
20 pixel
22 photodetector
24 substrate
27 reset gate
28 floating diffusion
29 reset drain
20 pixel
22 photodetector
24 substrate
26 transfer gate
27 reset gate
28 floating diffusion
29 reset drain
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A method and apparatus of employing an X-Y addressable MOS imager to obtain increased dynamic range wherein the X-Y addressable imager as a semiconductor based sensor having an array of pixels formed in rows and column, with a plurality of the pixels formed such that each pixel within the plurality of pixels has a photodetector, a sense node and a transfer mechanism for transferring charge from the photodetector to the sense node, and with a reset mechanism for resetting the sense node to a predetermined potential. An integration period for the photodetector is initiated through operation of the transfer mechanism followed by initiating an integration period for the sense node through operation of the reset mechanism and reading charge from both sense node and photodetector accumulated during their respective integration periods.
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A portion of the disclosure of this patent document contains material which is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent disclosure, as it appears in the Patent and Trademark Office patent files or records, but otherwise reserves all copyright rights whatsoever.
CROSS-REFERENCE TO OTHER APPLICATIONS
The following applications of common assignee contain some common disclosure, and are believed to have effective filing dates identical with that of the present application:
EXPERT SYSTEM WITH NATURAL-LANGUAGE RULE UPDATING filed Sept. 30, 1987; Ser. No. 103,050
PROCESS CONTROL SYSTEM WITH RECONFIGURABLE EXPERT RULES AND CONTROL MODULES filed Sept. 30, 1987; Ser. No. 103,014
PROCESS CONTROL SYSTEM WITH ACTION LOGGING filed Sept. 30, 1987; Ser. No. 103,118
PROCESS CONTROL SYSTEM WITH ON-LINE RECONFIGURABLE MODULES filed Sept. 30, 1987; Ser. No. 103,047
and PROCESS CONTROL SYSTEM WITH MULTIPLE MODULE SEQUENCE OPTIONS, filed Sept. 30, 1987; Ser. No. 103,124
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to expert systems (also known as knowledge-based systems), to process control systems, and to hybrids thereof.
2. Discussion of Related Art
Various known teachings which are believed to be related to various ones of the innovations disclosed in the present application will now be discussed. However, applicant specifically notes that not every idea discussed in this section is necessarily prior art. For example, the characterizations of the particular patents and publications discussed may relate them to inventive concepts in a way which is itself based on knowledge of some of the inventive concepts. Moreover, the following discussion attempts to fairly present various suggested technical alternatives (to the best of applicant's knowledge), even though the teachings of some of those technical alternatives may not be "prior art" under the patent laws of the United States or of other countries. Similarly, the Summary of the Invention section of the present application may contain some discussion of prior art teachings, interspersed with discussion of generally applicable innovative teachings and/or specific discussion of the best mode as presently contemplated, and applicant specifically notes that statements made in the Summary section do not necessarily delimit the various inventions claimed in the present application or in related applications.
Process Control Generally
To compete in global markets, manufacturers must continually improve the quality and cost of manufacture of their products. They must do this in the face of changing market needs, changing raw materials costs, and reduced staffing. Automatic computer control of the manufacturing process can play an important part in this, especially in the chemical process industry. Most process plants already have the basic automatic regulating controls (low level controls) needed to control the plant at a given operating point. These provide the foundation for higher level supervisory controls (referred to here as supervisor procedures or supervisors) that seek to improve quality, reduce cost, and increase plant uptime by moving the plant to a different operating point. These changes can be made directly via the lower level controls, or indirectly via the plant operator.
Although supervisory controls have been in use for years, they have lacked a number of desirable features. To best improve quality and cost, a supervisor procedure should:
help control the quality of the end product;
reduce the cost of operating the plant;
help avoid unnecessary upsets or shutdowns;
work effectively with plant operators;
act in concert with standard operating procedures; and
be supportable by plant operating and support people.
To measure quality, a supervisor procedure should ideally have access to measurements of the basic properties of the product which affect its value and usefulness to the customer. Since most product properties measurements are sampled (and are measured in a laboratory), the supervisor should have access to a historical process database which can store these measurements as well the basic process data from the lower level control systems. Since sampled measurements and the process itself normally include some components of random variation, the supervisor should include statistical tests which can determine if a sequence of sampled measurements is varying normally around its aim value (i.e. is "on aim"), or has shifted significantly from aim (is "off aim").
To control quality, a supervisor procedure should have the capability to change the operating point of the process (via the lower level controls) when a measured property goes off aim. It should have the ability to act in response to new data or statistical tests, or to act at regular time intervals. It should also be able to preemptively change the operating point when basic conditions (such as plant production rate) change. It should allow a number of independent control objectives, and new ones should be easy to add. Since the process may use any number of different low level controllers, the supervisor should be able to communicate with all of them.
To work effectively with plant operators, a supervisor procedure should be understandable. It should carry out its control actions in a way that is natural and understandable to operators. It should provide enough information about its current state and its past actions for the operator to judge its performance. It should inform the operator when it acts (or chooses not to act), explaining how much action was taken, where it was taken, why it was done, and what effect it might have. Since the effect of actions taken to control quality and reduce cost can last longer than a single shift, it should provide a record of all its actions.
To act appropriately under all circumstances, to reduce operating costs in a way consistent with quality, to help avoid unnecessary upsets and shutdowns, and to take operating procedures into account, a supervisor should ideally include the logical decision making capabilities of expert systems. Because decisions will normally focus on a specific task or area, many independent expert systems should be allowed. The expert systems should have access to the many sources of process measurements, laboratory measurements, and control system parameters. They should be able to reason symbolically using that information, and to make their decisions take effect through communication and control actions. To work effectively, the supervisor should be able to control its expert system functions in concert with its other functions.
To be supported by plant personnel, the supervisor should be easy to use. It should allow common control actions to be set up easily, with a means of customizing less common functions. It should allow control actions to be changed easily. It should have a simple means of specifying the informative messages to be generated about it actions. Its expert systems should allow process knowledge to be entered, stored, and updated in a way that plant support people understand. It should provide a simple, appropriate knowledge representation which naturally includes data retrieval, symbolic reasoning, and effective means of implementing decisions in the plant. The knowledge structure should allow any authorized plant expert to enter knowledge, without restricting access to those who know computer languages or have memorized special rule structures.
The present invention addresses many of these concerns.
Normally supervisory control has been thought of separately from another higher level of control called optimizing control, which seeks to minimize operating cost. In some cases, the requirement to minimize variation in product properties (i.e. to improve product quality) is absolutely primary, so that cost optimization only be performed as an objective secondary to quality objectives. In this environment, use of classical optimization techniques to achieve cost optimization may not be possible. In other cases, it has been possible to integrate a balance of supervisory and optimizing control into the supervisor.
Modularity
Supervisory control systems using a modular structure are well known. For example, the Process Monitoring and Control-1000 (PMC-1000) control package marketed by Hewlett Packard is a modular control package which can function as a supervisory control system. PMC modules, called blocks, perform alarming and limiting, proportional/integral/derivative control, trending, driving an electrical output, running programs, and other functions. Each block writes one or more output values into memory. To build PMC control structures, the user creates as many blocks as needed and links them to other block output values. A new runnable system must then be generated. Once the system is running, parameters such as gain constants can be changed, but the linking of blocks is fixed. PMC runs on a base time cycle, and blocks can only be scheduled to execute at multiples of the base cycle time. Although PMC maintains a historical database, it cannot be used for control, and does not effectively store intermittently sampled data. It is believed that there is no maximum number of blocks.
It is believed that some earlier discussion of the significance of modularity in process control software is found in Watson, "Process Control Using Modular Package Software," IEE Conference Publications number 102 (1973) (which is hereby incorporated by reference).
Historical Process Database
A database of historical process data is generally described in Hale and Sellars, "Historical Data Recording for Process Computers," 77 Chem. Eng'g Proqress 38 (1981) (which is hereby incorporated by reference).
Continuous Control Actions
In classical feedback and feedforward control, the prior art teaches that the best control results are achieved by making continuous changes to the process. In computer control, where cyclic operation forces changes to be made in discrete steps, many small, frequent steps are conventionally preferred. While in principle this gives the best possible control performance, such control actions are very difficult to visualize. In fact, it may be impossible to determine what actions have been taken by what control strategies, and how long the control strategies have been making changes. This makes it very difficult to judge whether control strategies are working properly, or even if they are working at all. This method of control also runs counter to the methods used by operators, who generally make a few significant changes and wait to see the effects.
In feedback control, the use of a deadband is a well known way of avoiding small actions caused by a noisy measurement. (That is, if the control variable falls within a specified deadband of values surrounding the goal value, the control value will not be manipulated.) This deadband, as is well known, helps to avoid instability in control systems. Statistical process control also tends to reduce the number of feedback control actions. However, neither technique is sufficient to make all control actions understandable, since some actions will not be considered noisy.
The use of a feedforward relation among control variables is also well known among those skilled in the art of process control. That is, in some cases, whenever one variable changes (e.g. if a particular control variable is manipulated for any reason), another variable will also be manipulated according to a predetermined relationship. For example, in a distillation process, it may be desirable to immediately decrease the heat input whenever the rate of feed of the crude feed stock is decreased. In feedforward control, a deadband is normally not used.
Control of Multiple Manipulated Variables
In many process control applications, several manipulated variables must be jointly controlled in a single control loop (e.g. in some relation to a single measured variable). A special (and very common) case of this is seen in many situations where a single manipulated variable can normally be used, but alternate manipulated variables should be used instead if the first-choice manipulated variable becomes constrained. When human operators optimally handle problems of this kind, their choice of which output to change will often be made heuristically, based on cost, quality, response dynamics, and process stability.
"Decoupling" is a conventional way of reducing multi-input multi-output problems to sets of single-input single-output problems. In decoupling, it is usually assumed that all of the manipulated variables should be changed.
A different but related problem arises when a number of manipulated variables ("knobs") can be changed to respond to a single measured variable. Operators often use a heuristic approach in choosing which knob (or knobs) to manipulate, and sometimes choose not to act. The heuristic approach may consider cost, quality, response dynamics, and process stability. It may include alternate knobs to be used when all of the preferred knobs are constrained. Classic control methods are not well suited to this approach.
Expert Systems Generally
The term "expert system" is used in the present application (in accordance with what is believed to be the general usage at present) to refer to a system which includes non-trivial amounts of knowledge about an underlying problem. Almost any control system which has been customized for a particular application might be argued to embody small amounts of relevant knowledge in its very structure, but the term expert system is generally used only for systems which contain enough accessible information that they can usefully supplement the knowledge of at least some (but normally not all) human users who must deal with problems of the type addressed. Expert systems at their best may serve to codify the expert knowledge of one person (a "domain expert"), so that that person's expertise can be distributed and made accessible to many less expert users who must address problems of a certain type. Some well-known successful examples include a medical diagnostic program (MYCIN) and a diagnostic program which assists mechanics working on diesel engines.
As these examples show, one very common area of application for expert systems has been fault diagnosis. Many other areas of application have been recognized; see generally Expert Systems (ed. R. Forsythe 1984) (which is hereby incorporated by reference); P. Harmon and D. King, Expert Systems (1985) (which is hereby incorporated by reference); and Donald Waterman, A Guide to Expert Systems (1984) (which is hereby incorporated by reference).
Knowledge Input and Updating
One of the very general problems in the area of expert systems is how knowledge is to be gotten into an expert system in the first place. That is, specialists in artificial intelligence often assume that a "knowledge engineer" (that is, a person who is experienced and competent in the specialized computer languages and software commonly used for artificial intelligence applications) will interview a "domain expert" (that is, a person who actually has expert knowledge of the type of problems which the expert system is desired to be able to address) to extract his expertise and program an expert system accordingly. However, there are some very important drawbacks to this paradigm. First, competent "knowledge engineers" are not readily available. In particular, the requirements of maintaining a real-world application (such as an expert system for chemical process control, as in the preferred embodiments disclosed below) are such that it is dangerous to rely on a sufficient supply of "knowledge engineers" to go through the iterations necessary to not only input the knowledge base reliably, but also maintain the software base once it is created.
The rapidly developing art of software engineering has shown that one of the key requirements for a large software system is that it be maintainable. Thus, for example, the software system must be set up so that, after the technologist who first puts together an expert system is gone, it can be maintained, modified, and updated as necessary by his successors.
Thus, one key problem in the area of expert systems is the problem of maintenance and updating. Especially in more complex real-world applications, it is necessary that a large software structure, such as that required for a sophisticated expert system, be maintainable. For example, in an expert control system, control strategies may be modified, new control strategies may be introduced, sensor and/or actuator types and/or locations may be changed, and the economic factors relevant to cost versus throughput versus purity tradeoffs may change. Normally, expert systems attempt to maintain some degree of maintainability by keeping the inference rules which the processor executes separate from the software structure for the processor itself. However, this normally tends to lead to a larger software structure which operates more slowly.
Specialists in expert systems also commonly assume that expert systems must be built in a symbolic processing environment, e.g. in environments using LISP or PROLOG. Even for complex processes, a single large knowledge base is usually assumed. The program which processes the knowledge therefore requires complex procedures for processing the knowledge base, and these are typically coded separately from the knowledge. This leads to large software structures which execute slowly on conventional computers. Specialized "LISP machines" are commonly recommended to speed up the inference process.
Expert System Knowledge Structures
Published material regarding knowledge based systems (expert systems) has proposed several classifications for the types of rules which are to be used. For example, U.S. Pat. No. 4,658,370 to Erman et al., which is hereby incorporated by reference, describes "a tool . . . for building and interpreting a knowledge base having separate portions encoding control knowledge, factual knowledge, and judgmental rules." (Abstract). The method described in this patent still appears to rely on the availability of a "knowledge engineer." This patent appears to focus on the application of an expert system as a consultation driver for extracting the relevant items of knowledge from a human observer. Knowledge is separated into factual knowledge such as classes, attributes, allowed values, etc., which describe the objects in the domain; judgmental knowledge, which describes the domain (and its objects) in the form of rules; and control knowledge describing the problem solving process to be used by the inference procedure in processing the knowledge. (The control knowledge has nothing to do with control of an external process.) This knowledge structure is designed to make the task of knowledge engineering easier, and to make the knowledge system and its reasoning during a consultation easier to understand. The knowledge base is written in a specialized programming language. This is a very powerful structure, which requires a very high skill level.
Expert system development tools which are designed to make the input of knowledge easier have been developed. U.S. Pat. No. 4,648,044 to Hardy, et al., describes "a tool for building a knowledge system . . . [which] includes a knowledge base in an easily understood English-like language expressing facts, rules, and meta-facts for specifying how the rules are to be applied to solve a specific problem". (Abstract). Although this tool is not as complex as some current expert systems tools, the knowledge must be entered in a rigidly structured format. The user must learn a specialized language before he can program the knowledge base. Despite some simplification in the development process, a fairly high skill level is still required.
Expert Systems for Process Control
Chemical processing plants are so complex that few people develop expertise except in limited areas of the process. Plants run around the clock, production rates on a single line are very high, and startup is usually long and costly, so improper operation can be very costly. It has also been found that, in a complex chemical processing plant, some operators can achieve substantially higher efficiencies than others, and it would be advantageous if the skill level of the best operators could be made generally available. Expert systems promise significant benefits in real-time analysis and control by making scarce expertise more widely available. However, application of expert systems in this area has not progressed as far as it has in interactive, consultative uses.
Integration of expert system software with process control software poses special problems:
First, there is the problem of how the software structure for an expert system is to be combined with the software for a process control system. Several expert systems which have been suggested for process control have used an expert system as the toplevel supervisor procedure for the control system.
Second, as discussed above, many process control strategies have difficulty with situations where there are multiple control parameters (inputs to the process) which could be manipulated. That is, for processes which have only one primary control parameter (as many do), the problem of what value to set for that control parameter is in significant ways a much simpler problem than the question of which one or ones of multiple control parameters should be addressed, and in which direction.
It should also be noted that the use of an expert system to design a new process (or to debug a newly introduced process) has significantly different features from the problem of optimally controlling an existing process. Similarly, while expert systems have also been applied to the automatic distribution of jobs to multiple workstations through an automated materials handling system (an example of this is the DISPATCHER Factory Control System developed by Carnegie Group Inc.), the queuing problems presented by the allocation of different types of materials in batches to many parallel assembly workstations making different products are quite different from the problems in continuously operating single line processes, particularly chemical processes.
"RESCU"
The system known as "RESCU" resulted from a collaborative demonstration project between British government and industry. See, e.g., Shaw, "RESCU online real-time artificial intelligence," 4 Computer-Aided Engineering J. 29 (1987) (which is hereby incorporated by reference); and the Digest of the IEE Colloquium on `Real-Time Expert Systems in Process Control`, held 29 Nov. 1985 at Salford, U.K. (which is hereby incorporated by reference). From available information, it appears that this is a real-time expert system which was developed to provide advice on quality control in an detergent plant. The system searches for a hypothesis about the plant which is supported by process data, and uses it as the basis for advice. This system also uses a single knowledge base for the entire plant and thus requires complex inference control methods.
"Falcon"
"Falcon" is a fault diagnosis system for a chemical reactor, which monitors up to 30 process measurements and seeks to identify a set of up to 25 failures in the process. This was developed as a demonstration project between DuPont, the Foxboro Company, and the University of Delaware, and is described, for example, in D. Rowan, "Using an Expert System for Fault Diagnosis," in the Feb. 1987 issue of Control Engineering, which is hereby incorporated by reference. See also "Troubleshooting Comes On Line in the CPI" in the Oct. 13, 1986, issue of Chemical Engineering at page 14, which is hereby incorporated by reference. This system required several man years of development, and because it is programmed in LISP, it has proven difficult to maintain the knowledge base through process changes.
"ONSPEC Superintendent"
The "ONSPEC Superintendent" (TM), marketed by Heuristics Inc., is a real-time expert systems package which monitors data from the ONSPEC (TM) control system. See Manoff, "On-Line Process Simulation Techniques in Industrial Control including Parameter Identification and Estimation Techniques," in Proceedings of the Eleventh Annual Advanced Control Conference (1985) (which is hereby incorporated by reference); and Manoff, "Control Software Comes to Personal Computers," at page 66 of the Mar. 1984 issue of Control Engineering (which is hereby incorporated by reference). The "Superintendent" monitors for conformance with safety and control procedures and documents exceptions. It can also notify operators, generate reports, and cause control outputs.
"PICON"
The PICON (TM) system, which was marketed by Lisp Machines, Inc. (LMI), was apparently primarily intended for real-time analysis of upset or emergency conditions in chemical processes. It can monitor up to 20,000 input process measurements or alarms from a distributed control system. It uses a single knowledge base (e.g. containing thousands of rules) for an entire process. To handle such a large number of rules, it runs on a LISP computer and includes complex inference control methods. PICON must be customized by a LISP programmer before the knowledge base can be entered. The domain expert then enters knowledge through a combination of graphics icons and Lisp-like rule constructions. See, for example, L. Hawkinson et al . . . "A Real-Time Expert System for Process Control" in Artificial Intelligence Applications in Chemistry (American Chemical Society 1986), which is hereby incorporated by reference, and the R. Moore et al. article in the May 1985 issue of InTech at page 55, which is hereby incorporated by reference.
Self-tuning Controllers
Another development which should be distinguished is work related to so-called "self-tuning controllers." Self-tuning single- and multiple-loop controllers contain real-time expert systems which analyze the performance of the controller (See "Process Controllers Don Expert Guises", in Chemical Eng'g, June 24, 1985). These expert systems adjust the tuning parameters of the controller. They affect only low-level parts of the system, and use a fixed rule base embedded in a microprocessor.
SUMMARY OF THE INVENTION
In this section various ones of the innovative teachings presented in the present application will now be discussed, and some of their respective advantages described. Of course, not all of the discussions in this section define necessary features of the invention (or inventions), for at least the following reasons: (1) various parts of the following discussion will relate to some (but not all) classes of novel embodiments disclosed; (2) various parts of the following discussion will relate to innovative teachings disclosed but not claimed in this specific application as filed; (3) various parts of the following discussion will relate specifically to the "best mode contemplated by the inventor of carrying out his invention" (as expressly required by the patent laws of the United States), and will therefore discuss features which are particularly related to this subclass of embodiments, and are not necessary parts of the claimed invention; and (4) the following discussion is generally quite heuristic, and therefore focusses on particular points without explicitly distinguishing between the features and advantages of particular subclasses of embodiments and those inherent in the invention generally.
Various novel embodiments described in the present application provide significant and independent innovations in several areas, including:
systems and methods for translating a domain expert's knowledge into an expert system without using a knowledge engineer;
software structures and methods for operating a sophisticated control system while also exploiting expert system capabilities;
generally applicable methods for controlling a continuous process; and
innovations, applicable to expert systems generally, which help provide highly maintainable and user-friendly experts.
Various classes of embodiments described herein provide a process control system, wherein a process which operates substantially continuously is controlled by a system which includes (in addition to a process control system which is closely coupled to the underlying process and which operates fairly close to real time, i.e. which has a maximum response time less than the minimum response time which would normally be necessary to stably control the underlying process) at least some of the following features:
(1) A supervisor procedure, which has a modular structure, and retrieves process measurements from the process control system (or other process data collection systems), passes control parameters to the process control system, and communicates with people. Preferably, the supervisor includes the capability for statistical process control. The supervisor preferably runs on a computer system separate from the process control system.
(2) The supervisor procedure can preferably call on one or more expert system procedures as subroutines. This is particularly useful in control applications where there are multiple possible manipulated variables, since the expert system(s) can specify which manipulated variable (or variables) is to be adjusted to achieve the end result change desired, and the supervisor system can then address simpler one-dimensional control problems.
(3) Preferably, at least some users can call on a build-supervisor procedure which permits them to define or redefine modules of the supervisor procedure by editing highly constrained templates. The templates use a standardized data interface (as seen by the user), which facilitates the use in control actions of data from a wide variety of systems. The templates in the available template set preferably contains highly constrained portions (which are optimized for the most common functions), and pointers to functions which can be customized by the user.
(4) Preferably, the build-supervisor user can also call on a build-user program procedure, which allows fully customized control functions to be programmed by sophisticated users. The build-user program procedure can also be used to create customized message generation functions. These can be used to generate messages describing the actions of the supervisor, and also to call other sub-procedures, such as the expert procedures.
(5) Preferably at least some users are also permitted to call on a build-expert procedure which can be used to construct an expert system. Knowledge is specified by user input to a set of highly constrained, substantially natural language templates. The templates use a standardized data interface (as seen by the user), which facilitates the use in the expert system of data from a wide variety of systems. The completed templates can then be compiled to produce a runnable expert system. Preferably, the user can also retrieve, examine, and modify the input from previously specified templates. Thus, an expert system can be modified by recalling the templates which specified the current expert system, modifying them, and recompiling to generate a new runnable expert.
(6) A historical process database advantageously standardizes the access to current and historical process data by the supervisor and expert procedures. This is particularly useful for collecting the results of laboratory characterizations over time of the underlying process.
Control of Continuous Processes
The goals in management of a substantially continuous process include the following:
(1) Maximizing quality: In the chemical process industry, it is important to reduce variation in measured properties of the product, and to control the average measured properties at specified aim values.
(2) Minimization of cost of manufacture: The process must be operated in a way that efficiently uses energy and feedstocks without compromising quality objectives. Upsets and inadvertent process shutdowns, which adversely affect quality and production rate, and reduce the total utility (fractional uptime) of the plant, are all costly and must be avoided.
Control of Multiple Manipulated Variables
As noted above, in many process control applications, several manipulated variables must be jointly controlled in a single control loop (e.g. in some relation to a single measured variable). A special (and very common) case of this is seen in many situations where a single manipulated variable can normally be used, but alternate manipulated variables should be used instead if the first-choice manipulated variable becomes constrained. When human operators optimally handle problems of this kind, their choice of which output to change will often be made heuristically, based on cost, quality, response dynamics, and process stability.
One novel approach to this problem (which is used in several of the preferred embodiments below) is to decompose the multiple-variable problem into a set of single-variable problems. An expert procedure is used to decide which control parameter(s) to adjust, and one or more from a set of single-input single-output procedures are used to make the adjustment(s). Not only does this facilitate quality, cost, and plant operability objectives, but it results in control strategies which act properly over a much wider range of conditions. Correct actions are taken, where conventional control methods would make no action or wrong actions. This improves the usefulness of the control strategy to the operator, and leads to higher use of the controls.
The various novel ideas described below are particularly advantageous in such multiple control parameter problems. In the presently preferred embodiment discussed below, a dimethyl terephthalate process (DMT) process is presented as an actual example to show the advantages achieved by the various novel ideas disclosed in this context.
Discrete Control Actions
As mentioned above, control systems that continuously change manipulated parameters are very difficult to monitor. Since operators depend on the supervisor procedure to maintain important product properties and process operating conditions, it is important that they be able to understand and judge supervisor performance. By restricting supervisor changes to a reasonably small number of significant discrete actions, supervisor performance becomes much more understandable.
One novel teaching stated in the present application is an integrated system for process control in which a process supervisor procedure (which is preferably the top level procedure) defines parameters for one or more control systems (or control procedures). The supervisor procedure changes control parameters only in discrete actions, and the thresholds for the decision to act are preferably made large enough (for each control parameter) that every action must be a significant change.
A related novel teaching herein is that every control action taken by the supervisor should be reported out to plant personnel in a substantially natural language message. Preferably, instances where action would be desirable but is not possible (because of constraints or other unusual circumstances) should also be reported. Preferably, a cumulative record of the messages is kept, and is available for review by operators and plant support people. Preferably, the message should report the time, amount, location, and reason for each action. Other relevant information, such as the time stamp of relevant sampled data, and the nature of statistical deviations from aim should preferably be included as well. Since every action is significant, and the number of actions is reduced, the cumulative record provides a meaningful record of supervisor performance.
This is particularly advantageous for systems where some of the relevant time constants are so slow that dynamic process responses last several hours (or longer). A new operator coming on duty at a shift change can use the cumulative record to judge what effects to expect from supervisor actions on the previous shift.
The use of a deadband in feedforward action is one novel means that is advantageously used to discretize supervisor actions. Feedforward action is taken only when the measured value changes by more than the deadband from its value at the last action. This generates a series of discrete changes in the manipulated variable, which can be effectively logged and evaluated by operators.
Statistical filtering of discretely measured values also serves to reduce control actions to a few significant changes. Statistical tests, as is well known, distinguish normal variation around the average from significant deviations from the average. In most cases, a number of measurements will be needed to indicate a deviation. By only acting on statistical deviations, relatively few, but significant, actions will result.
Expert Systems for Process Control
A general problem with expert systems is how the expert system software is to be integrated with process control software. Several expert systems which have been suggested for process control have used an expert system as the top-level supervisor procedure for the control system. However, several of the novel embodiments disclosed herein achieve substantial advantages by departing from this conventional structure. For one thing, if the expert system is the top level procedure, then it becomes more difficult to accommodate more than one expert in the system (or, to put this another way, the potential modularity of the expert system cannot be fully exploited). Thus, one significant advantage of several of the novel embodiments disclosed here is that use of more than one expert system within a single integrated system becomes much more advantageous.
Types of Process Control Systems
It should also be noted that the use of an expert system to design a new process (or to debug a newly introduced process) has significantly different features from the problem of optimally controlling an existing process. While various ones of the novel ideas disclosed herein may have significant applications to such problems as well, the presently preferred embodiment is especially directed to the problem of optimally controlling an existing operating process, and the various novel ideas disclosed herein have particular advantages in this context.
A significant realization underlying several of the innovations disclosed in the present application is that the structure of expert systems for process control applications can advantageously be significantly different from that of other expert system problems (such as consultative expert systems problems, in which a human is queried for information). The Hardy et al. and Erman et al. patents illustrate this difference. Consultative expert systems seek to substantiate one of a number of possible causes by interactively querying the user about the symptoms. Such systems must use complex knowledge representations and inference methods to minimize the number of user queries by carefully selecting the information they solicit. Moreover, since the user is not an expert, the system should be able to explain why it is requesting information.
In contrast, the real-time process problem is much simpler. The information needed by the expert is typically in the form of process measurements, which can be rapidly retrieved from process control and data systems without human intervention. There is much less need to minimize the requests for information. In fact, it may be faster to retrieve all the data that could be relevant to the problem than to determine what data is relevant. Moreover, since the experts will run automatically, there is no need to explain the reasoning during the inference process. As long as the rulebase is not too large, the process control expert can operate effectively using a simple "forward chaining" (or data driven) inference method. There is no need for the complex "backward chaining" procedures used in the consultative systems. Moreover, if a number of modular expert subprocedures are used within a single process, each expert tends to be smaller, and is more likely to work effectively in forward chaining mode. The presently preferred embodiment is especially directed to process control and monitoring, and the novel ideas disclosed herein have particular advantages in this context. However, various ones of the novel ideas may have significant applications to other problems as well.
It is believed to be a significant innovation to use expert system techniques to point to the direction of action in a multi-parameter control problem, as discussed above. One advantage is that the use of the expert permits more cases to be handled; for example, when one control parameter is up against its limits, the expert system can specify another parameter to be changed. The expert can also be especially advantageous in preventing a wrong action from being taken: in some types of processes it is conceivable that erroneous control strategies could potentially cause property damage or injuries, and the natural language inference rules of the expert (possibly combined with a more quantitative optimization scheme) can usefully ensure that this cannot happen. Thus, one advantage of various of the process control expert system embodiments disclosed in the present application is that they facilitate reliable implementation of a control strategy which (primarily) prevents a clearly wrong action from being taken, and (secondarily) permits minimizing costs.
In particular, it is especially advantageous to use a knowledge based (functional) where the rules are constrained to be of the three types described in the context of a process control application. The retrieval rules permit the predominantly quantitative sensor data (and other input data) to be translated into a format which is suitable for expert system application, and the control rules provide a translation back from expert system reasoning into an output which matches the constraints of the control problem.
The present invention is particularly advantageous in controlling processes which are substantially continuous, as distinguished from job shop processes. That is, while some computer-integrated manufacturing systems focus primarily on issues of queuing, throughput, statistical sampling of workpieces for inspection, etc., substantially continuous processes (such as bulk chemical synthesis and/or refining processes) typically demand more attention to issues of controlling continuous flows.
Expert Systems Generally
The present application contains many teachings which solve specific problems and offer corresponding advantages in the sub-class of expert systems used for process control, or even the sub-sub-class of expert systems used for control of substantially continuous processes. However, the present application also discloses many novel features which could be adopted into many other types of expert systems, and/or into many other types of control applications, while still retaining many (if not all) of the advantages obtained in the context of the presently contemplated best mode.
Similarly, while the present application describes numerous novel features which are particularly applicable to rule-based forward-chaining expert systems, some of the innovations described herein are believed to be very broadly novel, and could be adapted for use with other types of expert systems too.
Natural-Language Rule Statements
One of the innovative teachings in the present application provides an expert system tool in which knowledge is entered into the knowledge base through a limited set of pre-defined, highly constrained, natural-language knowledge structures which are presented as templates. In typical previous expert systems, knowledge is coded in the strict syntactical format of a rule or computer language, which allows great flexibility in knowledge representation. The person entering the knowledge (hereafter referred to as the developer) must learn the syntax, must choose an appropriate knowledge representations, and must formulate syntactically correct input.
In contrast, by restricting the developer to constrained, pre-defined structures, the need to learn rule or language syntax and structure is eliminated. Moreover, if the number of such pre-defined knowledge structures is small enough, the total knowledge representation in the expert system can be easily understood. Thus, a knowledge engineer is not needed. The domain expert can enter the knowledge to build an expert system directly. The developer's input can then be translated automatically into an operational expert system. The developer need not be concerned with or aware of the specific language or system used to implement the expert.
Another innovative teaching is that the knowledge entered into the pre-defined natural-language structures is stored in substantially natural-language form. This permits the knowledge to be revised at any time in the form in which it was originally entered: the developer simply recalls the stored template information, modifies it, and stores the modified knowledge. This is also simple enough to be done by the domain expert. The modified knowledge can then be automatically translated into a modified operational expert.
Another significant advantage of several of the disclosed novel embodiments for creating an expert system is that the expert can be significantly more compact and faster in execution. This is achieved by integrating the expert system's rules with the code which performs the inference function. This allows many independent runnable expert systems to be created. Moreover, the ease and simplicity of knowledge updating can still be preserved by maintaining the natural language form of the knowledge. The knowledge base can easily be reviewed and modified without hindrance from the specific inference method used in the runnable system.
Another novel feature of several of the disclosed embodiments is the use of a standardized data interface (as seen by the user) in the knowledge templates, which facilitates the use in the knowledge base of data from a wide variety of systems. Expert systems are allowed to require data from process or laboratory measurements (both current and historical), or data collected from other sources (such as on-line analyzers), or data and parameters from the process control systems. A standard interface to all such data sources facilitates use of the data in expert systems, since domain experts usually lack the programming expertise that would otherwise be needed to access these data sources.
Expert System Rule Types
As mentioned above, previous expert systems tools normally use a rule or computer language which allows great flexibility in knowledge representation. One innovative teaching in the present application is the restriction of the knowledge structure within an expert system to rules of three highly constrained types. The three rule types are: (1) retrieval rules, which each assign one of several descriptors to a name in accordance with the values of numeric inputs; (2) analysis rules, which each can assign a descriptor to a name in accordance with the descriptor/name assignments made by other rules; and (3) action rules, which either execute or don't execute a command in accordance with the descriptor/name assignments made by other rules.
Preferably only the retrieval rules include numeric operations. Preferably only the action rules can enable execution of an external command (i.e. of a command which does not merely affect the operation of expert procedure). Preferably each of the action rules requires only a logical test for the assignment of a descriptor to a name. Preferably none of the action rules can assign a descriptor to a name.
While this organization of an expert system's structure is especially advantageous in the context of a process control expert system, it can also be applied to other types of expert systems. In a process control system, the relevant inputs will normally be process data, laboratory data, or control system parameters. The relevant outputs will normally be executable procedures which affect the operation of control or supervisor systems, or communicate with operators or domain experts. This teaching could also be applied to expert systems generally, in which other input and output functions are more important.
For example, in consultative use, retrieval rules need not be confined to numeric inputs, but could accept the natural language descriptor/name assignments as input from the user. To better control the requests for input, such consultative retrieval rules could advantageously execute contingent upon a test for the previous assignment of a descriptor to a name.
In general, this structuring of the inference rules provides for a more understandable expert. The retrieval rules provide access to process and control system data, and translate from quantitative input data into a natural language form. The emulation of natural-language reasoning is concentrated as much as possible in the analysis rules, which capture knowledge in a form which might be used to communicate between domain experts. The action rules translate from the natural language inference process back to output procedures which are meaningful in the computer and control system being used.
Modular Organization
The organization preferably used for process control has substantial advantages. The top level procedure is a modular process supervisory controller. The supervisor modules allow flexible specification of timing and coordination with other modules. Modules carry out commonly used control functions; using data specified through a standard data interface, as well as calling user customized functions. User customized functions might generate messages, perform unusual control actions, or call expert system procedures. Using the build-supervisor procedure, users can define or redefine modules by editing highly constrained templates which include a standard data interface specification. The standardized data interface (as seen by the user) facilitates communications with an extremely wide variety of systems. Dynamic revision is achieved by storing the user input to the constrained templates as data in a storage area accessible to both the supervisor and build-supervisor procedures. The running supervisor examines the stored data to determine which functions have been specified for that module, and what data sources have been specified through the standard data interface. The supervisor then calls an appropriate modular function and passes the user-specified data.
This organization is especially advantageous in providing parallelism and branching in control strategies. That is, the modular organization of the presently preferred embodiment permits at least the following capabilities:
(a) control strategies for more than one independent control application can be defined and updated;
(b) control strategies for more than one lower level process control system can be defined and updated;
(c) alternative control strategies can be defined and stored, so that an expert system (or other software or user command) can switch or select between control strategies merely by selecting or "de-selecting" modules;
(d) timing and coordination of module functions is facilitated;
(e) multiple independent expert system procedures can be utilized within a single supervisor;
(f) more than one user can define control strategies by accessing different modules, simultaneously if desired.
Another innovative teaching herein is that each supervisor module (or, less preferably, less than all of the module types) should preferably contain a pointer to optional user-customized functions. These functions can be used to generate informative messages about module actions, or a sophisticated user can implement unusual or non-standard control functions, or other customization utilities (such as the build-expert procedure in the presently preferred embodiment) can be used to generate functions accessed in this manner.
This structure is "modular" in the sense that users can call up and modify the various blocks separately; but, as will be discussed below, the command procedures which perform the standardized block functions are not necessarily separate within the source code. That is, modularity is advantageously achieved by storing the template-constrained user inputs to each block as data; when the user wishes to modify the block, the data is translated back into corresponding fields in the template.
Preferably, one of the modular functions in the supervisor is statistical filtering. This is particularly useful in that statistical filtering can be introduced wherever it is advantageous, without requiring extensive custom programming by the users. As described above, statistical filtering is advantageous both for avoiding overreaction to insignificant changes, and also for aiding the understanding by plant operators by reducing the number of actions.
One of the novel teachings contained in the present application is that the use of statistical filtering helps to minimize the number of control parameter adjustments performed by the expert system, which in turn is very advantageous (as discussed below) in providing an understandable log of control actions taken.
Sequencing Modular Blocks
One innovative teaching herein is a system for process control having a modular supervisor procedure which includes novel module timing and sequencing methods. Users can preferably specify modules by editing highly constrained templates, which include several specifiers for methods to be used in controlling and coordinating module execution. Preferably the module timing options include: (1) execute module function at fixed time intervals; (2) execute module function when new data becomes available for a specified data source; (3) execute module function whenever another module executes; (4) execute module function only on programmatic request; and combinations of these. Preferably a standardized data interface is used to specify the data source for the second of these options.
Integration of Expert Procedures
The integration of expert systems into process control has been a challenging problem. Most previous attempts to use expert systems in process control have used LISP based expert systems running on a dedicated machine, often a symbolic processing machine. Usually only one expert system with a single large knowledge base is created for a process. Since the knowledge base could contain many rules, a complex knowledge representation and inference process are needed to make inferences fast enough for real-time use. The expert system typically runs independently, scheduling its own activities, and thus is effectively the "top level" procedure. Using a top level expert makes it more difficult to accommodate more than one expert system. (Another way to regard this area of advantage is to note that, without the inventions contained in the present application, the potential modularity of the expert system cannot be fully exploited.)
Several of the novel embodiments described herein achieve substantial advantages by using more than one expert system subprocedure within a single integrated system. Since expert decisions will normally focus on a specific task or area, the modularity of the problems can be exploited in the structure of the expert system. Also, if the experts run under control of the supervisor, it is much easier to coordinate the decisions of the expert systems with the control actions of the supervisor. Since many important uses of expert systems will affect control actions, this is an important factor.
Another advantage of a modular structure, where expert systems are included as independent procedures called by the supervisor, is that the overall process control system is more reliable. A badly or incompletely functioning expert system within an overall supervisor system will affect only the functions it specifically interacts with. However, the failure of a top level expert system, which controls timing and execution of control functions, could disable all supervisor functions. The modular structure also has significant advantages in maintenance and debugging.
Thus, the organization preferably used for process control has substantial advantages. The top level procedure is a cycling procedure which functions as a process control supervisor. The supervisor process can call on one or more expert system procedures, and the user can call on a build-expert procedure which can reconfigure one of the expert systems already present, or create a new expert system. The supervisor procedure can preferably also call on a historical data base.
The modular organization described is especially advantageous, as discussed above, in providing parallelism and branching in control strategies. This is especially advantageous in process control situations, since the appropriate strategies for different circumstances can be fully pre-defined by the user, and he can rapidly switch between pre-defined strategies as the need arises.
Historical Process Database
The use of a historical database of process data in combination with a process supervisor procedure and/or expert system procedure is particularly advantageous. In the presently preferred embodiment, a historical database is used which can provide a time-stamp with each piece of output data, to clearly indicate provenance, and can retrieve the stored data (for a given parameter) which bears the time-stamp closest to a given time. The historical database can preferably maintain a record of continuously measured process data (such as temperature, pressure, flow rate), as well as discretely sampled, time-delayed measurements, such as laboratory measurements. The database greatly facilitates the use of laboratory (or other sampled type) measurements. Because of the time delay in making laboratory measurements, the value of the measurement when it becomes available in the database will correspond to the continuously measured data for the instant at which the measurement sample was actually taken, which might be several hours in the past. The historical database allows time delayed measurements and their corresponding continuous measurements to be used together. This is advantageous for balancing component material flows in the process. In the presently preferred embodiment, the historical process database may be thought of as providing a way to "buffer" time-stamped data and provide a standardized data interface, but it also permits other functions to be served.
The historical database also advantageously provides a basis for statistical tests. Some statistical tests will require a number of past measurements, which can be retrieved from the database. The database also advantageously allows the calculation of time average values of measurements. This can be useful in dampening noisy signals for use in a control action. In general, the database advantageously serves to buffer data input from a number of sources, standardizing access from the supervisor and expert procedures.
One of the innovative teachings in the present application is an integrated system for process control in which a process supervisor procedure (which is preferably the top-level procedure) is configured as a modular software structure, with modules which can be revised by a user at any time, without significantly interrupting the operation of the process supervisor. The supervisor can define control parameters for many process control procedures, and can retrieve data from many sources (preferably including a historical database of process data, which can provide time-stamped data). The supervisor can also call on various expert subprocedures. Preferably the expert subprocedures can also be modified by an authorized user at any time, by calling up and editing a set of natural-language rule templates which correspond to the rules being executed by the expert subprocedure.
One of the innovative teachings in the present application is an integrated system for process control in which the user can customize the process supervisor procedure with reference to a standardized data interface. The data values to be used by the supervisor are specified in the standard interface by two identifiers. The first identifies which (software) system and type of value is desired. The value of a setpoint in a particular distributed control system, the value of a sensor measurement in a particular process monitoring system, the value of a constraint from a process control or supervisor system, and time averages of sensor measurements from a particular historical database are examples of this. The second identifier specifies which one of that type of value is desired, for example the loop number in the distributed control system.
Data values specified through the standard interface may be used as measured values, manipulated values, or as switch status values indicating an on/off status. Preferably the interface allows the user to specify data in any of the relevant process control and data collection systems used for the process, or for related processes. Preferably, the interface also allows specification of data (both current and historical) in a historical process database. Since multiple control systems (or even multiple historical databases) may be relevant to the process, the standard interface greatly facilitates the use of relevant data from a wide variety of sources.
BRIEF DESCRIPTION OF THE DRAWING
The present invention will be described with reference to the accompanying drawings, wherein:
FIG. 1 schematically shows the structure of hardware and procedures preferably used to embody the novel process control system with expert system capabilities provided by various of the innovative features contained in the present application.
FIG. 2 is a schematic representation of the flow of information in the expert system structure preferably used.
FIG. 3 shows the template used for a retrieval rule in the presently referred embodiment, together with a sample of a retrieval rule which has been entered into the template.
FIG. 4 shows an example of a different kind of retrieval rule known as a calculation rule.
FIG. 5 shows an example of an analysis rule 220.
FIG. 6 shows the presently preferred embodiment of the template for action rules, and an example of one action rule which has been stated in this format.
FIG. 7 shows an example of a chemical synthesis processing layout in which the method taught by the present invention has been successfully demonstrated.
FIG. 8 schematically shows the structure preferably used for the supervisor procedure 130 and the build-supervisor procedure 810.
FIG. 9 shows a menu which, in the presently preferred embodiment, is presented to the user by the build-supervisor procedure 810 to select a template to provide user inputs to define or modify a block within the supervisor procedure.
FIGS. 10-13 show specific templates which, in the presently preferred embodiment, are presented to the user by the build-supervisor procedure to provide input to define or modify a feedback, feedforward, statistical filtering, or program block, respectively.
FIG. 14 shows a block-editing utility menu presented to the user, in the presently preferred embodiment, by the build-supervisor procedure.
FIG. 15 shows a flow chart for the base cycle procedure used in the supervisor procedure in the presently preferred embodiment.
FIG. 16 shows a menu which, in the presently preferred embodiment, is the top-level menu presented to the user by the build-supervisor procedure, and FIG. 17 shows a menu which is the top-level menu within the build-expert procedure.
FIG. 18 is another schematic representation of the interrelations among the various procedures which permit use customization of functionality.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
General Organization of Hardware and Procedures
FIG. 1 schematically shows the structure of hardware and procedures preferably used to embody the novel process control system (with expert system capabilities) provided by various of the innovative features contained in the present application. An underlying process (for example a chemical process) is very schematically represented as a single pipe 160, on which sensors 156 and one actuator 158 are explicitly shown. Of course, real world examples are substantially more complex; FIG. 7 shows the chemical process flow of a sample system in which the presently preferred embodiment has been successfully demonstrated. The various actuators 158 are controlled, in accordance with feedback signals received from various sensors 156, by one or more controllers 154.
In the presently preferred embodiment, the controller 154 is configured as a pneumatic proportional, integral, derivative (PID) controller. However, a wide variety of other controller technologies and configurations could be used. Pneumatic controllers are used in this example because they are common in the chemical process industry, and match well with the feedback requirements of chemical process control. Alternatively, an all-electronic distributed control system could be used instead. Moreover, the controller functionality could be different, e.g. a proportional/integral controller or a proportional controller could be used instead. In the presently preferred embodiment, the PID controller 154 is directly controlled by a computer control system 152. (This system 152 is referred to, in the various examples of user menus shown, as "PCS" (process control system.) The computer controller system 152 and the PID controller 154 may be regarded together as a single first level controller 150, and could easily be configured in that fashion (as with a distributed digital control system) to implement the present invention.
The control system 150 receives at least some of its parameters 132 (e.g. setpoints or feedforward ratios) from a supervisor procedure 130, which is preferably a higher level of control software. (In many of the sample user menus and forms shown, the supervisor procedure 130 is referred to briefly as "ACS.") The supervisor not only receives inputs 157 indirectly (or directly) from various sensors 156, it also receives lab measurement data 162, and also can issue calls to and receive inputs from the expert system 120, as will be described below.
In the presently preferred embodiment, the supervisor and build-supervisor procedures run on a minicomputer (e.g. a VAX 11/785), while the computer control system 152 is a PDP-11.
The supervisor 130 is preferably also connected to a historical process data base 140, which directly or indirectly receives the inputs from the sensors 157 and the off-line lab measurements 162. Thus, when the supervisor needs to access a value 157 or 162, it is not necessary for it to call on a physical device or read a real-time signal. It can simply call a stored value (together with a time stamp) from the database 140. However, many of the advantages of the present invention could also be obtained without using the historical process data base 140.
In addition, the supervisor 130 preferably also embodies a statistical control system. Statistical control systems, as are well known in the art of chemical processes, are advantageous when the process characteristics and measurement characteristics are subject to significant random variation, as they normally are in the chemical process industry. Statistical filtering tests are preferably performed to filter out statistically normal variation, and ascertain whether a process has significantly deviated from its current goal or average. (Alternatively, the statistical filtering functions could be performed elsewhere in software, e.g. in the database software.)
The supervisor procedure 130 is preferably run as a cycling process, and can call multiple expert systems 120 when indicated. (In many of the sample user menus and forms shown, the expert and build-expert procedures are referred to briefly as "PACE.")
A sample realistic process context (in which numerous innovative features have been successfully demonstrated) will first be described. The operation of the historical process database will next be described, since that provides a standardized data interface to which many of the other functions connect. Next, the functioning of the build-supervisor procedure will be described in detail, since that provides many details of how the supervisor is configured in the presently preferred embodiment, and after that the organization of the supervisor procedure itself will be discussed in greater detail. In later sections, the structure of the expert systems preferably used will be described in detail, and the operation of the build-expert procedure which constructs the expert systems will also be described in detail.
Sample Process Context
FIG. 7 schematically shows a sample embodiment of a chemical process incorporating several novel features described in the present application. The system shown is one in which various novel aspects set forth in the present application have been advantageously demonstrated.
It should be understood that the present invention provides a tool of very broad applicability, which can be used in many processes very different from that of FIG. 7. Thus, for example, various of the claims herein may refer to sensors which sense "conditions" in a process, or to actuators which change "conditions" in a process, without reference to whether one sensor or many sensors is used, whether one or several parameters is sensed by respective ones of the sensors, whether the actuators are valves, motors, or other kinds of devices, etc.
FIG. 7 shows part of the distillation train of a process in which paraxylene is air oxidized to make terephthallic acid, which is then esterified with methanol and refined to dimethyl terephthallate (DMT). DMT is sold as a bulk product, and commonly used as a polyester precursor. The esterification process will produce a significant fraction of the impurity methyl formyl benzoate (MFB). One of the key objectives in a DMT synthesis process is controlling the compositional fraction of MFB, since it affects the properties of products made from DMT. The refining train shown in FIG. 7 will reduce the average MFB fraction to a fairly constant level which is (in this example) about 22 ppm (by weight).
The crude feed 702 will typically have a composition which is (by weight) about 74% DMT, about 20% orthoxylene (and related components which tend to recycle with the orthoxylene), about 5% methyl hydrogen terephthallate (MHT), and about 0.2% of methyl formyl benzoate (MFB). The MFB-depleted product 740 is preferably further refined to reduce the MHT fraction.
The crude feed 702 is fed into approximately the middle of a first distillation column 710. The column 710 is heated at its base by a steam reboiler 712. The steam flow is controlled by a flow controller 714 (which is connected to an actuator 716 and a sensor 718.) Similarly, the feed flow controller 704 is connected to an actuator 706, and a sensor 708. The column 710, as operated in the presently preferred embodiment, has internal pressures and temperatures which range from about 230 Torr at about 230° C. at its bottom to about 55 Torr at about 70° C. at its top. The vapor stream 720 is passed through a condenser 722, and some of the resulting condensate is fed back into the column as reflux 724. The product stream 726 has a mass flow rate of about 20% of the crude feed 702, and is recycled. A bottom product 728 is fed to the top of a second distillation column 730. The second distillation column has a steam reboiler 732 near its bottom (controlled by a steam flow controller 734, actuator 736, and sensor 738). The pressures and temperatures in the second column 730 (which in the user screens of the presently preferred embodiment is frequently referred to as the "MFB column") range from about 240° C. at about 235 Torr at the bottom of the column to about 70 Torr and about 190° C. at the top of the column. The bottom product 740 of the column 730 (which has a mass flow of about 0.8 of the crude feed 702) is the MFB-purified product. (In this product the fraction of MFB will on average have been reduced to about 22 ppm, for the conditions given.) The top product 742 of the column 730 is passed through a condenser 744 and reintroduced into column 710 as a bottom feed. (Column 710 is referred to, in the specific example given below, as the "xylene column".) The mass flow in the loop 728/742 is quite large; typically the mass flow of flow 728 will be about three times the mass flow of the crude feed 702.
In addition, a third distillation column, in the presently preferred embodiment, is operated in parallel with a middle section of column 710. This third column 750 is fed a side draw stream 752 from the first column 710. The vapor stream 754 of column 750 is passed through a condenser, and part of the condensate is reintroduced to column 750 as a reflux 758. Most of the remaining condensate is reintroduced to first column 710 as an upper middle feed. Similarly, the liquid stream 762 of third column 750 is partly reintroduced as a bottom feed after being vaporized in the reboiler 764, but is also partly fed back into column 710 as a lower middle feed 766. The additional separation provided by the third column 750 enhances the net compositional segregation of MFB. The middle product 768 of the third column 750 is a low-flow-rate product flow (typically 0.003 times the mass flow of the crude feed 702), and this product flow removes most of the undesired MFB impurity from the system. The temperatures and pressures in the third column 750 range from (in this example) about 230° C. at about 260 Torr at the bottom of the column to about 60 Torr at about 125° C. at the top of the column. Stream 761 is a small purge stream removing intermediate materials.
In the sample embodiment, the three primary control points for control of MFB composition are the steam feed to the MFB column reboiler 730, which is controlled by flow controller 734; the steam feed to the xylene column reboiler 710, which is controlled by flow controller 714; and the feed of crude feed stock to the xylene column 710, which is controlled by flow controller 704. Numerous other controllers, pumps, and other process equipment maintain the temperatures, pressures, and flow rates at other points in the process. In accordance with principles well known in the art of chemical engineering, this serves to maintain mass and energy balances and compositional trends consistent with the ultimate control objective, which is to maintain a high and constant purity in the product stream 740.
Historical Process Database
In the presently preferred embodiment (as shown in FIG. 1), the supervisor 130 receives data primarily through a historical process data base 140, which directly or indirectly receives the inputs from sensors 157 and off-line laboratory measurements 162. Thus, when the supervisor needs to access a value 157 or 162, it is not necessary for it to call on a physical device or read a real-time signal, since it can simply call a stored value (together with a time stamp) from the database 140.
In the preferred embodiment, every data value provided by the historical database has a timestamp attached. Data are received in at least two ways: first, some parameters are received as nearly continuous data flows (more precisely, as high-sampling-rate time series). For example, the data 157 from sensors 156 (e.g. temperature sensors) will be received as a series of digital values from analog-to-digital converters 155. In the presently preferred embodiment, compression algorithms are used to reduce the storage requirements of this data, and permit a usefully long period of time to be represented without requiring impractical amounts of storage space. However, this operation (which includes both compression and decompression algorithms) is essentially invisible to the supervisor procedure 130.
Secondly, lab analysis data 162 can also be stored in the historical database 140. For example, compositional measurements must normally be done offline. A physical sample will be pulled from the physical process flow and sent to the laboratory for analysis. The resulting lab analysis value is entered into the historical database, timestamped with the time the sample was taken.
A third source of data is simulations: running processes can be simulated, using any of a variety of currently available simulation methods, and predicted conditions can be stored in the historical database (together with the proper timestamp). Thus, for example, control strategies can access data generated by complex real-time simulations.
Thus, many of the advantages of the database 140 derive from the fact that it can provide a timestamp to accompany every piece of data it provides. In addition, in the presently preferred embodiment, the database also stores the name and units for each parameter. As presently practiced, the database is also able to perform a variety of other functions, including monitoring, activating alarms if certain sensed measurements reach certain critical levels, output processing (i.e. loading data out to physical devices), generating plots of selected parameters over time, as well as other common database functions (e.g. generating reports).
This structure is quite flexible: for example, in alternative embodiments, one supervisor procedure could interface to multiple databases 140, and/or one database 140 could receive calls from more than one supervisor procedure 130 (which optionally could be running on different systems).
Supervisor and Build-Supervisor Procedures
The present application describes some very advantageous features of novelty in the supervisor procedure 130 and build-supervisor procedure 810, which could optionally and less preferably be incorporated in embodiments which did not include at least some of the innovative features described in the context of the expert and build-expert systems 110 and 120.
The supervisor procedure 130 preferably used contains a modular software structure which greatly facilitates initial setup and also modification. Preferably the supervisor procedure 130 is a cycling procedure constructed as a set of blocks. That is, each block defines a core procedure which (as seen by the user, both initially and whenever called up for modification) is substantially self-contained, and which (in the presently preferred embodiment) is of one of four types. Preferably each block is either a feedforward block, a feedback block, a statistical filter block, or a program block. (That is, preferably each block is configured by user inputs to a template for one of these block types.) Preferably each kind of block also has the capability to call a user subroutine, and in fact the "program blocks" used in the presently preferred embodiment perform no other function.
The functional templates and data interface definitions for the most commonly used functions are pre-defined, but the user can also add code of his own if he wishes to do so. Providing standardized templates for the most commonly used functions expedites initial functional definition, and also facilitates maintenance, but sophisticated users are not prevented from writing their own customized functions (such as messaging).
Feedback blocks are used when a manipulated parameter must be adjusted to keep a measured parameter near a desired goal. Feedforward blocks are used when two parameters (which are not necessarily in a causal relation) are linked, i.e. when a manipulated parameter must be adjusted to keep it in some ratio (or other relation) to a measured parameter. Statistical filtering blocks are used, in the presently preferred embodiment, to provide the advantages of statistical process control, and to facilitate minimizing the number of control parameter adjustment actions.
Preferably a maximum number of blocks is predefined. (In the presently preferred embodiment, 200 blocks is the preset maximum, and this number is large enough to serve the control needs of several different systems simultaneously.) The imposition of a maximum helps to maintain the software, by limiting the number of functions which can be crowded into any one software structure, and by motivating users to delete obsolete block definitions.
Thus, a software structure like that described can be used to control several systems and/or used by several users. The provision of "ownership" identification for each block, which may optionally be combined with access privilege restrictions, advantageously helps to preserve maintainability in multi-user environments.
FIG. 8 shows the preferred organization of the supervisor procedure 130. The top level loop (shown as a base cycle controller procedure 802), which calls the various blocks 851, 852, 853, sequentially, is preferably a cycling procedure. For example, the dormant time waiting block 891 might be set, in the dimethyl terephthalate synthesis application described, so that the base cycle procedure 802 is executed every pb 15 minutes (and therefore the entire sequence of blocks 851 etc. is called for possible execution every 15 minutes). The base cycle procedure also preferably performs some overhead functions. For example, the base cycle procedure 802 optionally contains the appropriate commands for branching on interrupts 804, and for initialization after a start command 806. Secondly, the base cycle procedure 802, upon calling each block, will preferably look at the header of the block (which is stored as data in shared memory, as discussed below), and usually also at some external information, such as the system clock value or the time stamp of a variable, to see if that block is due to execute. In the presently preferred embodiment, each block will also have status flags which indicate whether it may be executed, and will also have timing options which can be used by the user to specify, for example, that a particular block is to be executed only every 175 minutes.
The base cycle procedure 802 is not the only procedure which is relatively "high-level" with respect to the blocks 851, 852, etc. The build-supervisor procedure 810 is able to present the user with templates 812, and to (effectively) change the operation of the blocks 851, 852, etc., by changing shared memory values in accordance with the user's inputs to the templates 812.
That is, the real time control actions of the supervisor procedure blocks are supervised by the base cycle procedure 802. The base cycle procedure is responsible for determining when blocks are on/off, when blocks should be initialized, and when blocks should be executed. It also controls the timing of the base scan through all blocks.
In the presently preferred embodiment, each time the base cycle procedure executes a block, it checks the block type label (in shared memory) and calls the appropriate subroutine. That is, a single block of executable code is used for all of the feedback blocks, and similarly another block of code is used for all the feedforward blocks, etc., so that all 200 blocks require only four subroutines for their standard functions. Each time the base cycle routine executes a feedback block, it calls up the user-defined parameter set for that particular block, and passes those parameters to the subroutine which performs feedback functions in accordance with those parameters.
Base Cycle Procedure
FIG. 15 shows a flow chart of the logic preferably used in the base cycle procedure 802. The sequence of actions used in the main control program, when it is first started (e.g. by submitting it to a job queue) is:
Check to see if more than 30 minutes has passed since the last control cycle in the supervisor procedure. If so, initialize all blocks whose status is "On", "Active", or "Just turned on". (Initialization sequence is given below).
Start the control cycle loop: (This loop is shown as l510 in the flow chart of FIG. 15.)
Set the system status to "Running-Computing".
Compute the next cycle time by adding the base scan interval to the current time.
Start a loop through all blocks, starting with block number 1 and counting up to the maximum nu;ioer of blocks (This loop is shown as 1520 in the flow chart of FIG. 15):
Check block status:
Get the switch status of the block. If the block is switching with an external switch parameter, get its status. (The switch status will be "On" if the external switch is on, or "Off" if the external switch is off.) If the loop is switched manually, the switch status is the same as the block's current status.
If the switch status is "On", "Active", "Toggled On", or "Just turned on", the block is on.
If the block is on, and the current block status is not "On" or "Just turned on", then the block is just being turned on. Set the Block Status to "Just turned on".
If the block is on, and the current block status is "On" or "Just turned on", then the block is continuing to be on. Set the Block Status to "On".
If the block is not on, it is off. Set the block status to "Off".
If the block status is "Off", "Inactive", or "Failed", loop back up and start the next block.
If the block status is "Just turned on", INITIALIZE the block (These steps are shown as 1524 in the flow chart of FIG. 15):
If the block has a measured variable, set the "Last measured time" equal to the current time of the measured variable.
If the block has a Key block, set the "Key block time" equal to the "Last execution time" of the key block.
Set the "Last execution time" of the block to the current time.
If the block is a feedforward block, set the "Old measured value" equal to the current value of the measured variable.
If the block has a measured variable, get its current time.
If the block has a key block, get its last execution time.
If the block timing option includes fixed interval, and if the elapsed time since the "last execution time" of the block is greater than or equal to the execution time interval, set the execute flag for the block.
If the block timing option includes keying off the measured variable, and if the current time of the measured variable is more recent than the "last measured time" of the block, set the "last measured time" for the block equal to the current time of the measured variable, and set the execute flag for the block.
If the block timing option includes keying off another block, and if the last execution time of the key block is more recent than the "key block time", set the "key block time" equal to the last execution time of the key block, and set the execute flag for the block.
If the execute flag for the block is set, set the last execution time for the block equal to the current time, and execute the block. Only execute the block once, even if more than one timing option was satisfied. (The block execution procedures are discussed in greater detail below, and are shown generally as 1530 in the flow chart of FIG. 15.)
If more blocks need to be processed, loop back to the next block.
This is the end of the loop 1520 through all the blocks.
Set the system status to "Running-Sleeping".
Set a wake up timer for the next cycle time computed above, and go to sleep until the timer expires, or until awakened by a request to terminate the program.
Wake up. Check to see if interrupted to terminate. If so, set the system status to "Terminated normally", and stop completely.
If not terminated, branch back to the start of the control cycle loop 1510.
Sample Source Code
The source code for the procedure which actually performs this function, in the presently preferred embodiment, is as follows. Due to the formatting requirements of patent application, some portions of this and other portions of source code provided herein contain statements which are wrapped across more than one line (and hence would need to be restored to single-line format, or appropriate leaders inserted, before being loaded for execution); but those skilled in the art will readily recognize these instances, and can readily correct them to produce formally perfect code.
TABLE 1__________________________________________________________________________C**********************************C Control.forCC Main control program for the Advanced ControlC System,C a high level optimization and control systemC running on the Vax, using Vantage facilities.CC***********************************C Program Control Include `ACS$includes:Block --parameters.inc/nolist`Include `ACS$includes:Van --functions.inc/nolist`Include `ACS$includes:Sys --functions.inc/nolist`Include `ACS$includes:Manip --params.inc`Include `ACS$includes:Meas --params.inc`Include `ACS$includes:Filter --params.inc`Include `ACS$includes:ACSserv.inc`Include `ACS$includes:ACSstatus.inc`CInteger*4 BlockInteger*4 Integer --NowCharacter*20 Character --nowInteger*4 Timbuf(2)Integer*4 Measured --time --stampInteger*4 Key --block --exec --timeLogical*2 Execute --blockLogical SuccessLogical FirstCharacter*18 Debug --timeLogical Force --initializationParameter (Force --initialization = .True.)Logical Dont --force --initializationParameter (Dont --force --initialization = .False. )CInteger*2 Meas --typeInteger*2 Meas --varInteger*2 Filt --typeInteger*2 Filt --varCInteger*4 Event --flag --stateInteger*4 Timer --flagInteger*4 Interrupt --flagCharacter*9 Cluster --nameParameter ( Cluster --name = `ACS --FLAGS` )Integer*4 Flag --maskCLogical Interrupt --flag --setInterrupt --flag --set( ) = Btest(Event --flag --state,1)CTimer --flag = 64Interrupt --flag = 65First = .True.Flag --mask = 0Flag --mask = Ibset ( Flag --mask , 0 )Flag --mask = Ibset ( Flag --mask , 1 )CC. . .Record control program startup in the log fileCVan --status = Vss$ --from --ascii --time ( ' ' , Integer --now )Van --status = Vss$ --to --ascii --time ( Integer --now ,1 Character --now )Write (6,*) ` Started the ACS control program at `,1 Character --nowCC. . .Create the event flag cluster , clear interrupt flagCSys --status = Sys$ascefc ( %Val(Timer --flag ) ,1 %descr(Cluster --name) , 0 , )Sys --status = sys$clref ( %val(Interrupt --flag ))CC. . .Check to see if ACS --control has been down for more thanC 30 minutes. If so, initialize all active blocks.CVan --status = Vss$ --from --ascii --time ( ' ' , Integer --now )If ( Integer --now - Integer --next --cycle .gt. 30*60 ) Then Do 10 Block = 1,Max --blocksIf ( ( Block --status(Block)(1:2) .eq. `On` ) .or.1 ( Block --status(Block)(1:6) .eq. `Active` ) .or.1 ( Block --status(Block)(1:14) .eq. `Just turned on` ) )1 Call Initialize --block ( Block ) ContinueEnd IfCC. . .The main block control loop1 ContinueCC. . .Set system status to RunningCSystem --status = `Running-Computing `CC. . .Set Wake up time to ACS --base --scan minutes from nowCVan --status = Vss$ --from --ascii --time ( ' ' , Integer --now )Van --status = Vss$ --to --ascii --time ( Integer --now ,1 Character --now )Integer --next --cycle = Integer --now + ACS --base --scan*60Call Vss$ --get --systime ( Integer --next --cycle , Timbuf )CC. . .Loop through all the blocksCDo 100 Block = 1,Max --blocksCC. . .Update the block Status from the info coming from PCSCCall Check --block --status ( Block )CC. . .Check the block status, if inactive or off, skip itCIf ( ( Block --status(Block)(1:8) .eq. `Inactive` ) .or.1 ( Block --status(Block)(1:6) .eq. `Failed` ) .or.1 ( Block --status(Block)(1:10) .eq. `On-holding`) .or.1 ( Block --status(Block)(1:3) .eq. `Off` ) ) Then Go To 100End ifd If ( First )d 1 write(6,*) ` Block: `,block,`Status = `1 block --status(block)CC. . .If the block has just been turned on, initialize itCIf (Block --status(Block)(1:14) .eq. `Just turned on` ) Then Call Initialize --block( Block )End ifCC. . .Check to see if it is time to execute the blockCC. . .Use appropriate calls for the block typeCIf (1 ( Block --type ( Block )(1:8 ) .eq. `Feedback` ) .or.1 ( Block --type ( Block )(1:11) .eq. `Feedforward` ) .or.1 ( Block --type ( Block )(1:7 ) .eq. `Program` )1 ) Then ACS --status = ACS --get --meas --var --type ( Block , Meas --type ) If ( Meas --type .eq. Cur --val --van --var ) Then ACS --status = ACS --get --meas --var --num ( Block , Meas --var ) Van --status = Vss$g --curtime ( Meas --var ,1 Measured -- time --stamp )Else Measured --time --stamp = 0End IfCElse If (1 ( Block --type ( Block )(1:8 1:8 ) .eq. `Shewhart` )1 ) ThenACS --status = ACS --get --filtered --var --type ( Block , Filt --typeIf ( Filt --type .eq. Van --var --filter ) Then ACS --status = ACS --get --filtered --var --num ( Block , Filt --var Van --status = Vss$g --curtime ( Filt --var ,1 Measured --time --stamp )Else Measured --time --stamp = 0End IfEnd IfCC. . .Get exec time of key block, if definedCKey --block = Var --num2(Block)If ( Key --block .ne. Empty ) Then Key --block -- exec --time = Last --execution --time ( Key --block)Else Key --block --exec --time = 0End IfCExecute --block = .False.d If ( First .eq. .True. ) Thend Van --STATUS = vss$ --to --ascii --time ( integer --now , Debug--time )d write(6,*) `Block = `,blockd write(6,*) `Integer --now = `,Debug --timed Van --STATUS = vss$ --to --ascii --time ( last --execution --time(block)d 1 , Debug --time )d write(6,*) `last --execution --time = `,debug --timed Van --STATUS = vss$ --to --ascii --time ((-1)*Frequency(block)*60d 1 , Debug --time )d write(6,*) `Frequency(block) = `,Debug -- timed Van --STATUS = vss$ --to --ascii --time ( last --measured --time(block)d 1 , Debug --time )d write(6,*) `last --measured --time = `,Debug --timed Van --STATUS = vss$ --to --ascii --time ( measured --time --stampd 1 , Debug --time )d write(6,*) `measured --time --stamp = `,Debug --timed write(6,*) `timing --option = `, Var --num3(Block)d End IfCI --timing --option = Var --num3(Block)If ( ( I --timing --option .eq. Interval ) .and.1 ( Integer --now - Last --execution --time(Block) .ge.1 Frequency(Block)*60) ) Then1 Last --execution --time(Block) = Integer --nowLast --measured --time(Block) = Measured -- time --stampExecute --block = .True.CElse If ( I --timing --option .eq.1 Key --off --measured --variable )ThenIf ( Measured --time --stamp .gt.1 Last --measured --time(Block) ) Then Last --execution --time(Block) = Integer --now Last --measured --time(Block) = Measured --time --stamp Execute --block = .True. End IfCElse If ( I --timing --option .eq.1 Key --off --ACS --block ) ThenIf ( Key --block --exec --time .gt.1 Fix --time(Block) ) Then Last --execution --time(Block) = Integer --now Last --measured --time(Block) = Measured --time --stamp Fix --time(block) = Key --block -- exec --time Execute --block = .True. End IfCElse If ( I --timing --option .eq.1 Intrvl --and --key --off --ACS --block) ThenIf (1 ( Key --block --exec --time .gt.1 Fix --time(Block) ) .or.1 ( Integer --now - Last --execution --time(Block) .ge.1 Frequency(Block)*60)1 ) Then Last --execution --time(Block) = Integer --now Last --measured --time(Block) = Measured --time --stamp Fix --time(block) = Key --block --exec --time Execute --block = .True. End IfCElse If ( I --timing --option .eq.1 Intrvl --and --key --off --meas --var) ThenIf ( 1 ( Measured --time --stamp .gt.1 Last --measured --time(Block) ) .or.1 ( Integer --now - Last --execution --time(Block) .ge.1 Frequency(Block)*60)1 ) Then Last --execution --time(Block) = Integer --now Last --measured --time(Block) = Measured --time --stamp Fix --time(block) = Key --block --exec --time Execute --block = .True.End IfCElse If ( I --timing --option .eq.1 Key --off --meas --var --and --block) ThenIf (1 ( Key --block --exec --time .gt.1 Fix --time(Block) ) .or.1 ( Measured --time --stamp .gt.1 Last --measured --time(Block) )1 ) Then Last --execution --time(Block) = Integer --now Last --measured --time(Block) = Measured --time --stamp Fix --time(block) = Key --block --exec --time Execute --block = .True. End IfCElse If ( I --timing --option .eq.1 Intrvl --and --Key --meas --and --block)ThenIf (1 ( Key --block --exec --time .gt.1 Fix --time(Block) ) .or.1 ( Measured --time --stamp .gt.1 Last --measured --time(Block) ) .or.1 ( Integer --now - Last --execution --time(Block) .ge.1 Frequency(Block)*60)l ) Then Last --execution --time(Block) = Integer --now Last --measured --time(Block) = Measured --time --stamp Fix --time(block) = Key --block --exec --time Execute --block = .True.End IfEnd ifCC. . .If Time to execute, call the Subroutine for the appropriate blockCIf ( Execute --block .eq. .True. ) Then If ( Block --type(Block)(1:11) .eq. `Feedforward` ) then Call Feedforward --block(Block) Else If ( Block --type(Block)(1:8 ) .eq. `Feedback` ) then Call Feedback --block(Block) Else if ( Block --type(Block)(1:7 ) .eq. `Program` ) then Call Program --block ( Block) Else if ( Block --type(Block)(1:8 ) .eq. `Shewhart` ) then Call Shewhart --block( Block)End ifEnd ifC 100 ContinueCC. . .All Blocks checked and executed if needed; go to sleep untilneededC 102 ContinueCSys --status = Sys$setimr ( %val(Timer --flag) , %ref(Timbuf),, )If (Sys --status .eq. %loc(Ss$ --normal) ) Thend Write(6,*) ` Successfully set timer.`ElseWrite(6,*) ` Error return from setimr in Control at `,1 Character --nowEnd IfCSystem --status = `Running-Sleeping `Sys --status = Sys$wflor ( %val(Timer --flag) , %val(Flag --mask)If ( .not. Sys --status ) Call Lib$signal(%val(Sys --status))CSys --status = sys$readef ( %val(Timer --flag ) ,1 %ref(Event --flag --state) )If ( .not. Sys --status ) Call Lib$signal(%val(Sys --status))CIf ( ( Sys --status .ne. %loc(Ss$ --wasclr) ) .and.1 ( Sys --status .ne. %loc(Ss$ --wasset) ) ) Then Write(6,*) ` Problem reading event flag status`End IfCC. .Test the interrupt bit- if set, process the requestCIf ( Interrupt --flag --set( ) ) Thend Write(6,*) `got an interrupt` Call Shutdown ( Event --flag --state )Elsed Write(6,*) `Timer expired.`End IfCFirst = .False.Go To 1CEnd__________________________________________________________________________
Copyright (c) 1987 E.I. duPont de Nemours & Co., all rights reserved.
Build-Supervisor Procedure
The build-supervisor procedure 810 presents templates 812 to the user and stores the user responses to these templates in a "global section" portion of memory (i.e. a shared or commonly accessible portion of memory). That is, the user inputs to the templates for the various blocks 851, 852, etc., are stored where the base cycle procedure 802 can access them and the build-supervisor procedure 810 can also access them. Thus, an authorized user can at any time interactively call up data from shared memory space 814, see these parameters in the context of the templates 812, and modify the functions of the various blocks 852, 853, etc. and/or define new blocks (and/or delete existing blocks), while the base cycle procedure 802 continues to call the various blocks on the appropriate schedule. That is, the base cycle procedure 802 is preferably a cycling procedure which satisfies the real-time process control demands of the underlying process, while the build-supervisor procedure 810 retains the capability for reconfiguring the operation of the various blocks in the supervisor, according to user input.
It should be noted that the structural features and advantages of the build-supervisor procedure are not entirely separate from those of the supervisor procedure. The two procedures are preferably operated separately, but they provide an advantageous combination. The features of the supervisor procedure are partly designed to advantageously facilitate use of the build-supervisor procedure, and the features of the build-supervisor procedure are partly designed to advantageously facilitate use of the supervisor procedure.
In the presently preferred embodiment, the nexus between the build-supervisor procedure and the supervisor procedure is somewhat different from the nexus between the build-expert procedure and the operating expert procedures. The user entries made into the more constrained parts of the templates can be transferred fairly directly to the operating supervisor procedure: the build-supervisor procedure stores values (corresponding to the data input by the user in the accessible fields of the templates) in a shared section of memory, which is immediately accessible by the supervisor procedure as soon as the stored status value for the block is changed to "Active". By contrast, if the customized user routines (including the expert routines generated by the build-expert software) are modified, they must be compiled and linked with the supervisor procedure.
The build-supervisor procedure 810 preferably also has the capability to stop or restart the base cycle procedure 802, independently of whether the build-supervisor procedure 810 has updated the shared memory 814 in accordance with user inputs to templates 812.
Top-Level Menu
The user who begins an interaction with the build-supervisor procedure is first presented with a menu which (in the presently preferred embodiment) resembles that shown as FIG. 16. This menu provides options which permit the user to setup (or modify) blocks, to monitor blocks, to call block-management utilities, to exit, or to go into a structured environment for writing user programs.
If the user chooses block setup, he next sees a menu like that shown in FIG. 9. This menu is presented to the user by the build-supervisor procedure 810 to select a specific existing template 812' (i.e. a template with the previously defined data values of a particular block are shown in the appropriate fields of the template) or a blank template 812 of a given type to provide user inputs to define or modify a block 851, 852, etc.
This form allows the user to choose which block to enter setup parameters for, and, if the block is a new one, allows a choice of which type block it will be. To go back to the previous form (in this case the top-level menu), he can press the "-" key on the keypad.
To set up a new block, the user can either enter a block number which he knows is not in use, or the build-supervisor procedure will provide him with the lowest number block which is not in use. To enter a block number, the user can simply type the number in the block number field and press the return key. To get the build-supervisor procedure to find the lowest number unused block, the user can press keypad 8. The cursor will move to the block type field and the build-supervisor procedure will request that the user enter the number from the list for the type of block desired. The build-supervisor procedure will then present the user with a block setup form for that block type. If the user mistakenly enters a block number which is already in use, the build-supervisor procedure will go directly to the setup form for that block, but the user can simply press keypad minus on the setup form to go back to the block setup selection form and try again. To enter or modify setup parameters for an existing block, the user can simply enter the block number and press the return key, and the build-supervisor procedure will present the block setup form for that block.
In the best mode as presently practiced, all four block setup forms have some common features. Keypad 9 will move the cursor from anywhere on the form up to the block number field. Keypad 8 will find the lowest number available block and set it up as the same block type as the form showing on the screen. Keypad 7 tests all the parameters on the block and changes the block status to switch it on or off, or requests new data if the user has not yet supplied it. (In addition, many of the parameters are checked for gross error as the user enters them.)
The various block setup forms shown as FIGS. 10 through 13 will be individually described below; but first, some features common to some or all of the block setup forms, and some features characteristic of the operation of the blocks thus defined, will be described.
When a block is turned on, the block status will not go directly to "On." (The full system of block status options (in this embodiment) is described below.) Depending on how the block is set up to be switched on and off, the status will change to "Toggled on" or "Active". The base cycle procedure will update the status as the block is executed, changing to "Just turned on" and then to "On". When turning a block off, the status will change to "Off" or "Inactive", again depending on how the block is set up to switch. These status sequencing rules facilitate use of initialization and/or shutdown steps in controlling block functionality.
Any time a parameter is entered or changed on a setup form, the block status will be set to "Inactive." This means that the block parameters have not been checked to assure that everything needed has been entered and is consistent. If a parameter is changed on a block which is currently on, the block must be toggled from "Inactive" to "Active" or "Toggled On" using Keypad 7.
Data Source Specification
The templates presented to the user for block customization include a standardized data interface. The data values to be used by the supervisor are specified in the standard interface by two identifiers. The first identifies which (software) system and type of value is desired. The value of a setpoint in a particular distributed control system, the value of a sensor measurement in a particular process monitoring system, the value of a constraint from a process control or supervisor system, and time averages of sensor measurements from a particular historical database are examples of this. The second identifier specifies which one of that type of value is desired, for example the loop number in the distributed control system.
For example, in FIG. 10 the user has entered "4" in the highlighted area 1002 after the phrase "Measured Variable Type:". This particular identifier (i.e. the value entered in this field by the user) indicates that the variable type here is a current value of a variable from the historical database, and the build-supervisor procedure adds an abbreviated indication of this ("Current Val Hist Dbase Var #") onto the user's screen as soon as the user has entered this value in the field 1002. (If the user entered a different code in the field, a different short legend might be shown. For example, as seen in FIG. 10, the user has indicated a variable type of "2" after the phrase "Manipulated Var Type", indicating that the manipulated variable is to be a loop goal of the DMT control system.) As the second identifier, the user has indicated a value of "2990" in field 1004, to indicate (in this example) which particular Database variable's current value is to be used. For this identifier too, the build-supervisor procedure adds an abbreviated indication of its interpretation of this identifier ("DMT PRD MFB SHWRT DEVIAT") onto the user's screen as soon as the user has entered this value in the field 1004.
Data values specified through the standard interface may be used as measured values, manipulated values, or as switch status values indicating an on/off status. Preferably the interface allows the user to specify data in any of the relevant process control and data collection systems used for the process, or for related processes. Preferably, the interface also allows specification of data (both current and historical) in a historical process database. Since multiple control systems (or even multiple historical databases) may be relevant to the process, the standard interface greatly facilitates the use of relevant data from a wide variety of sources.
Block Timing Information
In the presently preferred embodiment, all blocks except the Shewhart block provide the same block timing options. Block timing determines when a block will perform its control actions. The build-supervisor procedure provides three fundamental block timing options, which can be used in any combination, providing a total of 7 block timing options. The three fundamental options are:
Fixed Time Interval: the block will execute at a fixed time interval. The user specifies the time interval, e.g. in minutes. (Note that a combination of this option and the following has been specified in the example of FIG. 13, by the user's entry of "5" into field 1306.)
Key Off Measured Variable: the block will execute every time a new value is entered into the process database for the measured variable. The measured variable must be a "sampled" type variable. (Note that this option has been specified in the example of FIG. 10, by the user's entry of "2" into field 1006.)
Key Off Another ACS Block: the block will execute every time a (specified) lower numbered block executes. The user specifies which block will be the key block. Any combination of one, two or three timing options can be used. Blocks using a combination timing option execute whenever any of the specified timing options are satisfied. (Note that this option has been specified in the example of FIG. 11, by the user's entry of "3" into field 1006.)
Block timing options are represented on the setup forms by a number code. The user enters the number code corresponding to the desired timing option. If the timing option includes fixed interval timing, an execution time interval must also be specified. If the block is to key off another block, the key block number must be specified.
In future alternative embodiments, the block timing options set forth here may be especially advantageous in multi-processor embodiments: the separation of the control action specifications in multiple blocks shows the inherent parallelism of the problem, while the keying options in which one block keys off another show the block sequencing constraints which delimit the parallelism. The standardized data interface used in the presently preferred embodiment may also be advantageous in this context, by allowing block execution to be keyed off events external to the supervisor.
Primary Block Switching
The supervisor procedure provides several ways to switch block actions on and off. If the block needs to be turned on and off by an operator, the build-supervisor procedure allows the user to specify an external switch system and a switchable entity within that system which the block on/off status is to follow. For example, the user may specify a specific control system and a loop number within that system. The block will turn on when that loop is on, and off when that loop is off. The standardized data interface allows any accessible control system to act as the switch system. As a further alternative, the blocks can be set to switch on and off only under the control of the developer (i.e. under the control of the build-supervisor user). In this case, the block can only be switched using the toggle on/off function on the block setup form.
The external switch system is represented on the block setup forms by a number. The user enters the number corresponding to the external switch system he wants to use. The entity within the switch system (e.g. the loop number) is entered in the next field. (In the example of FIG. 10, the user entries in fields 1008 and 1010 have specified an external switching variable.) If the block is to be turned on and off only from the build-supervisor procedure setup form, a zero is entered for the switch system number, and the word "Manual" will show in the field for the switch entity number. (This option has been selected in the example of FIG. 13.)
Secondary Block Switching
The supervisor also provides secondary means of controlling block execution. Blocks which have been turned "on" by their primary switch controls may be "selected", "de-selected", or "held" by programmatic requests. The status of selected blocks changes to "On-selected". Selected blocks continue to function as if they were "On". The status of blocks which are deselected by programmatic request changes to "On-deselected". De-selected blocks take no control action. However, they differ from blocks which are "off" because they continue to maintain all their internal information so that they are always ready to execute if "selected". The status of blocks which are held by programmatic request changes to "on- holding". The programmatic request includes the length of time the block is stay on hold. Blocks which are holding act as if they were off. When the holding time expires, the status of holding blocks changes to "Just turned on," and they initialize.
One advantage of these block switching options is that they provide a way to embed alternative control strategies in the supervisor procedure. That is, control strategies can be readily changed merely by selecting some blocks in the supervisor procedure and/or deselecting other blocks. This is advantageous in terms of software documentation, since it means that alternative control strategies can be documented and maintained within the same software structure. It is also advantageous in interfacing to other procedures: for example, the expert systems called by the presently preferred embodiment will frequently take action by selecting and/or deselecting blocks of the supervisor procedure.
These block control options facilitate the use of one supervisor procedure to interface to multiple controllers, and the use of one supervisor procedure by different users to control different processes. The block status system permits one or more blocks to be updated without interfering with the running supervisor process; in fact, in optional environments, multiple users could be permitted to update different blocks at the same time.
Block Description Fields
All blocks allow the user to enter three descriptive fields. These fields are for user reference and can be searched when printing lists of block parameters. They have no effect on block actions. The "control application name" field allows the user to group blocks that are part of the same control application by giving them all the same application name. (In the example of FIG. 10, the user entry in field 1014 has specified "MFB Control". Note that the examples of FIGS. 11, 12, and 13 show corresponding entries in this field.) The block description field allows the user to describe the block's specific action or purpose. (In the example of FIG. 13, the user entry in field 1316 has explained that this is a "Block to run expert deciding where to take MFB feedback action".) The ownership field specifies which user has control of the block. (In the example of FIG. 10, the user entry in field 1012 has specified "Skeirik". Note that the examples of FIGS. 11, 12, and 13 show corresponding entries in this field.) This field facilitates use of the organization described in environments where multiple users are defining blocks which run within the same supervisor procedure.
Of course, in multi-user environments it may be desirable to allow some users a greater degree of access than others. Thus, for example, some users may be authorized to edit a block, while others may be authorized to toggle the block on or off but not to edit it, and others may be authorized to monitor block operation but not authorized to change it. Similarly, access to expert systems may be constrained by giving greater authorization to some users than to others; some users may be permitted to make calls to the expert system but not to edit the rulebase, and other users may not be permitted to do either. In the presently preferred embodiment, all of these choices can readily be implemented by using the file ownership and access control list options available in the VMS operating systems, but of course this functionality could be implemented in many other ways instead.
Action Logging
The supervisor procedure provides a means of reporting control actions and/or logging them in a file for recall. Control action messages are written by a user routine. Control blocks call user routines after their control actions are complete, and pass data regarding their actions. The action log file field allows the user to enter the name of the file to which logging messages will be written. The same log file can be used for more than one block (e.g. if the two blocks' actions are part of the same control application). (For example, note that field 1018 in the example of FIG. 10 and field 1118 in the example of FIG. 11 both specify "MFBCONTROL" as the action logging file.) The log file name is limited to letter and number characters, and no spaces are allowed (except after the end of the name).
Block Status
Note that, in the example of FIG. 10, a block status of "On-selected" is displayed in area 1020. This is not a field into which the user can directly enter data, but it will change in response to user actions (e.g. the user can toggle the block on or off by hitting keypad 7). The block status codes used in the presently preferred embodiment reflect several aspects of block setup and execution, including:
Proper configuration of block parameters;
On/off status of block;
Failure of block actions; and
Failure of user routines.
Some common block status values are:
"Inactive:" this indicates that the block has not been properly configured and toggled on, or that a parameter was changed. This is also the normal "off" status of a block which has been configured to switch on and off with a switch system variable, if the user toggles it off from the setup form.
"On:" this is the normal status for blocks which are performing their control actions.
"Off:" this is the normal status, for a block which has been configured to switch on and off with a switch system variable, when that variable is in its off state. This is also the normal status for blocks which are configured to switch on and off through the setup form only and have been toggled off from the setup form.
"Active:" this is the status to which a block is toggled on if it is configured to switch on and off with a switch system variable. This status will change on the next cycle of the control program, to "On" or to another value, depending on the state of the switch system variable.
"Toggled on:" this is the status to which a block is toggled on if it is configured to switch on and off through the setup form only. This status will change on the next cycle of the control program.
"Just turned on:" this is a normal transition state for blocks going from an "off" status (eg: off, inactive) to "On" status. Blocks whose status is "Just turned on" will be initialized by the base cycle procedure, which resets the last execution time and the measured variable and key block times used for block timing. Feedforward blocks initialize the "old" measured variable value to the current value.
"On-selected": indicates that a block which is on has been selected by a programmatic request. The block continues to function as if it were On.
"On-deselected": indicates that a block which is on has been de-selected by a programmatic request. The block takes no control actions, but continues to maintain its internal parameters as if it were On. This keeps the block ready to act if selected.
"On-holding": indicates that a block has been put on hold for a specified length of time by a programmatic request. The block takes no control action. A block that has been holding will re-initialize and go back to "On" status when the holding period expires.
"On-Failed usr routin:" this status indicates that a user routine called by this block had a fatal error which was bypassed by the supervisor procedure on the most recent execution of the block. Fatal errors in user routines are reported in the control program log file (not the same as action log files), and can be reviewed using the "List log file" option on the System Functions screen, described in the section on block monitoring.
"On-Recovrd usr Error:" this indicates that a fatal error was bypassed in the user routine, but that the user routine ran successfully on a later execution. Again, the log file will give more details about what happened.
"On-Err . . . :" many abnormal status values can indicate that problems were encountered in block execution, e.g. problems in the input or output of data to control systems. The latter part of the status field gives some indication of the problem. Most such errors are also recorded in the control program log file.
Various other block status values can readily be inserted, along the lines demonstrated by these examples.
Feedback Blocks
FIG. 10 shows a sample of a template 812 presented to the user to define a feedback block. In the specific example shown, the block being worked on is block number three of the 200 available blocks 851, 852, etc., and the various data values shown in this Figure reflect the entries which have been made at some time to define this particular block.
The feedback block provides proportional feedback action. In feedback action, the user specifies a measured value (called the "measured variable") and a goal value (setpoint) at which he wants to maintain it. Feedback action calculates the "error" in the measured variable (measured variable value-goal), and computes its action by multiplying the error times the "proportional gain". The current value of the "manipulated variable" is changed by the amount of the calculated action.
The basic feedback action can be altered by several additional parameters. A deadband around the goal can be specified. If the measured value falls within plus or minus the deadband of goal, no action is taken. The amount of action taken can be limited to a fixed amount. The range over which the value of the manipulated variable can be changed can be limited to keep it within operable limits. Screening limits can be specified on the measured variable value, in which case measured values outside the screening limits will be ignored. Block timing and switching and the block description fields follow the general outlines given above.
Specifying a feedback block on the block setup selection form (FIG. 9) brings up a feedback block setup form, as shown in FIG. 10.
Parameters
The parameters which the user is asked to specify include:
Measured variable type: a number code representing the software system and the type of entity which the block should use for the measured variable. (A sample response might be a number code indicating a Historical database variable.)
Measured variable number: the number of the entity within the specified system which the block will use for the measured variable. For example, if the measured variable type is a historical database variable, the measured variable number is the number of the variable in the historical database. After the measured variable type is entered, the label next to this field will show what type of data is needed. When the measured variable number is entered, other fields will also be filled in: the name and units for the measured variable, deadband and goal; units and default values for the max and min measured values. If block timing is to key off entry of new data into the measured variable, only discretely sampled variable types can be used.
Goal: the value at which the measured variable is to be "held". The value is entered in entered in the units of the measured variable.
Manipulated variable type: a number code representing the "target system" -- the software package and the type of entity which the block should manipulate. Examples are: control system loop goal, historical database variable, a setpoint in a distributed control system, or a setpoint for a programmable loop controller.
Manipulated variable number: the number of the entity within the target system which the block will manipulate. For example, if the manipulated variable type is a control system loop goal, the manipulated variable number would be the number of the loop whose goal is to be changed. The label next to this field will show what type of information is needed; in this case the label would show "Cont Sys loop #".
Proportional gain: the constant relating the change in the manipulated variable to the error. The units of the gain are shown to the right of the field after the measured and manipulated variable have been specified. Control action is calculated:
Error=[Measured variable value-goal value]
Manipulated delta=Error*[Proportional gain]
The manipulated delta is added (subject to limits) to the current value of the manipulated variable.
Deadband: A range around goal value. If the value of the measured variable falls within a range defined by the goal plus or minus the deadband, no action is taken.
Timing option, execution time interval, and Key block number: these parameters are those described above.
External switch system and switch number: these parameters are described above.
Maximum manip delta: the maximum change that can be made in the manipulated variable's value in one control action.
Minimum and maximum value of the manipulated variable: limit values outside which control action will not move the value of the manipulated variable. If a computer control action would put the manipulated value outside the limits, the value is set equal to the limit. If the manipulated value is moved outside the limits (by operator action, for example) the next control action will return the value to within the limits.
Minimum and maximum value of measured variable: Screening limits for reasonable values of the measured variable. Any time the measured variable value falls outside these limits, the value will be ignored and no action is taken.
Action log file: this specifies the name of the log file for action logging.
Feedback Block Operation
The sequence of actions performed by each feedback block, when executed by the base cycle routine, is:
If block status is "On-deselected", do no further actions;
Get the current value of the measured variable (If not accessible, set status to "On-err . . ." and do no further actions);
Get the current time stamp of the measured variable;
Test the value of the measured variable. If it is outside the minimum and maximum allowed values, set status to "On-msrd out of lims" and do no further actions.
Get the current value of the manipulated variable. If not accessible, set status to "On-err . . . " and do no further actions.
Compute the error (=Measured value-Goal).
If absolute value is less than the deadband, do no further actions.
Compute the change in the manipulated variable:
Delta.sub.-- manip=Error * proportional Gain
If the absolute delta is greater that the maximum allowed delta, set it equal to the maximum (maintaining proper sign).
Compute the new value of the manipulated variable:
New manip value=Current manip value+delta.sub.-- manip
If the value is outside the max/min limits, set it equal to the nearest limit. If limited, recompute the delta using the limit.
Change the manipulated variable value to the new value computed. If not accessible, change status to "On-err . . . " and do no further actions.
Load user array values for use by the user routine.
If delta -- manip is not zero, update the past action values and times.
Call the user routine.
Data passed to the user routine
In the presently preferred embodiment, each feedback block is able to pass information about its actions to the user routine, by using a commonly accessible memory block named "User -- vars." (The use of this data by the user routines is described in more detail below.) The data passed by the feedback block may include:
"User -- integer(1)" - the time stamp of the measured variable (from the database);
"User -- integer(2)" - the time the action was taken;
"User -- real(1)" - the change in the value of the manipulated variable;
"User -- real(2)" - the computed error; and
"User -- character(1)" - a string (alphanumeric) sequence which describes the block type; for feedback blocks this is set to be =`Feedback`.
Sample Source Code
The source code for the procedure which actually performs this function, in the presently preferred embodiment, is as follows.
TABLE 2__________________________________________________________________________C***********************************C Feedback.sub.-- block.forCC ACS subroutine to do feedback action on the Vax, communicatingC directly with the target system.CCC***********************************C Subroutine Feedback.sub.-- block ( Block )C Include `ACS$includes:Block.sub.-- parameters.inc/nolist` Include `ACS$includes:Van.sub.-- functions.inc/nolist` Include `ACS$includes:User.sub.-- vars.inc/nolist` Include `ACS$includes:ACSstatus.inc/nolist` Include `ACS$includes:ACSserv.inc` Include `Acs$includes:TIserv.inc` Include `Acs$includes:TIstatus.inc` Include `ACS$includes:Manip.sub.-- params.inc` Include `ACS$includes:Meas.sub.-- params.inc`CC Integer*2 Meas.sub.-- var.sub.-- system Integer*2 Meas.sub.-- var.sub.-- number Integer*2 Manip.sub.-- var.sub.-- system Integer*2 Manip.sub.-- var.sub.-- number Integer*4 Block Integer*4 Measured.sub.-- time.sub.-- stamp Integer*4 Integer.sub.-- Now Character*20 now.sub.-- time Real*4 Measured.sub.-- value Real*4 Current.sub.-- manipulated.sub.-- value Real*4 New.sub.-- manipulated.sub.-- valueCC Special handling for `On-deselected` status - do nothingC If ( Block.sub.-- status(Block)(1:13) .eq. `On-deselected`) ThenReturn End IfC ACS.sub.-- status = ACS.sub.-- get.sub.-- meas.sub.-- var.sub.-- type ( Block , MEAS.sub.-- VAR.sub.-- system ) Manip.sub.-- var.sub.-- system = Manipulated.sub.-- variable(Block) Manip.sub.-- var.sub.-- number = New.sub.-- manipulated.sub.-- variable(Block)D Write(6,*) ` Calling new.sub.-- feedback - block = `,blockCC Get the measured valueC Van.sub.-- status = Vss$.sub.-- from.sub.-- ascii.sub.-- time ( ` ` , Integer.sub.-- now ) van.sub.-- status = Vss$.sub.-- to.sub.-- ascii.sub.-- time( Integer.sub.-- now , now.sub.-- time )CC Measured Value is TPA PCS loop goalC If ( Meas.sub.-- var.sub.-- system .eq. PCS.sub.-- TPA.sub.-- Loop.sub.-- goal ) ThenACS.sub.-- status = ACS.sub.-- get.sub.-- pcs.sub.-- goal( `TPA ` , 1 Measured.sub.-- variable(Block) , Measured.sub.-- value )If ( ACS.sub.-- Status .ne. %loc(ACS.sub.-- success) ) ThenC If PCS goal value not available, don't execute Block.sub.-- status(Block) = `On-Err-PCS goal get`Write( 6, *) `Feedback exit due to measured var not availawrite(6,*)` ACS Block: `,block,` at: ',now.sub.-- time ReturnEnd IfCC Measured Value is DMT PCS loop goalC Else If ( MEAS.sub.-- var.sub.-- system .eq. PCS.sub.-- DMT.sub.-- loop.sub.-- goal ) ThenACS.sub.-- status = ACS.sub.-- get.sub.-- pcs.sub.-- goal( `DMT ` , 1 Measured.sub.-- variable(Block) , Measured.sub.-- value )If ( ACS.sub.-- Status .ne. %loc(ACS.sub.-- success) ) ThenC If PCS goal value not available, don't execute Block.sub.-- status(Block) = `On-Err-PCS goal get`Write( 6, *) `Feedback exit due to measured var not availawrite(6,*)` ACS Block: `,block,` at: `,now.sub.-- time ReturnEnd IfCC Measured Value is ACS block goalC Else If ( MEAS.sub.-- var.sub.-- system .eq. ACS.sub.-- block.sub.-- goal ) ThenACS.sub.-- status = ACS.sub.-- get.sub.-- goal ( 1 Measured.sub.-- variable(Block) , Measured.sub.-- value )If ( ACS.sub.-- Status .ne. %loc(ACS.sub.-- success) ) ThenC If ACS goal Value not available, don't execute Block.sub.-- status(Block) = `On-Err-ACS goal get`Write( 6, *) `Feedback exit due to measured var not availawrite(6,*)` ACS Block: `,block,` at: `,now.sub.-- time ReturnEnd IfCC Measured Value is Vantage variableC Else If ( Meas.sub.-- var.sub.-- system .eq. cur.sub.-- val.sub.-- Van.sub.-- var ) ThenVan.sub.-- Status = Vss$g.sub.-- current( Measured.sub.-- variable(Bl ock) , 1 Measured.sub.-- value )If ( Van.sub.-- Status .ne. %loc(vss.sub.-- normal) ) ThenC If Variable Value not available, don't execute Block.sub.-- status(Block) = `On-Failed Msrd var ` Write( 6, *) `Feedback exit due to measured var not availa write(6,*)` ACS Block: `,block,` at: `,now.sub.-- time ReturnEnd IfC end if Van.sub.-- status = Vss$g.sub.-- curtime ( Measured.sub.-- variable(Bl ock) ,1 Measured.sub.-- time.sub.-- stamp )CC Check the Measured variable to see if it is within limitsC If ( (Measured.sub.-- value .lt. Measured.sub.-- min(block) ) .or. 1 (Measured.sub.-- value .gt. Measured.sub.-- max(block) ) ) ThenC Reject the data point Write( 6, *) `Feedback exit due to out of limts measured` write(6,*)` ACS Block: `,block,` at: `,now.sub.-- time Block.sub.-- status(Block) = `On-Msrd out of lims ` ReturnEnd ifCCC Get the current manipulated valueCCCC Target is TPA PCS loop goalC If ( Manip.sub.-- var.sub.-- system .eq. PCS.sub.-- TPA.sub.-- Loop ) ThenACS.sub.-- status = ACS.sub.-- get.sub.-- pcs.sub.-- goal( `TPA ` , 1 Manip.sub.-- var.sub.-- number , Current.sub.-- manipulated.sub.-- value , )If ( ACS.sub.-- Status .ne. %loc(ACS.sub.-- success) ) ThenC If PCS goal value not available, don' t execute Block.sub.-- status(Block) = `On-Err-PCS goal get` ReturnEnd IfCC Target is DMT PCS loop goalC Else If ( Manip.sub.-- var.sub.-- system .eq. PCS.sub.-- DMT.sub.-- loop ) ThenACS.sub.-- status = ACS.sub.-- get.sub.-- pcs.sub.-- goal( `DMT ` , 1 Manip.sub.-- var.sub.-- number , Current.sub.-- manipulated.sub.-- value )If ( ACS.sub.-- Status .ne. %loc(ACS.sub.-- success) ) ThenC If PCS goal value not available, don't execute Block.sub.-- status(Block) = `On-Err-PCS goal get` ReturnEnd IfCC Target is ACS block goalC Else If ( Manip.sub.-- var.sub.-- system .eq. ACS.sub.-- block ) ThenACS.sub.-- status = ACS.sub.-- get.sub.-- goal ( Manip.sub.-- var.sub.-- number ,1 Current.sub. -- manipulated.sub.-- value ) If ( ACS.sub.-- Status .ne. %loc(ACS.sub.-- success) ) ThenC If ACS goal Value not available, don't execute Block.sub.-- status(Block) = `On-Err-ACS goal get` ReturnEnd IfCC Target is Vantage variableC Else If ( Manip.sub.-- var.sub.-- system .eq.1 Vantage.sub.-- variable ) ThenVan.sub.-- Status = Geteuval ( Manip.sub.-- var.sub.-- number ,1 Current.sub.-- manipulated.sub.-- value )If ( Van.sub.-- Status .ne. %loc(vss.sub.-- success) ) ThenC If Variable Value not available, don't execute Block.sub.-- status(Block) = `On-Err-Vant var get ` ReturnEnd IfCC Target is Texas Instruments PM550 controller setpoint in CRDC Else If ( ( Manip.sub.-- var.sub.-- system .ge. Low.sub.-- PM550 ) .and.1 ( Manip.sub.-- var.sub.-- system .le. Hi.sub.-- PM550 ) ) ThenC If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.-- PM550.sub.-- 01 ) ThenACS.sub.-- status = TI.sub.-- get.sub.-- loop.sub.-- setpoint ( `TI.sub.-- PM550.sub.-- 01.sub.-- PORT` ,1 Manip.sub.-- var.sub.-- number , Current.sub.-- manipulated.sub.--value ) Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 02 ) Then ACS.sub.-- status = TI.sub.-- get.sub.-- loop.sub.-- setpoint (`TI.sub.-- PM550.sub.-- 02.sub.-- PORT` ,1 Manip.sub.-- var.sub.-- number , Current.sub.-- manipulated.sub.--value ) Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 03 ) Then ACS.sub.-- status = TI.sub.-- get.sub.-- loop.sub.-- setpoint (`TI.sub.-- PM550.sub.-- 03.sub.-- PORT` ,1 Manip.sub.-- var.sub.-- number , Current.sub.-- manipulated.sub.--value ) Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 04 ) Then ACS.sub.-- status = TI.sub.-- get.sub.-- loop.sub.-- setpoint (`TI.sub.-- PM550.sub.-- 04.sub.-- PORT` ,1 Manip.sub.-- var.sub.-- number , Current.sub.-- manipulated.sub.--value ) Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 05 ) Then ACS.sub.-- status = TI.sub.-- get.sub.-- loop.sub.-- setpoint (`TI.sub.-- PM550.sub.-- 05.sub.-- PORT` ,1 Manip.sub.-- var.sub.-- number , Current.sub.-- manipulated.sub.--value ) Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub. --PM550.sub.-- 06) Then ACS.sub.-- status = TI.sub.-- get.sub.-- loop.sub.-- setpoint (`TI.sub.-- PM550.sub.-- 06.sub.-- PORT` ,1 Manip.sub.-- var.sub.-- number , Current.sub.-- manipulated.sub.--value ) Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 07) Then ACS.sub.-- status = TI.sub.-- get.sub.-- loop.sub.-- setpoint (`TI.sub.-- PM550.sub.-- 07.sub.-- PORT` ,1 Manip.sub.-- var.sub.-- number , Current.sub.-- manipulated.sub.--value ) End If If ( ACS.sub.-- Status .ne. %loc(TI.sub.-- success) ) ThenC If PM550 setpoint value not available, don't execute Block.sub.-- status(Block) = `On-Err-TI setpnt get` Write( 6, *)1 ` Feedback exit - TI PM550 Manip var not gettable.` Write (6, *) ` ACS Block: ` ,block,` at `,now.sub.-- time Return End IfElse ! Other Manip device typeEnd IfCC Value is within limits - Test to see if the error is less th deadbandC Error = Measured.sub.-- value - Goal(Block) If ( Abs(Error) .lt. Absolute.sub.-- deadband(Block) ) Thend Write( 6, *) `Feedback error less than deadband`Return End IfCC Compute proportional Feedback Response-Test Delta to see if tooC Delta = Error * Proportional.sub.-- gain(Block) If ( Abs(Delta) .gt. Max.sub.-- manip.sub.-- delta(Block) ) Then Delta = Sign(Max.sub.-- manip.sub.-- delta(Block),Delta) End IfCC Calculate new manipulated value, check to see it within limitsC New.sub.-- manipulated.sub.-- value = Current.sub.-- manipulated.sub.- - value + DeltaC If ( New.sub.-- manipulated.sub.-- value .gt. Manipulated.sub.-- max(Block) ) ThenNew.sub.-- manipulated.sub.-- value = Manipulated.sub.-- max(Block) Else If ( New.sub.-- manipulated.sub.-- value .lt. Manipulated.sub.-- min(Block) )New.sub.-- manipulated.sub.-- value = Manipulated.sub.-- min(Block) End If Delta = New.sub.-- manipulated.sub.-- value - Current.sub.-- manipulat ed.sub.-- valueCC Transmit the new Manipulated Value to the manip variableCC Target is TPA PCS loop goalC If ( Manip.sub.-- var.sub.-- system .eq. PCS.sub.-- TPA.sub.-- Loop ) ThenACS.sub.-- status = ACS.sub.-- put.sub.-- pcs.sub.-- goal( `TPA ` , 1 Manip.sub.-- var.sub.-- number , New.sub.-- manipulated.sub.-- value )If ( ACS.sub.-- Status .ne. %loc(ACS.sub.-- success) ) ThenC If PCS goal value not available, don't execute Block.sub.-- status(Block) = `On-Err-PCS goal put` Write( 6, *) `Feedback exit due to failed manip var put. Write(6,*)` ACS Block: `,block,` at: `,now.sub.-- time ReturnEnd IfCC Target is DMT PCS loop goalC Else If ( Manip.sub.-- var.sub.-- system .eq. PCS.sub.-- DMT.sub.-- loop ) ThenACS.sub.-- status = ACS.sub.-- put.sub.-- pcs.sub.-- goal( `DMT ` , 1 Manip.sub.-- var.sub.-- number , New.sub.-- manipulated.sub.-- value )If ( ACS.sub.-- Status .ne. %loc(ACS.sub.-- success) ) ThenC If PCS goal value not available, don't execute Block.sub.-- status(Block) = `On-Err-PCS goal put` Write( 6, *) `Feedback exit due to failed manip var put. Write(6,*)` ACS Block: `,block,` at: ',now.sub.-- time ReturnEnd IfCC Target is ACS block goalC Else If ( Manip.sub.-- var.sub.-- system .eq. ACS.sub.-- block ) ThenACS.sub.-- status = ACS.sub.-- put.sub.-- goal ( Manip.sub.-- var.sub.-- number ,1 New.sub.-- manipulated.sub.-- value )If ( ACS.sub.-- Status .ne. %loc(ACS.sub.-- success) ) ThenC If ACS goal Value not available, don't execute Block.sub.-- status(Block) = `On-Err-ACS goal put` Write( 6, *) `Feedback exit due to failed manip var put. Write(6,*)` ACS Block: `,block,` at: ',now.sub.-- time ReturnEnd IfCC Target is Vantage variableCElse If ( Manip.sub.-- var.sub.-- system .eq.1 Vantage variable ) ThenVan.sub.-- status = Puteugen ( Manip.sub.-- var.sub.-- number ,1 New.sub.-- manipulated.sub.-- value )If ( Van.sub.-- Status .ne. %loc(vss.sub.-- success) ) ThenC If variable Value not available, don't execute Block.sub.-- status(Block) = `On-Err-Vant var put ` Write( 6, *) `Feedback exit due to failed manip var put. Write(6,*)` ACS Block: `,block,` at: ',now.sub.-- time ReturnEnd IfCC Target is Texas Instruments PM550 controller setpoint in CRDC Else If ( ( Manip.sub.-- var.sub.-- system .ge. Low.sub.-- PM550 ) .and. 1 ( Manip.sub.-- var.sub.-- system .le. Hi.sub.-- PM550 ) ) ThenCIf ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.-- PM550.sub.-- 01 ) Then ACS.sub.-- status = TI.sub.-- put.sub.-- loop.sub.-- setpoint ( `TI.sub.-- PM550.sub.-- 01.sub.-- PORT` , 1 Manip.sub.-- var.sub.-- number , New.sub.-- manipulated.sub.-- value )Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 02 ) Then ACS.sub.-- status = TI.sub.-- put.sub.-- loop.sub.-- setpoint ( `TI.sub.-- PM550.sub.-- 02.sub.-- PORT` , 1 Manip.sub.-- var.sub.-- number , New.sub.-- manipulated.sub.-- value )Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 03 ) Then ACS.sub.-- status = TI.sub.-- put.sub.-- loop.sub.-- setpoint ( `TI.sub.-- PM550.sub.-- 03.sub.-- PORT` , 1 Manip.sub.-- var.sub.-- number , New.sub.-- manipulated.sub.-- value )Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 04 ) Then ACS.sub.-- status = TI.sub.-- put.sub.-- loop.sub.-- setpoint ( `TI.sub.-- PM550.sub.-- 04.sub.-- PORT` , l Manip.sub.-- var.sub.-- number , New.sub.-- manipulated.sub.-- value )Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 05 ) Then ACS.sub.-- status = TI.sub.-- put.sub.-- loop.sub.-- setpoint ( `TI.sub.-- PM550.sub.-- 05.sub.-- PORT` , 1 Manip.sub.-- var.sub.-- number , New.sub.-- manipulated.sub.-- value )Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 06) Then ACS.sub.-- status = TI.sub.-- put.sub.-- loop.sub.-- setpoint ( `TI.sub.-- PM550.sub.-- 06.sub.-- PORT` , 1 Manip.sub.-- var.sub.-- number , New.sub.-- manipulated.sub.-- value )Else If ( Manip.sub.-- var.sub.-- system .eq. CRD.sub.-- ESCHS.sub.--PM550.sub.-- 07) Then ACS.sub.-- status = TI.sub.-- put.sub.-- loop.sub.-- setpoint ( `TI.sub.-- PM550.sub.-- 07.sub.-- PORT` , 1 Manip.sub.-- var.sub.-- number , New.sub.-- manipulated.sub.-- value )End IfIf ( ( ACS.sub.-- Status .ne. %loc(TI.sub.-- success) .and. 1 ( ACS.sub.-- status .ne. %loc(TI.sub.-- clamped) ) ThenC If PM550 setpoint value not accessible, dont execute Block.sub.-- status(Block) = `On-Err-TI setpnt put` Write( 6, *) ' Feedback exit - TI PM550 Manip V puttable.' Write (6, *) ` ACS Block: `,block,` at: `,now.sub.-- time ReturnEnd IfElse ! Other manip device typesEnd IfCC Load special arrays for user programs to log messages.C User.sub.-- integer(1) = Measured.sub.-- time.sub.-- stamp User.sub.-- integer(2) = Integer.sub.-- now User.sub.-- real(1) = Delta User.sub.-- real(2) = Error User.sub.-- character(1) = `Feedback `CC If Delta is non-zero, update past actionsC If ( Delta .ne. 0 ) ThenDo 90 J = 5,2,-1 Past.sub.-- action.sub.-- value(Block,J) = Past.sub.-- action.sub.--value(Block,J-1)90 Past.sub.-- action.sub.-- time (Block,J) = Past.sub.-- action.sub.-- time (Block,J-1)Past.sub.-- action.sub.-- value(Block,1) = DeltaPast.sub.-- action.sub.-- time (Block,1) = Integer.sub.-- nowEnd IfCC Call User subprograms for this blockC Call User.sub.-- programs(Block)CC All doneC Return End__________________________________________________________________________
Copyright (c) 1987 E.I. duPont de Nemours & Co., all rights reserved.
Feedforward Block
FIG. 11 shows a sample of a template 812 presented to the user by the build-supervisor procedure to define a feed forward block. In the specific example shown, the block being worked on is block number six of the 200 available blocks 851, 852, etc., and the various data values shown in this Figure reflect the entries which have been made at some time to define this particular block.
The feedforward block provides proportional feedforward action. In feedforward action, the user specifies a measured value (called the "measured variable") and a manipulated variable whose value is to be changed in proportion to (or, more generally, in accordance with) the change in value of the measured variable. Feedforward action begins when the "old measured value" is set equal to a current value (usually when the block is first turned on). The measured variable is then monitored for changes in value and the manipulated variable value is changed in proportion. The "old measured value" is then updated to the value at the time of this action. (The use of the "old measured value" in feedforward rules is one reason why an initialization stage is needed: if a feedforward block were switched from inactive status directly to on status, it might indicate a very large change to the manipulated variable if the delta were calculated from an out-of-date "old measured value.")
In the presently preferred embodiment, the basic feedforward action can be altered by several additional parameters. A deadband can be specified, so that, if the measured value changes by less than the deadband, no action is taken. The amount of action taken can be limited to a fixed amount. The range over which the value of the manipulated variable can be changed can be limited to keep it within operable limits. Screening limits can be specified on the measured variable value, so that measured values outside the screening limits are ignored. Block timing and switching options and the block description fields follow the general outlines given above.
In the presently preferred embodiment, specifying a feedforward block on the block setup selection form (FIG. 9) brings up a feedforward block setup form like that shown in FIG. 11.
Parameters
The parameters are:
Measured variable type: a number code representing the software system and the type of entity which the block should use for the measured variable.
Measured variable number: the number of the entity within the specified system which the block will use for the measured variable. For example, if the measured variable type is a historical database variable, the measured variable number is the number of the variable in the historical database. After the measured variable type is entered, the label next to this field will show what type of data is needed. When the measured variable number is entered, other fields will also be filled in: the name and units for the measured variable, deadband; units and default values for the max and min measured values. If block timing to key off entry of new data into the measured variable, only discretely sampled variable types can be used.
Goal: the goal field cannot be used for feedforward blocks.
Manipulated variable type: a number code representing the software package and the type of entity which the block should manipulate. Examples are: control system loop goal, historical database variable.
Manipulated variable number: the number of the entity within the specified system which the block will manipulate. For example, if the manipulated variable type is a control system loop goal, the manipulated variable number would be the number of the loop whose goal is to be changed. The label next to this field will show what type of information is needed; in this case the label would show "Cont Sys loop #".
Proportional gain: the constant relating the change in the manipulated variable's value to the change in the measured variable's value. The units of the gain are shown to the right of the field after the measured and manipulated variable have been specified. Control action is calculated as:
Measured delta=[Measured variable value-Old value]
Manipulated delta=Measured delta*[Proportional gain]
The manipulated delta is added (subject to limits) to the current value of the manipulated variable.
Deadband: A range around the "old measured value" (i.e. the measured value at the time of the last block action). If the value of the measured variable is within plus or minus the deadband of the old measured value, no action is taken and the old measured value is not changed.
Timing option, execution time interval, and Key block number: these parameters are described above.
Switch system and switch number: these are described above.
Maximum output delta: the maximum change that can be made in the manipulated variable's value in one control action.
Minimum and maximum value of the manipulated variable: limit values outside which control action will not move the value of the manipulated variable. If a computer control action would put the manipulated value outside the limits, the value is set equal to the limit. If the manipulated value is moved outside the limits (by operator action, for example) the next control action will return the value to within the limits.
Minimum and maximum value of measured variable: These define screening limits for reasonable values of the measured variable. Whenever the measured variable value falls outside these limits, the value will be ignored and no action is taken.
Action log file: this field is described above.
The use of a deadband in feedforward blocks is one of the features which tend to force process control into discrete steps, rather than continuous small changes. One advantage of this novel teaching is that full logging can be used: every single change made by the supervisor procedure can be logged, without generating an excessive number of messages. This in turn means that monitoring, diagnosis, and analysis of processes (and of process control systems) becomes much easier.
Block Operation
The sequence of actions performed by a feedforward block is:
Get the current value of the measured variable (If not accessible, set status to "On-err . . . " and do no further actions);
Test the value of the measured variable. If it falls outside the allowed range of values, set status to "On-msrd out of lims" and do no further actions.
Compute the change in the value of the measured variable: Delta measured=Measured value-Old measured value. If the absolute value of the change is less than the deadband, do no further actions.
Compute the change in the manipulated variable:
Delta.sub.-- =Delta measured*Proportional gain.
Set "old measured value" equal to the current value of the measured variable.
If block status is "On-deselected", do no further actions;
Check the magnitude of the manipulated value delta. If greater than the maximum allowed delta, set magnitude equal to the maximum.
Get the current value of the manipulated variable. If not accessible, set status to "On-err . . . " and do no further actions.
Compute the new value of the manipulated variable:
New manip value=Current manip value+delta.sub.-- manip.
If the value is outside the max/min limits, set it equal to the nearest limit. If limited, recompute the delta using the limit.
Change the manipulated variable value to the new value computed. If not accessible, change status to "On-err . . . " and do no further actions.
Load user array values for use by the user routine.
If delta -- manip is not zero, update the past action values and times.
Call the user routine.
Data passed to the user routine
The feedforward block passes information about its actions to the user routine through the User vars common block. The use of this data is described in more detail in the chapter covering User routines. In the presently preferred embodiment, the data passed by the feedforward block includes:
User -- integer(1) - the time stamp of the measured variable;
User -- integer(2) - the time the action was taken;
User -- real(1) - the change in the value of the manip variable;
User -- real(2) - the change in the value of the measured variable from the last time the "old measured value" was updated;
User -- character(1) -=`Feedforward`.
Sample Source Code
The source code for the procedure which actually performs this function, in the presently preferred embodiment, is as follows.
TABLE 3__________________________________________________________________________C************************************C FEEDFORWARD --block.FORCC Subroutine to do feedforward calculations on the Vax,C communicating directly with the target system.CCCC************************************C Subroutine Feedforward --block ( Block )C Include `ACS$includes:Block --parameters.inc/nolist` Include `ACS$includes:Van --functions.inc/nolist` Include `ACS$includes:User --vars.inc/nolist` Include `ACS$includes:ACSstatus.inc/nolist` Include `ACS$includes:ACSserv.inc` Include `Acs$includes:TIserv.inc` Include `Acs$includes:TIstatus.inc` Include `ACS$includes:Manip --params.inc` Include `ACS$includes:Meas --params.inc`C Integer*2 Manip --var --type Integer*2 Manip --var --num Integer*2 Meas --var --type Integer*2 Meas --var --num Integer*4 Block Real*4 Measured --value Real*4 Current --manipulated --value Real*4 New --manipulated --value Integer*4 Integer --Now Character*20 Character --now Integer*4 Measured --time --stampCVan --status = Vss$ --from --ascii --time ( ` ` , Integer --now )Van --status = Vss$ --to --ascii --time( Integer --now , Character --now)CC . . . Get the measured valueCACS --status = ACS --get --meas --var --type ( Block , Meas --var --type)ACS --status = ACS --get --meas --var --num ( Block , Meas --var --num )Measured --time --stamp = 0CC . . . Measured Value is TPA PCS loop goalC If ( Meas --var --type .eq. PCS --TPA --Loop --goal ) ThenACS --status = ACS --get --pcs --goal( `TPA ` , 1 Meas --var --num , Measured --value )If ( ACS --Status .ne. %loc(ACS --success) ) ThenC . . . If PCS goal value not available, don't execute Block --status(Block) = `On-Err-PCS goal get` Write( 6, *) `Feedback exit due to measured var not availa write(6,*)` ACS Block: `,block,` at: `,Character --now ReturnEnd IfCC . . . Measured Value is DMT PCS loop goalC Else If ( Meas --var --type .eq. PCS --DMT --loop --goal ) ThenACS --status = ACS --get --pcs --goal( `DMT `, 1 Meas --var --num , Measured --value )If ( ACS --Status .ne. %loc(ACS --success) ) ThenC . . . If PCS goal value not available, don't execute Block --status(Block) = `On-Err-PCS goal get`Write( 6, *) `Feedback exit due to measured var not availawrite(6,*)`ACS Block: `,block,` at: `,Character --now Return End IfCC . . . Measured Value is ACS block goalC Else If ( Meas --var --type .eq. ACS --block --goal ) ThenACS --status = ACS --get --goal ( 1 Meas --var --num , Measured --value )If ( ACS --Status .ne. %loc(ACS --success) ) ThenC . . . If ACS goal Value not available, don't execute Block --status(Block) = `On-Err-ACS goal get` Write( 6, *) `Feedback exit due to measured var not avai write(6,*)` ACS Block: `,block,` at: `,Character --now ReturnEnd IfCC . . . Measured Value is Vantage variableC Else If ( Meas --var --type .eq. cur --val --Van --var ) ThenVan --Status = Vss$g --current( Meas --var --num , 1 Measured --value )If ( Van --Status .ne. %loc(vss --normal) ) ThenC . . . If Variable Value not available, don't execute Block --status(Block) = `On-Failed Msrd var ` Write( 6, *) `Feedback exit due to measured var not availa write(6,*) ` ACS Block: `,block,` at: `,Character --now ReturnEnd IfVan --status = Vss$g --curtime ( Meas --var --num , 1 Measured --time --stamp )C End IfCC . . . Check the Measured variable to see if it is within limitsC If ( (Measured --value .lt. Measured --min(block) ) .or. 1 (Measured --value .gt. Measured --max(block) ) ) ThenC . . . Reject the data pointReturn End ifCC . . . Test to see if the change in the measured value is less th deadbandC Delta --meas = Measured --value - Old --measured --value(Block) If ( Abs( Delta --meas ) .lt. 1 Absolute --deadband(Block) ) ThenReturn End IfCC . . . Special action for `On-deselected` status - update old --meas --valu exit.C Old --measured --value(Block) = Measured --value If ( Block --status(Block)(1:13) .eq. `On-deselected` ) ThenReturn End IfCC . . . Value is within limits - Compute Feedforward ResponseCDelta --manip = Delta --meas * Proportional --gain(Block)CC . . . Test Delta --manip to see if too greatCIf ( Abs(Delta --manip) .gt. Max --manip --delta(Block) ) Then Delta --manip = Sign(Max --manip --delta(Block),Delta --manip)End IfCC . . . Get the current manipulated valueCACS --status = ACS --get --manip --var --sys ( Block , Manip --var --type)ACS --status = ACS --get --manip --var --num ( Block , Manip --var --num)CC . . . Target is TPA PCS loop goalCIf ( Manip --var --type .eq. PCS --TPA --Loop ) Then ACS --status = ACS --get --pcs --goal( `TPA ` ,1 Manip --var --num , Current --manipulated --value , ) If ( ACS --Status .ne. %loc(ACS --success) ) ThenC . . . If PCS goal value not available, don't execute Block --status(Block) = `On-Err-PCS goal get` ReturnEnd IfCC . . . Target is DMT PCS loop goalCElse If ( Manip --var --type .eq. PCS --DMT --loop ) Then ACS --status = ACS --get --pcs --goal( `DMT ` ,1 Manip --var --num , Current --manipulated --value ) If ( ACS --Status .ne. %loc(ACS --success) ) ThenC . . . If PCS goal value not available, don't execute Block --status(Block) = `On-Err-PCS goal get` Return End IfCC . . . Target is ACS block goalCElse If ( Manip --var --type .eq. ACS --block ) Then ACS --status = ACS --get --goal ( Manip --var --num ,1 Current --manipulated --value ) If ( ACS --Status .ne. %loc(ACS --success) ) ThenC . . . If ACS goal Value not available, don't execute Block --status(Block) = `On-Err-ACS goal get` ReturnEnd IfCC . . . Target is Vantage variableC Else If ( Manip --var --type .eq. 1 Vantage --variable ) ThenVan --Status = Geteuval ( Manip --var --num , 1 Current --manipulated --value )If ( Van --Status .ne. %loc(vss --success) ) ThenC . . . If Variable Value not available, don't execute Block --status(Block) = `On-Err-Vant var get ` ReturnEnd IfCC . . . Target is Texas Instruments PM550 controller setpoint in CRDC Else If ( ( Manip --var --type .ge. Low --PM550 ) .and. 1 ( Manip --var --type .le. Hi --PM550 ) ) ThenCIf ( Manip --var --type .eq. CRD --ESCHS --PM550 --01 ) Then ACS --status = TI --get --loop --setpoint ( `TI --PM550 --01 --PORT` , 1 Manip --var --num , Current --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --02 ) Then ACS --status = TI --get -- loop --setpoint ( `TI --PM550 --02 --PORT` , 1 Manip --var --num , Current --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --03 ) Then ACS --status = TI --get --loop --setpoint ( `TI --PM550 --03 --PORT` , 1 Manip --var --num , Current --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --04 ) Then ACS --status = TI --get --loop --setpoint ( `TI --PM550 --04 --PORT` , 1 Manip --var --num , Current --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --05 ) Then ACS --status = TI --get --loop --setpoint ( `TI --PM550 --05 --PORT` , 1 Manip --var --num , Current --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --06) Then ACS --status = TI --get --loop --setpoint ( `TI --PM550 --06 --PORT` , 1 Manip --var --num , Current --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --07) Then ACS --status = TI --get --loop --setpoint ( `TI --PM550 --07 --PORT` , 1 Manip --var --num , Current --manipulated --value )End IfIf ( ACS --Status .ne. %loc(TI --success) ) ThenC . . . If PM550 setpoint value not available, don't execute Block --status(Block) = `On-Err-TI setpnt get` Write( 6, *) 1 `Feedforward exit - TI PM550 Manip var not accessible Write (6, *) ` ACS Block: `,block,` at: `,now --time ReturnEnd If Else ! Other Manip device type End IfCC . . . Calculate new manipulated value, check to see it within limitsC New --manipulated --value = Current --Manipulated --value + Delta --maniC If ( New --manipulated --value .gt. Manipulated --max(Block) ) ThenNew --manipulated --value = Manipulated -- max(Block) Else If ( New --manipulated --value .lt. Manipulated --min(Block) )New --manipulated --value = Manipulated --min(Block) End If Delta --manip = New --manipulated --value - Current --Manipulated --valuCC . . . Transmit the New Manipulated Value to the manipulated variableCC . . . Target is TPA PCS loop goalCIf ( Manip --var --type .eq. PCS --TPA --Loop ) Then ACS --status = ACS --put --pcs --goal( `TPA ` ,1 Manip --var --num , New --manipulated --value ) If ( ACS --Status .ne. %loc(ACS --success) ) ThenC . . . If PCS goal value not available, don't execute Block --status(Block) = `On-Err-PCS goal put` Write( 6, *) `Feedback exit due to failed manip var put. Write(6,*) ` ACS Block: `,block,` at: `,now --time ReturnEnd IfCC . . . Target is DMT PCS loop goalCElse If ( Manip --var --type .eq. PCS --DMT --loop ) Then ACS --status = ACS --put --pcs --goal( `DMT ` ,1 Manip --var --num , New --manipulated --value ) If ( ACS --Status .ne. %loc(ACS --success) ) ThenC . . . If PCS goal value not available, don't execute Block --status(Block) = `On-Err-PCS goal put` Write( 6, *) `Feedback exit due to failed manip var put. Write(6,*)` ACS Block: `,block,` at: `,now --time ReturnEnd IfCC . . . Target is ACS block goalCElse If ( Manip --var --type .eq. ACS --block ) Then ACS --status = ACS --put --goal ( Manip --var --num ,1 New --manipulated --value ) If ( ACS --Status .ne. %loc(ACS --success) ) ThenC . . . If ACS goal Value not available, don't execute Block --status(Block) = `On-Err-ACS goal put` Write( 6, *) `Feedback exit due to failed manip var put. Write(6,*)` ACS Block: `,block,` at: `,now time ReturnEnd IfCC . . . Target is Vantage variableCElse If ( Manip --var --type .eq.1 Vantage --variable ) Then Van --status = Puteugen ( Manip --var --num ,1 New --manipulated --value ) If ( Van --Status .ne. %loc(vss --success) ) ThenC . . . If Variable Value not available, don't execute Block --status(Block) = `On-Err-Vant var put ` Write( 6, *) `Feedback exit due to failed manip var put. Write(6,*)` ACS Block: `,block,` at: `,now --time ReturnEnd IfCC . . . Target is Texas Instruments PM550 controller setpoint in CRDC Else If ( ( Manip --var --type .ge. Low --PM550 ) .and. 1 ( Manip --var --type .le. Hi --PM550 ) ) ThenCIf ( Manip --var --type .eq. CRD --ESCHS --PM550 --01 ) Then ACS --status = TI --put --loop --setpoint ( `TI --PM550 --01 --PORT` , 1 Manip --var --num , New --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --02 ) Then ACS --status = TI --put --loop --setpoint ( `TI --PM550 --02 --PORT` , 1 Manip --var --num , New --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --03 ) Then ACS --status = TI --put --loop --setpoint ( `TI --PM550 --03 --PORT` , 1 Manip --var --num , New --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --04 ) Then ACS --status = TI --put --loop --setpoint ( `TI --PM550 --04 --PORT` , 1 Manip --var --num , New --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --05 ) Then ACS --status = TI --put --loop --setpoint ( `TI --PM550 --05 --PORT` , 1 Manip --var --num , New --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --06) Then ACS --status = TI --put --loop --setpoint ( `TI --PM550 --06 --PORT` , 1 Manip --var --num , New --manipulated --value )Else If ( Manip --var --type .eq. CRD --ESCHS --PM550 --07) Then ACS --status = TI --put -- loop --setpoint ( `TI --PM550 --07 --PORT` , 1 Manip --var --num , New --manipulated --value )End IfIf ( ACS --Status .ne. %loc(TI --success) ) ThenC . . . If PM550 setpoint value not available, don't execute Block --status(Block) = `On-Err-TI setpnt put` Write( 6, *)1 ` Feedforward exit - TI PM550 Manip var not puttable.`Write (6, *) ` ACS Block: `,block,` at: `,now --timeReturn End IfElse ! Other Manip device typeEnd IfCC . . . Load special arrays for user programs to log messages.CUser --integer(1) = Measured --time --stampUser --integer(2) = Integer --nowUser --real(1) = Delta --manipUser --real(2) = Delta --measUser --character(1) = `Feedforward `CC . . . If Delta is non-zero, update past actionsCIf ( Delta --manip .ne. 0 ) Then Do 90 J = 5,2,-1 Past --action --value(Block,J) = Past --action --value(Block,J-1)90 Past --action --time(Block,J) = Past --action --time (Block,J-1) Past --action --value(Block,l) = Delta --manip Past --action --time (Block,l) = Integer --nowEnd IfCC . . . Call User subprograms for this blockCCall User --programs(Block)ReturnEnd__________________________________________________________________________
Copyright (c) 1987 E.I. duPont de Nemours & Co., all rights reserved.
Statistical Filtering Blocks
FIG. 12 shows a sample of a template 812 presented to the user by the build-supervisor procedure to define a statistical filtering block. In the specific example shown, the block being worked on is block number one of the 200 available blocks 851, 852, etc., and the various data values shown in this Figure reflect the entries which have been made at some time to define this particular block.
The Shewhart block provides statistical filtering of a sampled measurement using Shewhart tests. The user specifies an aim value (field 1222 in FIG. 12) and a standard deviation (sigma) (field 1224 in FIG. 12) which characterizes the normal variability in the measurement. The Shewhart tests a series of rules to determine whether the sequence of measurements are statistically the same as ("on aim") or different from ("off aim") the normal variability with the average at the aim. After each test, the Shewhart block stores in the process database an estimate of the deviation from aim and a value indicating what rule was broken.
In the presently preferred embodiment, Shewhart blocks do not allow timing options to be specified. They perform their tests only when a new measurement is entered into the database for the filtered variable. In the presently preferred embodiment, the conditions tested for by the Shewhart block are:
Was the last point more than 3 sigma different from aim?
Were two of the last three points more than 2 sigma different from aim in the same direction?
Were four of the last five points more than 1 sigma different from aim in the same direction?
Were the last seven points all off aim on the same side of aim?
The rules are tested in the order shown. For the second and third rules, the test is first applied to the last two (or four) points in a row, then to the last three (or five) points. If any rule is violated, the process is off aim, and a deviation from aim is calculated by averaging the points which broke the rule. For example, if the last four points were outside the 1 sigma limit, the average of the four is taken as the deviation. If four of the last five points were outside the 1 sigma limits, the average of the last five points is taken.
The basic Shewhart action can be altered by several additional parameters. A fix time interval can be specified (in field 1226), so that, if one of the Shewhart tests shows a rule violation, Shewhart tests will be suspended for this interval after the time of the sample that violated the rule. This is useful in process control to allow control action in response to a rule violation to have time to move the process back to a statistically "on aim" position before taking any further actions. The range of calculated deviations can be limited, as specified by the data entered into fields 1228 and 1230. Screening limits can be applied to the filtered variable, so that measurements falling outside the range defined in fields 1232 and 1234 are ignored.
The Shewhart block differs from the feedback and feedforward blocks in that it requires resources outside of the supervisor procedure. It uses two process database variables to store its computed deviation from aim and its rule value. To configure a Shewhart block, in this sample embodiment, the user must get database variables allocated and properly configured. Since this is usually a database system manger's function, the details are not covered here.
Specifying a "Shewhart" (i.e. statistical filtering) block on the block setup selection form (FIG. 9) brings up the Shewhart block setup form shown in FIG. 12.
Parameters
The parameters shown on this form include:
Filtered variable type: a number code representing the software system and the type of entity which the block should use for the filtered variable.
Filtered variable number: the number of the entity within the specified system which the block will use for the filtered variable. For example, if the filtered variable type is a historical database variable, the filtered variable number is the number of the variable in the historical database. After the filtered variable type is entered, the label next to this field will show what type of data is needed. When the filtered variable number is entered, other fields will also be filled in: the name and units for the filtered variable, aim, and sigma; units and default values for the max and min filtered values. Since Shewhart block timing always keys off entry of new data into the filtered variable, only discretely sampled variable types can be used.
Deviation variable type: a number code representing the software system and the type of entity into which the block should store the computed value of deviation from aim.
Deviation variable number: the number of the entity within the specified system into the block will store the computed deviation from aim. For example, if the deviation variable type is a historical database variable, the deviation variable number is the number of the variable in the historical database. After the deviation variable type is entered, the label next to this field will show what type of data is needed. When the deviation variable number is entered, other information will be automatically filled in by the build-supervisor procedure; in the example of FIG. 12, region 1236 indicates the pre-stored designation of historical database variable 2084. Such automatically completed information will preferably include the name and units for the deviation variable; units and default values for the max and min deviation values. Since Shewhart blocks execute on entry of new data into the filtered variable, only discretely stored deviation variable types can be used.
Rule variable type: a number code representing the software system and the type of entity into which the block should store a number code indicating which rule was broken.
Rule variable number: the number of the entity within the specified system into the block will store a number code indicating which rule was broken. For example, if the rule variable type is a historical database variable, the rule variable number is the number of the variable in the historical database. After the rule variable type is entered, the label next to this field will show what type of data is needed. When the rule variable number is entered, the name and units for the rule variable will also be filled in. Since Shewhart blocks execute on entry of new data into the filtered variable, only discretely stored rule variable types can be used.
Aim: the "on aim" value of the filtered variable.
Sigma: the standard deviation the filtered variable when the measurement is "on aim".
Fix time: A time interval after rule violations during which no rule tests are done. New measurements entered during the fix time interval are ignored. The fix time is entered as a delta time character string: "ddd hh:mm:ss" where "ddd" is the number of days, "hh" is the number of hours, "mm" is the number of minutes, and "ss" is the number of seconds. The fix time is taken from the timestamp of the filtered variable value which caused the deviation to be identified. The timestamp of later samples is compared against this, and if the difference is less than the fix time interval the sample is ignored.
Switch system and switch number: these are described above.
Minimum and maximum value of the calculated deviation: limits on the allowed value of the calculated deviation from aim. Deviations outside this range are set equal to the closest limit.
Minimum and maximum value of filtered variable: Screening limits for reasonable values of the filtered variable. Any time the filtered variable value falls outside these limits, the value will be ignored and no action is taken.
Action log file: this field is described above.
Block Operation
In the presently preferred embodiment, the sequence of actions performed by the Shewhart block is:
If the block status is "On-deselected", do no further calculations.
Retrieve the last 7 values of the filtered variable. If not available, do no further calculations.
Check the last value of the filtered variable. If it is outside the allowed limits, do no further calculations.
Search backward through the stored values of the deviation variable for the most recent non-zero value. If a non-zero value is found within one fix time interval before the present instant, do no further calculations.
Compute the cutoff time=time of last non-zero deviation plus the fix time.
Initialize the deviation and rule values (to zero).
Begin testing Shewhart rules:
If the last point is older than the cutoff time, do no further calculations.
If the last point is outside the 3 sigma limits (i.e. Abs(point-aim) is greater than 3 sigma), then:
Deviation=Last point-aim
Rule=1
Skip remaining rules.
If the second newest point is older than the cutoff time, Skip remaining rules.
If the last 2 points are both either greater than aim+2 sigma or less than aim -2 sigma, then:
Deviation=Sum(last 2 points)/2-Aim
ti Rule=3
Skip remaining rules.
If 2 out of the last 3 points are both either greater than aim+2 sigma or less than aim-2 sigma, then:
Deviation=Sum(last 3 points)/3-Aim
Rule=3
Skip remaining rules.
If the last 4 points are all either greater than aim+sigma or less than aim-sigma, then:
Deviation=Sum(last 4 points)/4-Aim
Rule=5
35 Skip remaining rules.
If 4 of the last 5 points are all either greater than aim+sigma or less than aim-sigma, then:
Deviation=Sum(last 5 points)/5-Aim
Rule=5
Skip remaining rules.
If all of the last 7 points are greater than aim or all less than aim, then:
Deviation=Sum(last 7 point)/7-Aim
Rule=7
Skip remaining rules.
Check and store result:
If the deviation is outside the allowable limits, set equal to the closest limit.
Store the deviation value and rule value in the respective variables. These values are time stamped the same as the last filtered value.
If the deviation is non-zero, update past actions.
Call the user routine.
Of course, other statistical filtering methods could be used instead. It is generally realized that statistical filtering is highly advantageous, and that numerous algorithms can be used to accomplish statistical filtering. The Shewhart algorithm used in the presently preferred embodiment could be replaced by any of a wide variety of other known algorithms.
Sample Source Code
The source code for the procedure which actually performs this function, in the presently preferred embodiment, is as follows.
TABLE 4__________________________________________________________________________C *******************************C Shewhart --block.forCCC ********************************C Subroutine Shewhart --block ( Block)C Include `ACS$includes:Block --parameters.inc/nolist` Include `acs$includes:ACSserv.inc/nolist` Include `acs$includes:ACSstatus.inc/nolist` Include `ACS$includes:Van --functions.inc/nolist` Include `ACS$includes:Filter --params.inc/nolist` Include `ACS$includes:dev --params.inc/nolist` Include `ACS$includes:rule --params.inc/nolist` Include `ACS$includes:User --yars.inc` Integer*4 Block Integer Error --lun Parameter ( Error --lun = 6 ) Character*20 Store --time Character*20 now --time Integer*2 Filtered --variable Integer*2 Deviation --variable Integer*2 Rule --variable Integer*2 Filtered --variable --type Integer*2 Deviation --variable --type Integer*2 Rule --variable --type Integer*4 I4 --deviation --variable Integer*4 I4 --rule --variable Real*4 Aim Real*4 Sigma Integer*4 Integer --fix --time Integer*4 Cutoff --time Integer*4 Safe --time Real*4 Deviation Real*4 Rule Real*4 Last --filtered -- value Logical All --same --sign Logical Need --violation Integer*4 Num --points Parameter (Num --points = 7) Real*4 Point(Num --points) Integer*4 Times(Num --points) Character*18 Char --times(Num --points) Integer*4 Num --points1 Parameter (Num --points1 = 8) Real*4 Point1(Num --points1) Integer*4 Times1(Num --points1) Character*18 Char --times1(Num --points1) Real*4 Violation --value(1) Integer*4 Violation --time(1) Integer*4 Newest --time Integer*4 Oldest --time Integer*4 Buffer --size Logical*1 First --request Integer*4 Block --location Integer*4 Entry --count Integer*4 Begin --span --status Byte Interp --flags Integer*4 Begin --span --time Integer*4 End --span --time Integer*4 Num --points --retrieved Integer*4 Integer --Now Integer*2 Start --pointCC....Special case for `On-deselected` statusC If ( Block --status(Block)(1:13) .eq. `On-deselected` ) Then Return End IfCC...Set the value of the local variablesC ACS --status = ACS --get --filtered --var --type(Block,filtered --variable Filtered --variable = Measured --variable(Block) ACS --status = ACS --get --dev --var --type ( Block , deviation --variabl) Deviation --variable = Manipulated --variable(Block) ACS --status = ACS --get --rule --var --type ( Block , rule --variable --typ Rule --variable = New --manipulated --variable(Block) Aim = Goal(Block) Sigma = Absolute --deadband(Block) Integer --fix --time = Fix --time(Block)C Van --status = Vss$ --from --ascii --time ( '', Integer --now ) Van --status = Vss$ --to --ascii --time ( Integer --now , now --time )d Van --status = Vss$ --to --ascii --time ( Integer --now , Store --time )d write(6,202) ' Calling Shewhart on var ',filtered --variable,' ad 1 Store --timed 202 format(//,a,' ',i5,' ',a,' ',a)CC...Retrieve enough points to test all the rulesC If ( Filtered --variable --type .eq. Van --var --filter ) ThenC Newest --time = Integer --now Oldest --time = Newest --time - 365*24*60*60 Buffer --size = Num --points First --request = .True. Num --points --retrieved = 0 Start --point = 1C Do 777 j = 1,Num --points Times(j) = 0777 Point(j) = 0.0C Van --status = %loc(vss --systemdown) Do While ( (Van --status .eq. %loc(vss systemdown)) .or. 1 (Van --status .eq. %loc(vss --unavaildata)) )C Van --status = Vss$ --Retrieve ( Filtered --variable , Newest --tim 1 Oldest --time , Buffer --size , Times(start --point) , 1 Point(Start --point) , 1 First --request , Block --location , Entry --count , 1 Begin --span --status , Interp --flags , Begin --span --time , 1 End --span --time ) Num --points --retrieved = Num --points --retrieved + Entry --count If ( Num --points --retrieved .lt. Num --points ) then Buffer --size = Buffer --size - Num --points --retrieved Start --point = Start --point + Entry count End Ifd write(6,*) `Finished data retr.`c End Docd do 11 J =1,Num --points.d 11 Van --status = Vss$ --to --ascii --time ( Times(j) , Char --times(j))d write(6,12) (Char --times(j),Point(j),j=1,num --points)d 12 Format( /,' Here are the times and points:',//d 1 (' ',a18,' ',f12.4 , / ) )d write(6,*) ` Got `,Num --points --retrieved,` points.` If ( Num --points --retrieved .lt. Num --points ) then Write(Error --lun,*) 1 `Shewhart Failed to get enough data on Variable `, 1 Filtered --variable write(error --lun,*)`from ACS block:`,block,` at:`,now --time Write(Error --lun,*) `Wanted `,Num --points,`; Got `, 1 Num --points --retrieved Return End Ifd write(6,*) `Got enough points.`CCC....Check the Measured variable to see if it is within limitsC Last -- filtered --value = Point(1) If ( (Last --filtered --value .lt. Measured --min(block) ) .or. 1 (Last --filtered --value .gt. Measured --max(block) ) ) TC.....Reject the data point Write( 6, *) `Shewhart exit due to out of limts filtered.` write(6,*)` ACS Block: `,block,` at: `,now --time Return End ifElse if ( Filtered --variable --type .eq. Van --run --2 --filter ) ThenC Newest --time = Integer --now Oldest --time = Newest --time - 365*24*60*60 Buffer --size = Num --points1 First --request = .True. Num --points --retrieved = 0 Start --point = 1C Do 1777 j = 1,Num --points1 Times1(j) = 01777 Point1(j) = 0.0C Van -- status = %loc(vss --systemdown) Do while ( (Van --status .eq. %loc(vss --systemdown)) .or. 1 (Van --status .eq. %loc(vss --unavaildata)) )c Van --status = Vss$ --Retrieve ( Filtered --variable , Newest --tim 1 Oldest --time , Buffer --size , Times1(start --point) , 1 Point1(Start --point) , 1 First --request , Block --location , Entry --count , 1 Begin --span --status , Interp --flags , Begin --span --time , 1 End --span --time ) Num --points --retrieved = Num --points --retrieved + Entry --count If ( Num --points --retrieved .lt. Num --points1 ) then Buffer --size = Buffer --size - Num --points --retrieved Start --point = Start --point + Entry --count End Ifd write(6,*) `Finished data retr.`c End Docd do 111 J =1,Num --points1d 111 Van --status = Vss$ --to --ascii --time ( Times1(j) , Char --times1(j))d write(6,112) (Char --times1(j),Point1(j),j=1,num --points1)d 112 Format( /,` Here are the times and points:`,//d 1 (' ',a18,' ',f12.4 , / ) )d write(6,*) ` Got `,Num --points --retrieved,` points.` If ( Num --points --retrieved .lt. Num --points1 ) then Write(Error --lun,*) 1 `Shewhart Failed to get enough data on Variable `, 1 Filtered --variable write(error --lun,*)`from ACS block:`,block,` at:`,now --time Write(Error --lun,*) `Wanted ',Num --points1,`, Got `, 1 Num --points --retrieved Return End Ifd write(6,*) `Got enough points.`CCC....Check the Measured variable to see if it is within limitsC Last --filtered --value = (Point1(1)+Point1(2))/2. If ( (Last --filtered --value .lt. Measured --min(block) ) .or. 1 (Last --filtered --value .gt. Measured --max(block) ) ) TC.....Reject the data point Write( 6, *) `Shewhart exit due to out of limts filtered.` write(6,*)` ACS Block: `,block,` at: `,now --time Return End ifC Do j = 1,num --points ! running average point(j) = (point1(j)+point1(j+1))/2 times(j) = times1(j) end doElse ! Improper filtered type Write( 6, *) `Shewhart exit due to invalid filtered var type.` write(6,*)` ACS Block: `,block,` at: `,now --time ReturnEnd If ! Filtered typesCCC....Check to see if the last violation was within the Fix time -C If so, do no calculations.CC...Retrieve the last stored nonzero deviation from aimCIf ( Deviation --variable --type .eq. Van --var --dev ) ThenC Newest --time = Integer now Oldest --time = Newest --time - 365*24*60*60 Buffer --size = 1 First --request = .True. Need --violation = .True. Do While ( Need --violation )c Van --status = Vss$ --Retrieve ( Deviation --variable , Newest --i 1 Oldest --time , Buffer --size , Violation --time , 1 Violation --value , 1 First --request , Block --location , Entry --count , 1 Begin --span --status , Interp --flags , Begin --span --time , 1 End --span --time )c If ( ( Van --status .ne. %loc(vss --systemdown) ) .and. 1 ( Van --status .ne. %loc(vss --unavaildata)) .and. 1 ( Van --status .ne. %loc(vss --notallfound)) ) Thenc Write(6,*)` Shewhart Violation retr - status vss --badva write(6,*)` ACS Block: `,block,` at: `,now --timec Else If( Van --status .eq. %loc(Vss --badtime) ) then Write(6,*)` Shewhart Violation retr - status vss --badti write(6,*)` ACS Block: `,block,` at: `,now --timec Else If( Van --status .eq. %loc(Vss --badtimespan) ) then Write(6,*)` Shewhart Violation retr - svss --badtimespan` write(6,*)` ACS Block: `,block,` at: `,now --timec Else If( Van --status .eq. %loc(Vss --badbufsize) ) then Write(6,*)` Shewhart Violation retr - status vss --badbu write(6,*)` ACS Block: `,block,` at: `,now --timec Else If( Van --status .eq. %loc(Vss --normal) ) then Write(6,*)` Shewhart Violation retr - status vss --norma write(6,*)` ACS Block: `,block,` at: `,now --timec Else If( Van --status .eq. %loc(Vss --nonefound) ) then Write(6,*)` Shewhart Violation retr - status vss --nonf write(6,*)' ACS Block: `,block,` at: `,now --timec Else If( Van --status .eq. %loc(Vss --nomoreonline) ) then Write(6,*)` Shewhart Violation retr - svss --nomoreonline` write(6,*)` ACS Block: `,block,` at: `,now --timec End If WRite(6,*) ` Van --status = `,Van --status Van --status = Vss.$ --to --ascii --time ( Violation --time(1) , Stor) Write(Error --lun,*) 1 `Shewhart-couldn''t get a non zero deviation - exiting` write(6,*)` ACS Block: `,block,`at: `,now --time Write(Error --lun,*) 1 ` Oldest violation got: ` ,Violation --value(1),` at `,Store -- Return End If If ( ( Abs(Violation --value(1)) .gt. 1. E-10 ) .or. 1 ( Violation --time(1) .lt. 1 (Times(7) - Abs( Integer --fix --time ))) ) Then Need --violation = .False. End Ifc End Do Else ! Improper deviation var type Write( 6, *) `Shewhart exit due to invalid deviation var type write(6,*)` ACS Block: `,block,` at: `,now --time Return End If ! Get last deviation for allowed deviation typesccd Van --status = Vss$ --to --ascii --time ( Violation --time(1) , Store --tid write(6,*) ` Got a violation of `,Violation --value(1),` at `,d 1 Store --timeCC....Go through the shewhart Rules - any point older than the last vioC time + the fix time is not acceptable.C Cutoff --time = Violation --time(1) + Abs(Integer --fix --time)d Van --status = Vss$ --to --ascii --time ( Cutoff --time , Store --time )d write(6,*) ` Cutoff time is `, Store --timec Deviation = 0.0 Rule = 0.0C If ( Times(1) .lt. Cutoff --time ) Returnd write(error --lun,*) `Testing 1 out of 1 rule.` If ( Abs(Point(1)-Aim) .gt. 3*Sigma ) Then Deviation = Point(1) - Aim Rule = 1.0 Go To 1000 End ifCC...Test 2 in a row outside 2 sigmaC If ( Times(2) .lt. Cutoff --time ) Go To 1000d write(error --lun,*) `Testing 2 out of 2 rule.` Sum --points = 0.0 Num --out --high = 0 Num --out --low = 0 Do 2 J = 1,2 Sum --points = Sum --points + Point(J) If ( (Point(J)-Aim) .gt. 2*Sigma ) Then Num --out --high = Num --out --high +1 Else If ( (Point(J)-Aim) .lt. -2*Sigma ) Then Num --out --low = Num --out --low + 1 End If2 Continue If ( ( Num --out --high .eq. 2 ) .or. 1 ( Num --out --low .eq. 2 ) ) Then Deviation = Sum --points/2 - Aim Rule = 3.0 Go To 1000 End IfCC...Test 2 out of 3 outside of 2 sigmaC If ( Times(3) .lt. Cutoff --time ) Go To 1000d write(error --lun,*) `Testing 2 out of 3 rule.` Sum --points = Sum --points + Point(3) If ( (Point(3)-Aim) .gt. 2*Sigma ) Then Num -- out --high = Num --out --high +1 Else If ( (Point(3)-Aim) .lt. -2*Sigma ) Then Num --out --low = Num --out --low + 1 End If If ( ( Num --out --high .eq. 2 ) .or. 1 ( Num --out --low .eq. 2 ) ) Then Deviation = Sum --points/3 - Aim Rule = 3.0 Go To 1000 End IfCC...Test 4 in a row outside 1 sigmaC If ( Times(4) .lt. Cutoff --time ) Go To 1000d write(error --lun,*) `Testing 4 out of 4 rule.` Sum --points = 0.0 Num --out --high = 0 Num --out --low = 0 Do 3 J = 1,4 Sum --points = Sum --points + Point(J) If ( (Point(J)-Aim) .gt. 1*Sigma ) Then Num --out --high = Num --out --high +1 Else If ( (Point(J)-Aim) .lt. -1*Sigma ) Then Num --out --low = Num --out --low + 1 End If3 Continue If ( ( Num --out --high .eq. 4 ) .or. 1 ( Num --out --low .eq. 4 ) ) Then Deviation = Sum --points/4 - Aim Rule = 5.0 Go To 1000 End IfCC...Test 4 out of 5 outside 1 sigmaC If ( Times(5) .lt. Cutoff --time ) Go To 1000d write(error --lun,*) `Testing 4 out of 5 rule.` Sum --points = Sum --points + Point(5) If ( (Point(5)-Aim) .gt. 1*Sigma ) Then Num --out --high = Num --out --high +1 Else If ( (Point(5)-Aim) .lt. -1*Sigma ) Then Num --out --low = Num -- out --low + 1 End If If ( ( Num --out --high .eq. 4 ) .or. 1 ( Num --out --low .eq. 4 ) ) Then Deviation = Sum --points/5 - Aim Rule = 5.0 Go To 1000 End IfCC...Test 7 in a row - same side of aimC If ( Times(7) .lt. Cutoff --time ) Go To 1000d write(error --lun,*) 'Testing 7 in a row rule.' Sum --points = 0.0 Sign --deviation = Sign( 1.0,(Aim-Point(1)) ) If ( (Aim-Point(1)) .ne. 0) Then All --same --sign = .True. else All --same --sign = .False. End if Do 4 J = 1,7 If ( (Aim-Point(J)) .eq. 0) Then All --same --sign = .False. Else If ( Sign( 1.0,(Aim-Point(J)) ) .ne. Sign --deviation All --same --sign = .False. End if Sum --points = Sum --points + Point(J) If ( All --same --sign ) then Deviation = Sum --points/7 - Aim Rule = 7.0 Go To 1000 End IfC1000 Continued write(6,*) `Got deviation, rule of `,deviation,ruleCC...Clamp the deviation at allowed limitsC If ( Deviation .gt. Manipulated --max(Block) ) Then Deviation = Manipulated --max(Block) Else If ( Deviation .lt. Manipulated --min(Block) ) Then Deviation = Manipulated --min(Block) End IfCC...Store the Computed Deviation and Rule number with TimestampCd Van --status = Vss$ --to --ascii --time ( Times(1) , Store --time )d write(6,*) `putting var `,i4 --deviation --variable,` at `,store --td 1` with value `,deviationc If ( Deviation --variable --type .eq. Van --var -- dev ) Then I4 deviation --variable = Deviation --variable Dmt --status = Dmt$ --putlab ( I4 --deviation --variable , Times(1) , 1 Deviation , 2 , .False. ) Else ! Other deviation types End If ! Deviation typescd write(6,*) ` Did putlabs -first status = `,dmt --statusd write(6,*) `putting var `,i4 --rule --variable,` at `,store --time,d 1` with value `,rulec If ( Rule --variable --type .eq. Van --var --rule ) Then I4 --rule --variable = rule --variable Dmt --status = Dmt$ --putlab ( I4 --rule --variable , Times(1) , 1 Rule , 2 , .False. ) Else ! Other rule types End If ! Rule typescc status = vss$ --mehclose() !close file just in cacd write(6,*) ` Did putlabs -second status = `,dmt --statusd write(6,*) ` Did putlabs -exiting`CC...If Deviation is non-zero, update past actionsC If ( Deviation .ne. 0 ) Then Do 90 J = 5,2,-1 Past --action --value(Block,J) = Past --action --value(Block,J- 1)90 Past --action --time (Block,J) = Past --action --time (Block,J-1) Past --action --value(Block,1) = Deviation Past --action --time (Block,1) = Times(1) End IfCC...Load user arrays for user programsC User --integer(1) = Integer --now ! Time of Tests User --integer(2) = Rule User --real(1) = Deviation Do J = 1 , Max ( Num --points , 18 ) User --integer(2+J) = Times(J) ! Time of samples used in test User --real (2+J) = Point(J) ! Value of samples used in tes End Do If ( Rule .eq. 0.0 ) Then User --character(1) = `On aim, No rules broken ` User --character(2) = `On aim, No rules broken.` Else If ( Rule .eq. 1.0 ) Then User --character(1) = 'Shewhart 1 out of 1 rule' User --character(2) = 'Shoe heart 1 out of 1 rule' Else If ( Rule .eq. 3.0 ) Then User --character(1) = `Shewhart 2 out of 3 rule` User --character(2) = `Shoe heart 2 out of 3 rule` Else If ( Rule .eq. 5.0 ) Then User --character(1) = `Shewhart 4 out of 5 rule` User --character(2) = `Shoe heart 4 out of 5 rule` Else If ( Rule .eq. 7.0 ) Then User --character(1) = `Shewhart 7 in a row rule` User --character(2) = `Shoe heart 7 in a row rule` End IfCC...Call User routineC Call User --programs ( Block ) Return End B5__________________________________________________________________________
(Copyright (c) 1987 E.I. Dupont de Nemours & Co., all rights reserved)
User-Defined Program Block
Figure 13 shows the form which (in the presently preferred embodiment) is presented to a user who has chosen the "User program" option from the menu shown in FIG. 9.
The user program block provides a means of controlling the execution of a user written FORTRAN subroutine. The block itself performs no control actions, but allows the user to specify a timing option and switch parameters for executing the block's user routine. A user routine exists for every block in the supervisor procedure. (In the example shown in FIG. 13, where the block shown is block number 2, the block will (selectively) make calls to BLOCK2 --USER -- ROUTINE.) Initially these routines (BLOCK1 -- USER -- ROUTINE, BLOCK2 -- USER -- ROUTINE, BLOCK3 -- USER -- ROUTINE, etc.) do nothing (i.e., their default content is merely the FORTRAN statements Return and End), but they can be modified by the user. The user program block only sets up parameters for controlling execution of the user program.
The user program timing options include keying off a measured variable. In this case the variable is not used for anything but timing. This option can be altered by specifying screening limits on the measured variable value (using fields 1332 and 1334), so that measured values outside the screening limits are ignored. Block timing and switching and the block description fields follow the general outlines given above.
Parameters
The parameters are:
Measured variable type: a number code representing the software system and the type of entity which the block should use for the measured variable.
Measured variable number: the number of the entity within the specified system which the block will use for the measured variable. For example, if the measured variable type is a historical database variable, the measured variable number is the number of the variable in the historical database. After the measured variable type is entered, the label next to this field will show what type of data is needed. When the measured variable number is entered, other fields will also be filled in: the name and units for the measured variable; units and default values for the max and min measured values.
Timing option, execution time interval, and Key block number: these parameters are described above.
Switch system and switch number: these are described above.
Minimum and maximum value of measured variable: These define screening limits for reasonable values of the measured variable. Whenever the measured variable value falls outside these limits, the value will be ignored and no action is taken.
Action log file: this field is described above.
Program Block Operation
The sequence of actions performed by a User program block is:
If block status is "On-deselected", do not execute the user routine.
If a measured variable is specified:
Get the current value of the measured variable (If not accessible, set status to "On-err . . . " and do not execute the user routine).
Test the value of the measured variable. If it outside the range of allowed values, set status to "On-msrd out of lims" and do not execute the user routine.
Execute the user routine. The routine name is derived from the block number. Block 1 calls Block1 -- user -- routine, block 199 calls Block199 -- user -- routine, etc.
If a fatal error occurs in the user routine, bypass the rest of the routine, and set the block status to "On-Failed usr routin".
If the block failed on the last execution, but did not fail on this execution, set the block status to "On".
Clear all the values in the user -- vars common block.
Build-User-Program Procedure
The build-supervisor procedure (in the presently preferred embodiment) also provides a structured environment for creating user programs. As will be described below, the build-expert procedure will create the source code for one or more customized expert systems; but the user must still insert a call to this expert code into one of the blocks in the supervisor procedure. The build-user-program procedure facilitates this, and also provides convenient support for sophisticated users who are able to write their own utilities.
In the presently preferred embodiment, this is a structured environment in which users can write FORTRAN subroutines and incorporate them into control blocks. User programs can be run as the only block function by defining a User Program block (as described above), or they can be used to take additional actions (such as message logging) in combination with feedback or feedforward control blocks.
At a minimum, a user with no programming knowledge can insert a one-line call into a user program block, to make use of an expert subprocedure created using the build-expert procedure. However, to take full advantage of the capability for user programming, the user should (in the presently preferred embodiment) already be comfortable programming in FORTRAN and using FORTRAN functions and subroutines, and in using the Vax EDT editor. The build-user-program environment 1810 in this embodiment is menu driven rather than forms driven, and therefore provides less online help than some of the other functions described.
Writing a basic user program involves 5 steps:
Selecting which block number's user program to edit;
Editing the file which contains the user program code for that block. The EDT editor 1812 is used to write and modify the FORTRAN language code;
Checking the code for errors in FORTRAN syntax;
Updating the supervisor procedure by incorporating the latest version of the user program into the base cycle procedure and running the new base cycle procedure; and
Monitoring user program execution to assure that the program is executing properly.
In the example shown in FIG. 16, the top level build-supervisor menu permits the user to enter the build-user-program environment by pressing keypad 5. While in the build-user-program environment, the user can edit the block user routine; check the block user routine for errors in FORTRAN syntax; and update the supervisor procedure by incorporating the new version of the block user routine. The first prompt from the user program menu asks what block number's routine the user wants to work on. Entering the block number and pressing return brings up another program menu, with options which will now be described.
Editing the user routine begins by selecting menu option 1 ("Edit user routine"). This will start the EDT editor. User routines of some sort already exist for all the blocks. Blocks which have never had any special programming have a user routine which does nothing--it consists simply of a RETURN statement followed by an END statement, and, if the block's user routine has never been worked on, this default routine will be brought up by the editor. To make a functioning routine, the user must add FORTRAN code before the RETURN statement to perform the desired function. (In the presently preferred embodiment, the user can simply edit the file like any other FORTRAN source code file on the VAX.) For example, code for logging messages or calling an expert subroutine can be inserted at this point.
Once the user has edited the user routine and returned to the menu, he can select option 5 to check for FORTRAN syntax errors. If the new routine has no FORTRAN syntax errors, the screen will show "The user's routine compiled with no errors in syntax." If the new coding has syntax errors, the user will see them reported on the terminal screen. The user can then correct the errors using Option 1 (edit), and repeat until all errors have been removed.
Once the user has a routine that compiles with no errors, he can include it in the running version of the supervisor procedure by using menu option 8 ("Update"). This will compile the user's routine, relink the base cycle procedure using the user's newly compiled routine, stop the procedure which is currently running, and restart the base cycle procedure using the newly linked version containing the user's new routine.
After compiling the user's routine, the build-supervisor procedure will ask if there are any other subroutines in separate files that need to be compiled. Some application may require more than one subroutine, and, if desired, they can be split up in separate files. To make a routine in a separate file, the user can select option 2 ("Edit a separate FORTRAN subroutine") to create and modify the file, and then select option 6 ("Check a separate subroutine for FORTRAN errors") to check for FORTRAN errors. To include the separate file into the supervisor procedure, the user can use the update option, then answer "Y:" when asked if any separate routines need to be compiled and included. The base cycle procedure can then be linked, and then restarted.
After the user's routine has been incorporated into the base cycle procedure, the user can monitor it to make sure it executes properly. There are two key indicators of a problem with the user's user routine: the block status and the control program log file. If the user's routine has an error which would normally cause a stand-alone FORTRAN program to terminate, the base cycle procedure will bypass the error and the remainder of the user's routine, and change the block status to "On-Failed usr routin". This can be seen using the block monitoring screen. If the user's routine fails once but runs successfully on a subsequent execution, the block status will be changed to "On-Recovrd Usr Error", and a message will be posted in the control program log file indicating which user routine had the error, when it occurred, and what the error was. The log file can be viewed using the "List log file" option on the System functions screen.
The user can print a listing of a user routine by using option 3 (or option 4 for a separate routine).
If the user's user routine fails and the user needs to retreat to the last version that was running, he can use the restore option (keypad 9). This will prompt the user for any separate routines that need to be restored, and retrieve the old versions saved by the build-supervisor procedure.
In the presently preferred embodiment, there are several include files which can be used in user routines: "User -- vars.inc" contains a common block which is used to pass information about control block actions to user routines. The common block contains a Real array, an integer array, and a character*80 array. Control blocks load values into these arrays for the amount of change made in the manipulated variable, the error in a feedback block, the time the action was taken, etc. The user program block zeros out these values after the user routine executes a RETURN statement. "ACSserv.inc" declares all the ACS service routines (which are integer*4 functions). "ACSstatus.inc" declares all the legal ACS status return values. These values must be declared external before they can be used. "Van -- functions.inc" declares some of the retrieval and time functions from the historical process database, and declares some of the status return values.
Of course, many different computer languages and architectures could be used in practising the present invention: the sample FORTRAN routines specified (as well as other features which, for example, relate specifically to the use of a VMS operating system) simply sets forth the best mode as presently practiced, but a tremendous variety of other languages, operating environments, and/or hardware could be used instead.
Block-Handling Utilities
FIG. 14 shows a menu which is preferably presented to a user who has elected to use the utilities provided in the build-supervisor procedure (e.g. by hitting keypad 9 when faced with the menu shown in FIG. 16). While these utilities are not necessary parts of every implementation of the innovative concepts described in the present application, they do help users to take advantage of the full power available.
In the presently preferred embodiment, the supervisor procedure includes the capabilities for copying and deleting blocks, and for printing listings of block setup parameters. Deleting a block (Keypad 7) removes all the block type and setup parameter data for the block, leaving it available for another use. Copying a block (Keypad 8) reproduces the block type and setup parameters of one block into another. Printing blocks (Keypad 9) allow the user to select blocks to be printed either by number range or by searching for string matches in the application name or block description fields, and makes full or abbreviated listings of block parameter data on the printer of the user's choice.
If the user elects to copy a block, the build-supervisor procedure prompts the user to enter in the "Source block" field 1402 the number of the block to copy. The build-supervisor procedure then fills in the information fields appropriately for that block, allowing the user to confirm that he has entered the right block number, and prompts the user again for the target block into which the block should be copied (field 1404). After this is entered the build-supervisor procedure fills in the information fields for the target block, and prompts the user again. When the user confirms that the block is to be copied, the block type and parameters are overwritten in the shared memory 814. After the block is copied, the build-supervisor procedure prompts the user again, asking whether the source block should be deleted or left unchanged. The build-supervisor procedure confirms that the source block was either deleted or not deleted.
Block information can only be copied into target blocks whose status is "Off" or "Inactive". To copy information into a block with an active status, the user must go to the block setup form for that block, and toggle the block off. This safeguard provides greater system integrity.
In the presently preferred embodiment, keypad 9 will initiate printing a listing of selected block parameters. The build-supervisor procedure will prompt the user to enter in field 1410 for the starting range of block numbers to print, or to hit return if he wishes to select blocks by string searches. To print a range of block numbers, the user can enter the lowest number block in the range, press return, then enter the higher number block (in field 1412) and press return. To select the blocks to be printed by search for string matches, the user can press return without entering a number for the starting block. To search the block description fields, the user can enter the desired string in the description search string field 1406. To search the block application name field, the user can press return without entering anything in the description field, and enter the desired string when prompted in the application name field 1408. In either case, the user can use capital and lower case letters interchangeably, since case is not checked in the string searches. The user need not fill in the whole search string field. A block will be selected to print if the string the user enters appears anywhere in the searched field.
The build-supervisor procedure will now prompt the user for a short or long list. A short list shows only the block number, type, description, and application name. A long list shows the entire setup form for that block. The build-supervisor procedure will clear the screen and prompt the user for the printer he wishes to use. The user can type the number of the printer if he knows it, or enter L to get a list of printers to choose from. The user's terminal screen and its attached printer can be selected, as well as Vax system printers. When the print job is completed, the build-supervisor procedure will report the number of blocks that were printed.
Monitoring
In addition, the supervisor procedure provides several functions for following the performance of control strategies as they operate. The block monitoring screen allows the actions of individual blocks to followed. The system functions screen shows the status of the supervisor procedure. The control system runs as a batch-type process on the Vax, and so it has a log file which contains all the error messages generated by the system.
A user who requests block-monitoring is presented with a block description form which includes a block number field in which he can insert the number of the block to be monitored. The remaining fields on the form then are filled in appropriately by the build-supervisor procedure, and are subsequently updated every 5 seconds. The information shown includes:
the current time;
the time at which the supervisor base cycle procedure will make its next scan through the blocks (and blocks which are due to execute will be executed);
the block type (which was specified during block setup, e.g. feedforward, feedback, etc.);
the block description (which was entered during setup);
the type, number, name and units of the measured variable which was specified in block setup (if none was specified (e.g. in a program block), this field will be blank);
the current value and time stamp of the measured variable (the time stamp for compressed variables is the time the last new value was received; for manual entry variables it is the time stamp of the last entered value; and if no measured variable was specified, this field is blank);
the goal value for feedback blocks (for other block types, this field is empty);
the number, name, units and type of manipulated variable;
the current value of the manipulated variable (with time stamp if one has been defined);
the timing option entered during block setup;
the execution time interval specified during block setup. If the block timing does not include any fixed frequency, this field is blank.
the time the block last did its scheduled actions (this is normally the last time the block was scheduled to execute according to its timing option parameters, regardless of whether the block acted to change the manipulated variable);
the current status of the block; and
the last five control actions made by the block (or, for Shewhart blocks, the last five deviation values) and the times at which they occurred.
In the presently preferred embodiments, a similar overhead function permits the user to take a look at the current status of key system parameters, including:
Base scan interval: the time interval at which the base cycle procedure scans through all the properly configured blocks, checking for changes in the on/off status, testing each according to its timing option and status to determine whether it should execute, and executing those that are due to execute.
Next base cycle time: the time at which the supervisor" procedure will actually do the next scan. This time should always be in the future, and should never be more than the base scan interval away.
Current system status: provides information about what the supervisor procedure system is currently doing. Since the supervisor procedure only does its actions once every base scan interval, the system spends most of its time sleeping - i.e. waiting for the next cycle time to come. The normal system status values are:
Running-Sleeping the normal status value. All control actions on the last scan have completed and the system is waiting for the next scan.
Running-Computing the system is currently performing block checks and executing blocks. Since calculations in the supervisor procedure finish rather quickly, this status will rarely be seen.
Terminated normally: This status indicates that the supervisor procedure system has been stopped in an orderly way. Normally this status value will only be seen if the system manager has stopped the system, or briefly when a user performs the Update function on the user program menu.
An authorized user can change the base scan interval, stop the supervisor process (together with any auxiliary processes used for communication with PCS or other control systems), restart the supervisor process (and any auxiliary processes), or view the log file to which the base cycle procedure writes error reports and messages.
Block Initialization
Blocks are initialized when they are first turned on, or when the supervisor procedure is restarted after an outage of 30 minutes or more and the block had already been on. Block initialization sets the "last execution time" of the block to the current time. The "last execution time" value is used in fixed interval timing and also as a block monitoring parameter. If the block has a measured variable, the "last measured time" is set equal to the current time of the measured variable. This parameter is used when block timing is keyed off the measured variable. If the block timing is set to key off another block, the key block time is set equal to the last execution time of the key block. For feedforward blocks, the "old measured value" is set equal to the current value of the measured variable.
Build-Expert and Expert Procedures
The procedures for constructing an expert system from a domain expert's knowledge will now be described, together with the procedures by which the expert system is called up by the operating software (preferably the process control supervisor procedure, as described above).
It should be noted that the structures and advantages of the build-expert procedure are not entirely separate from those of the expert procedure (or procedures) generated thereby. The two procedures are 2, preferably operated separately, but they are designed for advantageous combination. The features of the expert procedure are partly designed to advantageously facilitate use of the build-expert procedure, and the features of the build-expert procedure are partly designed to advantageously facilitate use of the expert procedure.
The build-expert procedure works especially advantageously as an integral part of the supervisor procedure, which (in the presently preferred embodiment) is a VAX-based layered control system. The build-expert procedure produces complete FORTRAN subroutines that execute the expert actions. The supervisor procedure (e.g. via a user program block) provides the functions for running an expert subroutine at specified times, and also provides callable routines that can be used by these subroutines to make and modify supervisor actions. The build-expert procedure can be used without the preferred supervisor procedure, but the user must provide a host program running at appropriate times to call the subroutines.
Preferred Menu Structure
In the presently preferred embodiment, the build-expert procedure is accessed by selecting the "User program" option on the top-level menu in the build-supervisor procedure (see FIG. 16), entering the desired block number, and then selecting the Expert system development option on the user program menu. This will take the user to the build-expert procedure, which (in the presently preferred embodiment) presents a menu as shown in FIG. 17.
From this menu the user can access setup templates for the 3 rule types. The user also has access to functions for printing the rulebase, and for building a new expert subroutine.
The rule templates used in the build-expert procedure allow the user to enter and modify the specification information for rules. The build-expert procedure is different from the build-supervisor procedure in the way it handles data. When a rule name is entered in the build-expert procedure and the RETURN or TAB key pressed, the letters are capitalized and the embedded spaces are transformed to underscores. This is how the build-expert procedure stores all character data. The other fields on rule templates are not transformed like this until the rule is stored. When the rule is recalled onto the template, the other fields will be capitalized with embedded blanks changed to underscores. In the presently preferred embodiment, the rule name, data type, and data number fields are the only fields on the rule templates for which the user's entry is checked immediately (others may be modified in the future to do this). The remaining fields can be filled in with any data that the template allows (some fields accept only integers, some only alphabetics, etc). The data on the remaining fields is tested only when the user presses the keypad "-" to store the rule. The build-expert procedure then examines the data for errors, and requests corrections if needed. The build-expert procedure always checks rule names (and condition names) to be sure they are valid and meaningful where entered. In the presently preferred embodiment, the build-expert procedure checks other data for most errors, but it does not check for all conceivable errors. Data entered on a rule template is NOT stored until the keypad "-" key is pressed to store the rule. Data on a template will not be stored if the rule name field is blank. Data on a template can be lost if the user enters the data, then modifies the rule name field before pressing keypad "-". All the rule templates have a "delete rule" (keypad "-") and "top of form" (keypad 9) softkey. The delete rule key will ask the user to confirm the deletion by pressing the key again, and then deletes the rule from the rulebase. The top of form key simply takes the user to the top of the template.
After all the rules have been entered, the FORTRAN expert subroutine must be generated using keypad 9, "Generate Expert". Changes made in the rules will not become effective until the expert is rebuilt. When the build-expert procedure is used within the build-user-program environment (as discussed above), the FORTRAN subroutine is generated in the same directory with the user program and is named Blockn -- expert -- system for, with the subroutine name Blockn -- expert -- system (n is the number of the block being worked on.) To use the expert from within the supervisor procedure, a one line user program must be written to call the expert. The one executable line is:
Call Blockn.sub.-- expert.sub.-- system.
Standardized Data Interface
The build-expert procedure uses a standard data interface. In the presently preferred embodiment, data sources are specified by a pair of integer parameters. One, the "data type", is a coded value which identifies the type of data desired and the data collection system from which the data is to come. The second , the "data number", identifies the specific data entity of that type within that system. Some data types (e.g. time averages) require a third parameter specifying the time over which to average.
This system has several advantages. First, it provides a simple method of data identification in a many-system environment. Secondly, it allows the rules to easily reference data of many types from many diverse (and possibly remote) sources without requiring the user to write any custom program code for data retrieval. Some useful data sources might include: any lower level process control system; any supervisor process (whether running on the same hardware system or another); any process database (whether running on the same hardware system or another); of any computer which collects or generates data ("computer" being defined very broadly to include, e.g., any system which includes a microprocessor, such as a microprocessor based single loop controller).
In the presently preferred embodiment, the data types allowed by the build expert procedure are: (1) the latest value of a database variable; (2) a time weighted average over a given time interval of the value of a database variable; (3) a simple average over a given time interval of the discrete data values of a database variable; (4) the feedback error of a feedback block in the supervisor process; (5) the change in the value of the measured variable of a supervisor feedforward block since the last time the block acted; (6),(7) the goal values of control loops in two particular lower level control systems; (8) the second most recent value of a discretely sample process database variable; (9),(10) the maximum and minimum limits for the manipulated variable value in a supervisor control block. Other sources could be used, for example any kind of parameter from any of the systems named in the previous paragraph, or system lexical functions (such as the system clock). As a further alternative, it might also be advantageous in some embodiments to make one of the options here a one-line blank, in which the user could enter a pointer to a callable procedure to fetch a variable value.
In the presently preferred embodiment, the user must specify the data type before the data number. When the data type is entered, a prompt line pops up on the template indicating the specific data type, which aids the user in entering the proper value for the data number. When the data number is entered, it is tested to be sure it is a meaningful entry for the data type specified. Some additional information is then displayed (such as a variable name and its units) to aid the user in confirming his input. These fields also serve to aid understanding of rule function and meaning when recalled for review or modification.
Constructing the Expert System
An expert system goes through four steps in using knowledge: (1) The expert gets information from the outside world; (2) analyzes that information using its rules; (3) deduces the correct conclusion from its analysis; (4) communicates its decision to the outside world.
Rules state that WHILE one thing is true THEN something else must be true. For example, WHILE the composition of water in the Feed mix drum is greater than 12%, we say "FEED MIX WATER COMPOSITION" is "HIGH". Or, WHILE "FEED MIX WATER COMPOSITION" is "HIGH", AND "DEHY COLUMN BOTTOMS WATER" is "HIGH", we say "TOTAL SYSTEM WATER" is "TOO HIGH". WHILE "TOTAL SYSTEM WATER" is "TOO HIGH", we "Give a high water warning message."
This simple example shows the three basic types of rules which are used in the build-expert procedure: the sample retrieval rule described tests the VALUE (12%) of a process measurement (FEED MIX WATER), and assigns a value (HIGH, LOW, etc.) describing the condition of the measurement. The sample analysis rule given tests for combinations of values defined by other rules. If it finds the combination, the analysis rule creates a new condition (TOTAL SYSTEM WATER) and assigns a value (TOO HIGH) describing that condition. The sample action rule described tests for one specific condition (TOTAL SYSTEM WATER) has one specific value (TOO HIGH), and takes a specified action (Give a high water warning message).
Sample Expert System
An example of construction of an expert system using novel methods and system as set forth in the present application will now be described in detail. The sample system here chooses an optimum control action from among three possibilities. A key element of the problem here is to control the composition of by-product MFB in the product stream of a refining train like that shown in FIG. 7. MFB is separated in two columns in series. Essentially equivalent response in MFB composition can be achieved by changing the steam flow to either column. Both columns use high value steam in their reboilers. The first, the Xylene column, dumps the steam energy to cooling water. The second column, the MFB column, recovers most of the energy by generating steam overhead. Equipment limitations constrain both steam flows to within high and low limits.
As column feed rate varies, steam loading can change from minimum steam on both columns to maximum steam on both columns. The optimum operation maximizes steam on the low cost column (MFB) and minimizes steam on the high cost column (XYL).
In this example, control of the MFB composition is done statistically. The laboratory measurements of MFB are statistically tested using Shewhart tests. The Shewhart tests determine the on aim status of MFB: Off aim high, Off aim low, or on aim. When MFB is off aim, the Shewhart test generates an estimate of how far off aim MFB is. This estimate can be used to compute the feedback action needed to bring MFB back to aim: off aim high requires an increase in steam to the two columns, off aim low requires a decrease.
The expert system which is sought to be developed should instruct the supervisor procedure to make the least cost control action. Plant startup, problems, or poor manual operation may distribute steam in a non-optimal way, and this cannot be known beforehand. The objective will be to move toward the optimum steam distribution through control action response to off aim conditions. Steam will not be shifted for cost savings only, since this complicates control and may negatively affect quality.
Although this may seem like a trivial decision, it actually involves considering 3 variables in the correct sequence. This is where the "expertise" gets into the "expert" system. Developing the logic is the task of the human expert, and the system disclosed herein merely expedites the transfer of that logic into the expert system. The process control decision tree which will be implemented, in the sample embodiment described, is as follows: First, decide whether to add or cut steam:
(1) If adding steam:
(1.1) First check the MFB column. If MFB column steam below maximum, add steam here.
(1.2) If the MFB column steam is maximum, then
(1.2.1) Check the Xylene column. If xylene column steam is below the maximum, add steam here.
(1.2.2) If xylene column steam is maximum, the user cannot add steam. To get MFB on aim, feed to the column must reduced. Cut column feed.
(2) If cutting steam:
(2.1) First, check the xylene column. If xylene column steam is above the minimum, cut steam here.
(2.2) If xylene column steam is minimum, then
(2.2.1) Check the MFB column. If MFB columns steam is above minimum, cut steam here.
(2.2.2) If MFB column steam is minimum, the user cannot cut steam. To get MFB on aim, Feed to the column must be increased. Add column feed.
It is highly desirable that the decision tree being implemented should cover all the possible cases, and that the conclusions should be mutually exclusive. If it does not cover all the possible cases, the expert will sometimes be unable to come to a conclusion. If the conclusions are not mutually exclusive, then more than one conclusion could exist. Although this might logically be possible, this condition might mean unpredictability as to which conclusion will be reached, so that there would not be a reproducible basis for action.
Domain experts, in performing the analytical steps which the expert system should ideally emulate, will carry out many steps implicitly; but implementing a process in a computer requires that each step be expressly spelled out. To make the decision, the user must first specify:
what measurements will be used to evaluate the process condition (in this example, MFB -- STEAM, XYL -- STEAM, DIRECTION -- OF -- CHANGE);
what ranges of values of the measurements (e.g. 40>XYL -- STEAM) match what status values for the measurements (e.g.MID -- RANGE);
what combinations of status values (e.g. MFB -- STEAM is MAX and XYL -- STEAM is MIN, and DIRECTION -- OF -- CHANGE is ADD) will result in what other conditions (e.g. ACTION is CHANGE -- XYL -- STEAM);
what must be done to make the desired action happen.
The detailed specifications needed to handle this problem are defined as follows:
Measurements: For MFB column steam, the goal on the computer loop for MFB steam is a good measure. In the sample system referred to, this is loop 30 in the "DMT PCS" system. For xylene column steam, the goal on the computer loop is a good measure. In the sample system referred to, this is loop 5 in the "DMT PCS" system. For the direction of change, the best measure is the feedback error on the control block that will be changing steam (in this case, the third block in the supervisor procedure). For MFB column steam, we know the operating limits of steam flow to the column (in thousands of pounds per hour (MPPH)):
MAX>49.5;
MIN<28.5;
MID>28.5<49.5.
And for the xylene column:
MAX>66.5
MIN<40.5
MID>40.5<66.5.
For the direction of action, we know that an off aim high condition means a steam increase. Our feedback block (in the supervisor procedure) is using the Shewhart deviation from aim as the measured variable, with an aim of 0.0. Thus if the feedback error is positive, we increase steam:
ADD if Feedback error>0
CUT if Feedback error<0 or=0
For the analysis of these conditions, we need to specify what combinations of conditions lead to what result. This expert provides only one result: it defines what the manipulated variable will be - xylene column steam ("xyl -- col -- steam"), MFB column steam ("MFB -- col -- steam"), or column feed ("column -- feed"). This logic results in the following rules:
TABLE 5______________________________________MANIPULATED --VARIABLE is MFB --COLUMN --STEAMWhileDirection --of --change is ADDand MFB --COL --STEAM is not MAXMANIPULATED --VARIABLE is XYL --COLUMN --STEAMWhileDirection --of --change is ADDand MFB --COL --STEAM is MAXand XYL --COL --STEAM is not MAXMANIPULATED --VARIABLE is COLUMN --FEED WhileDirection --of --change is ADDand MFB --COL --STEAM is MAXand XYL --COL --STEAM is MAXMANIPULATED --VARIABLE is XYL --COLUMN --STEAMWhileDirection --of --change is CUTand XYL --COL --STEAM is not MINMANIPULATED --VARIABLE is MFB --COLUMN --STEAMWhileDirection --of --change is CUTand XYL --COL --STEAM is MINand MFB --COL -- STEAM is not MINMANIPULATED --VARIABLE is COLUMN --FEED WhileDirection --of --change is CUTand XYL --COL --STEAM is MINand MFB --COL --STEAM is MIN______________________________________
Note that: (1) some of the conditions are negated, i.e. it is specified that a rule or condition must NOT have a certain value (MFB -- COL -- STEAM is NOT MIN). (2) More than one test can set the value of the same condition (MANIPULATED -- VARIABLE in this case). (3) More than one test can assign the same value to the same condition (i.e. the second and fourth both set MANIPULATED VARIABLE to XYL -- COL -- STEAM, under different conditions). By contrast, the retrieval rules each assign one of several descriptors to a name which is unique to that specific rule.
Finally, the expert must do something with its conclusion to change the way the supervisor acts. In this case, assume that there are three feedback blocks in the supervisor procedure, all having the Shewhart MFB deviation as measured variable, with aims of 0.0. One (#3) manipulates xyl -- COL -- steam, one (#4) MFB -- column steam, and one (#5) column feed rate. The supervisor procedure includes a FORTRAN callable function named ACS -- SELECT -- BLOCK, which allows only one block out of a set to take action. The others are "de-selected" and stand ready to act if selected. When ACS select block is called, the first block number in the argument list becomes selected, the others are deselected. Trailing zeros are ignored.
Thus, to enable the expert being built to change the control strategy, the following rules are added to the rule set:
______________________________________While MANIPULATED VARIABLE is XYL --COL --STEAM Thendo the FORTRAN statement:ACS --status = ACS --select --block ( 3, 4, 5, 0, 0, 0 )While MANIPULATED VARIABLE isMFB --COL --STEAMThendo the FORTRAN statement:ACS --status = ACS --select --block ( 4, 3, 5, 0, 0, 0 )While MANIPULATED VARIABLE isCOLUMN FEED Thendo the FORTRAN statement:ACS --status = ACS --select block ( 5, 3, 4, 0, 0, 0 )______________________________________
The foregoing data entries are all the inputs needed to define the expert system.
Within the supervisor procedure, an expert system can be developed for each block. Used in this way, the build-expert procedure will create the FORTRAN subroutine Blockn -- expert -- system (where n is the block number, i.e. the subroutines will be named BLOCK2 -- EXPERT -- SYSTEM etc.), compile it, and place it in the proper library so that it can be called from within a supervisor block (by a user routine).
Expert Rule Structure
This sample embodiment provides an example which may help clarify what an expert procedure does. Some more general teachings regarding expert system methods and structure will now be set forth.
FIG. 2 is a schematic representation of the organization preferably used for the knowledge base. Three main categories of rules are used, namely retrieval rules 210, analysis rules 220, and action rules 230.
Retrieval Rules
The retrieval rules 210 each will retrieve one or more quantitative inputs (which may be, e.g., sensor data 157 from one of the sensors 156, historical data 141 and/or laboratory measurements 162 from a historical data base 140, limits on variable values, goals 132 defined by the supervisor procedure 130, combinations of these, or other inputs). One of the significant advantages of the system described is that it provides a very convenient user interface for accessing quantitative inputs from a very wide range of sources: essentially any data object which can be reached by the host computer can be used. (The presently preferred embodiment uses DECnet and serial communication lines to link the computer which will be running the expert system with the various computers it may be calling on for data, but of course a wide variety of other networking, multiprocessor, and/or multitasking schemes could be used instead.)
In the presently preferred embodiment the retrieval rules are of two kinds: the simpler kind (referred to as "variable rules") will name one quantitative value (which may optionally be derived from several independently accessed quantitative inputs), and assign one of a predetermined set of descriptors (variable status values 222) to that name. Each of the more complex retrieval rules (referred to as "calculation rules") permits descriptors to be assigned selectively to a name in accordance with one or more calculated values (which may optionally be derived from a number of quantitative variables).
FIG. 3 shows the template used for a retrieval rule in the presently preferred embodiment, together with a sample of a retrieval rule which has been entered into the template. The areas in this drawing which are surrounded by dotted lines indicate the parts of the template which the user can modify, and which are preferably highlighted to the user in some fashion, e.g. by showing them in reverse video. In this example, the user has typed in the rule name as "xylene column steam." The build-expert software has automatically translated this rule name, by changing all the spaces in it to underscores, so that it appears as a one word name. (This can be conveniently used as part of a variable name in conventional computer languages.) Thus, the rule shown in FIG. 3, when translated into an expert procedure by the build-expert procedure, will define a set of variables whose names each begin with "XYLENE -- COLUMN -- STEAM."
For example, in the presently preferred embodiment the rule shown will translate into the following set of variables:
"XYLENE -- COLUMN -- STEAM -- STATUS" is a character variable (also known as a string or alphanumeric variable) which will have a string value which is either "MIN," "MAX," or "MID;"
"XYLENE -- COLUMN -- STEAM -- VALUE" will be a real variable, representing the quantitative value originally retrieved for the parameter;
"XYLENE -- COLUMN -- STEAM -- AGE" will be an integer variable representing the age of the quantitative value originally retrieved;
"XYLENE -- COLUMN -- STEAM -- ASTAT" will be a character variable which is defined to have values of "TOO -- OLD" or "OK," depending on whether the age value is within limits (note, for example, that this variable could easily be configured as a logical variable instead);
and "XYLENE -- COLUMN -- STEAM -- FIRED" will be a logical variable which indicates whether this particular rule has been fired (on a given pass).
In filling out the retrieval rule template, the user must fill in at least two of the classification blanks. However, in the presently preferred embodiment, only five classification ranges are permitted. (This limit could be changed, but there are significant advantages to permitting the user to input only a restricted number of ranges. Where the process control algorithm absolutely demands that the variable be classified into more ranges, two or more process variable rules could be used to label up to eight or more ranges.)
Another constraint used in the presently preferred embodiment is that the user must enter at least the first two open ended ranges. He may enter up to three bounded ranges, to provide a complete coverage of all cases, but he must enter at least two open ended range specifications.
In the presently preferred embodiment, the build-expert procedure checks to see that the ranges defined are comprehensive and non-overlapping, before the rule is permitted to be added to the rule base.
FIG. 4 shows an example of a different kind of retrieval rule, known as a calculation rule. The menu for this rule is (in the presently preferred embodiment) presented to the user as two screens. The user may specify up to ten quantitative inputs, of any of the types just referred to, as well as up to ten values arithmetically derived from these inputs (or constants). By having some of the derived values refer back to other ones that are derived values, quite complex formulas may be implemented. (One advantageous use of such formulas may be to relate off-line time-stamped laboratory measurements with the continuously-measured values of the same (past) time era, e.g. in a component material balance.) Moreover, notice that the variable values and calculated values thus assembled may be used not only to define a "key value" to be categorized, but also to define the limits of the various categories against which the key value is sought to be tested.
Analysis Rules
Analysis rules generally are used to embed the natural language reasoning as practiced by the domain expert. One important distinction between retrieval rules and analysis rules is that each retrieval rule has a unique name, but the analysis condition names defined by analysis rules are not necessarily unique. FIG. 5 shows an example of an analysis rule 220. Again, the portions of the template which the user can modify are shown inside dashed boxes. Note that the template preferably used defines an analysis condition name and assigns a descriptor to that analysis condition name if specific conditions are met. In the presently preferred embodiment, the only tests permitted are ANDed combinations of no more than five logical terms, each of which can consist only of a test for identity (or nonidentity) of two strings. Moreover, the string identity tests are preferably set up so that each of the comparisons either tests a retrieval rule name to see if a certain variable status value 212 was assigned by that rule, or tests an analysis condition name to see if a certain analysis status value 222 was assigned by one of the analysis rules. That is, as seen schematically in FIG. 2, there is potential for recursion among the analysis rules 220 considered as a group, since some of the analysis rules 220 can refer to the outputs of other analysis rules 220. Optionally the analysis rules could be sequenced so that there would never be any open-ended recursions, but in the presently preferred embodiment this extra constraint is not imposed.
Any one analysis condition name may (under various conditions) be assigned values by more than one analysis rule. That is, each analysis rule is preferably set up as an IF statement, and multiple such IF statements will typically be needed to specify the various possible values for any one analysis condition name.
In the presently preferred embodiment, the status of every analysis condition name and variable rule name are initially defined to be "unknown," and the logical comparisons are implemented so that no test will give a "true" result if one term of the comparison has a value of "unknown."
The order in which the analysis rules are executed may be of importance where an analysis condition name is multiply defined. That is, it may in some configurations be useful to permit the conditions of the various analysis rules 220 to be overlapping, so that, under some circumstances, more than one analysis rule may find a true precondition and attempt to assign a status value to the same analysis condition name. In this case, the sequence of execution of the analysis rules 220 can optionally be allowed to determine priority as between analysis rules. However, as mentioned above, this is not done in the presently preferred embodiment.
Moreover, more than one analysis rule may assign the same analysis status value 222 to the same analysis condition name, under different circumstances.
It can be advantageous, for purposes of documenting the reasoning embedded in the expert system, to give names to the analysis rules which include both the name and descriptor possibly linked by that rule: thus, for instance, a rule which is able to conclude that column operation is normal might be named "COLUMN -- OP -- NORMAL."
Action Rules
FIG. 6 shows the presently preferred embodiment of the template for action rules, and an example of one action rule which has been stated in this format. Again, the portions of the template which the user can modify are indicated by dashed boxes.
The user has chosen to name this particular action rule "Change Xylene Steam," which the build-expert software has translated into CHANGE -- XYLENE -- STEAM (for incorporation into various variable names such as "CHANGE -- XYLENE -- STEAM -- FIRED"). The names assigned to action rules are primarily important for documentation, so that, when this user or another user looks back through the rule base, the use of clear rule names for action rules will help to understand what the structure of the expert system's inference chaining is. In fact, it may be advantageous, as in the example shown, to generally pick analysis status values 222 which have fairly descriptive names, and then, to the extent possible, name the action rules identically with the corresponding analysis status values.
Note also that the action rules can refer back to a variable status value 212 as well as to an analysis status value 222.
Thus, in the presently preferred embodiment the action rules embody an absolute minimum of logic. They are used primarily as a translation from descriptive key words embedded within the inference chaining structure to the actual executable statements (or command procedures) which specify the action to be taken. Thus, one way to think about the advantages of the expert system organization preferably used is that the emulation of natural language reasoning is concentrated as much as possible in the analysis rules, while the retrieval rules are used to provide translation from quantitative measurements into input usable with natural language inference rules, and the action rules are used almost exclusively to provide translation from the natural language inference process back to executable command procedures which fit in well with the computer system used.
Each of the action rule templates also gives the user several choices for the action to be taken to implement the action rule if its precondition is met. The user can either insert an executable statement (in FORTRAN, in the presently preferred embodiment) or insert a pointer to a command procedure, or simply have the action rule send advisory messages. The third option is useful for debugging, since the expert can be observed to see what actions it would have taken, without risking costly errors in the actual control of the system.
In the example shown, an executable FORTRAN statement is used, but the statement specified merely passes an action code back to the supervisor process. In the example shown in FIG. 6, the procedure call given will cause the supervisor procedure to turn on the block whose number is given first, and turn off all other blocks whose numbers are given. Thus, the statement
acs.sub.-- status=acs.sub.-- select.sub.-- block (3, 4, 5, 0, 0, 0)
would change the status of block 3 to "on-selected" (assuming that it did not need to be initialized), and would set the status values of blocks 4 and 5 to "ondeselected." Thus, when the expert system has completed running, the supervisor procedure which called the expert procedure as a subroutine can selectively execute block functions depending on the values passed back to it by the subroutine.
Thus, the action rules permit a very large variety of actions to be performed. For example, one optional alternative embodiment provides synthetic-speech output; optionally this can be combined with a telephone connection, to permit dial-out alert messages (e.g. to a telephone number which may be selected depending on the time of day shown by the system clock, so that appropriate people can be notified at home if appropriate).
Another optional embodiment permits an action rule to call up a further sub-expert. This might be useful, for example, if one expert subprocedure had been customized to handle emergency situations - who should be called, what should be shut down, what alarms should be sounded.
Generating the Expert Procedure
After the user has input as many rule statements as needed, or has modified as many of an existing set of rule templates as he wishes to, he can then call the generate code option to translate the set of templates 115, including the user inputs which have been made into the rule templates, to create the expert system 120.
Generating Source Code
As a result of the constraints imposed in the various rule templates, the translation from the constrained format of the templates is so direct that the executable rules can be generated simply by a series of appropriate string-equivalent tests, string-append operations, logical-equivalence tests, arithmetic operations, and fetches.
Preferably three passes are performed: the first does appropriate character type declarations; the second loads the appropriate initializations for each rule; and the third translates the inference rules themselves.
An example of the initialization steps is seen in initialization of the analysis rules: an initial value such as "dont -- know" is assigned to each condition name, and the equivalence tests are redefined slightly by the translation procedure, so that, until some other value is assigned to the name by another rule, the statement
"name"="descriptor"
will be evaluated as false, and the statement
NOT("name"="descriptor")
will also be evaluated as false.
Sample Source Code
A portion of the source code for the procedure which actually performs this function, in the presently preferred embodiment, is as follows.
TABLE 6__________________________________________________________________________C*************************************C Build --expert.forCC Routine to generate FORTRAN expert system code usingC the process rulebase.CCC**************************************C Subroutine Build --expertC Include `pace$includes:Variable --rule --params.inc` Include `pace$includes:Expert --data.inc` Include `pace$includes:Analysis --commons.inc` Include `pace$includes:Analysis --rule.inc` Include `pace$includes:Action --commons.inc` Include `pace$includes:Action --rule.inc` Include `pace$includes:Action --params.inc`CLogical FirstLogical No --moreCharacter*25 Last --condCharacter*80 code --dir --fileCharacter*80 DirectoryInteger*2 L --dir.Character*39 Subroutine --nameCharacter*14 Subprocess --nameCharacter*3 CblockInteger*2 L --spCharacter*1 Search --stringInteger*2 SrlenC Call Fdv$Putl(` Generating Expert System code . . . `)CC...Rewind the code fileCd write(6,*) ` will rewind code file` Rewind ( Unit = Code --lun ) Next -- label = 2CC...Get the name of the expert system code file, pick out the C subrname from itCd Call Fdv$putl ( `Will translate logicals.`) Call Lib$sys --trnlog ( `PACE$RULES` ,, Directory ,,,) Call Lib$sys --trnlog ( `PACE$CODE` ,, Code --dir --file ,,,)d Call Fdv$putl ( `Did translate logicals.`) Istart = Index ( Code --dir --file, `]` ) Subroutine --name = Code --dir --file(Istart+1:80)//Blankd Call Fdv$putl ( `Will get index of ".".`) Iend = Index ( Subroutine --name, `.` )d Call Fdv$putl ( `Will clip subrout name.`) If ( Iend .gt. 1 ) Then Subroutine --name = Subroutine --name(1:Iend-1)//Blank Else Subroutine --name = `Expert`//Blank End Ifd Call Fdv$putl ( `Will trim subroutine name.`) Call Str$trim ( Subroutine --name, Subroutine --name, Srlen )d Write ( 6, 100 ) Subroutine --name Write ( Code --lun, 100 ) Subroutine --nameCC...construct a sub-process nameCIf ( Subroutine --name(1:5) .eq. `BLOCK` ) Thend Call Fdv$putl(`Is block.`)d Call Fdv$wait ( It ) Read ( Subroutine --name(6:8), `(I3)` ,err= 91 ) Iblockd Call Fdv$putl(`Is > 99.`)d Call Fdv$wait ( It ) Liblock = 3 Go To 93 91 Read ( Subroutine --name(6:7), `(I2)` ,err= 92 ) Iblockd Call Fdv$putl(`Is > 9.`)d Call Fdv$wait ( It ) liblock = 2 Go To 93 92 Read ( Subroutine --name(6:6), `(I1)` ,err= 93 ) Iblockd Call Fdv$putl(`Is < 10.`)d Call Fdv$wait ( It ) Liblock = 1 Go To 93 93 Write ( Cblock, ` (I3)` ) Iblock Istart = 4 - Liblock Subprocess --name = `B`//Cblock(Istart:3)//` --` L --sp = 3 + LiblockElse L --sp = 1End IfC100 Format( 1 ` Options /Extend --source`, /, 1 `C********************************************`,/, 1 `C`,/, 1 `C Expert System Code`,/, 1 `C`,/, 1 `C********************************************`,/, 1 `C`, /, 1 ` Subroutine `, A, /, 1 `C` , / ,1 ` Include "ACS$includes:ACSserv.inc" ` , / ,1 ` Include "ACS$includes:ACSstatus.inc" ` , / ,1 ` lnclude "ACS$includes:Sys --functions.inc" ` , / ,1 ` Include "($Jpidef)" ` , / ,1` Integer*4 Vss$ --to --ascii --time` , / ,1 ` Integer This --pass -- fires` , / ,1 ` Character*25 Unknown` , / ,1 ` Parameter Unknown = "Unknown ')`1 ` Character*25 OK` , / ,1 ` Parameter ( OK = "OK ")` , / ,1 ` Character*25 Too --old` , / ,1 ` Parameter ( Too --old = "Too --old ")`1 ` Integer*4 Now` , / ,1 ` Integer*4 Then` , / ,1 ` Character*18 C --now` , / ,1 ` Integer*4 Itemlist(4)` , / ,1 ` Integer*2 Code(2)` , / ,1 ` Equivalence ( Itemlist(1) , Code(1) )`, / ,1 ` Integer*4 Mode` , / ,1 ` Integer*2 Len` , / ,1 ` Character*80 Line` , / ,1 `C`1 )d write(6,*) ` wrote header info.`CC..Make declaration code for variable rulesCC First = .True.1 ContinueCC..Read A ruleCCall Read --var --rule --params ( First , No --more )If ( No --more ) Go To 200CC..Write out FORTRAN declarationsCCall Str$trim ( Rule --name , Rule --name , Len )Write ( Code --lun , 101 ) (Rule --name(1:len) , J=1,5 )101 Format (1 ` Real*4 ` , A , ` --value` , / ,1 ` Integer*4 ` , A , ` --age` , / ,1 ` Character*25 ` , A , ` --stat` , / ,1 ` Logical*1 ` , A , ` --fired` , / ,1 ` Character*10 ` , A , ` --astat` , / ,1 `C`1 )CGo To 1C200 ContinueCC..Make declaration code for calculation rulesCCall Declare --calc --rulesCC..Make declaration code for analysis rulesCCLast --cond = ` `First = .True.2 ContinueCC..Read A ruleCCall Read --anal --rule --params ( First , No --more )If ( No --more ) Go To 201CC..Write out FORTRAN declarationsCCall Str$trim (An --cond --name , An --cond --name , Len )Call Str$trim (An --rule --name , An --rule --name , ILen )Write ( Code --lun , 104 )If ( An --cond --name .ne. Last --cond )1 Write ( Code --lun , 102 ) (An --cond --name(1:len) )Write ( Code --lun , 103 ) (An --rule --name(1:Ilen) )Last --cond = An --cond --name102 Format ( 1 ` Character*25 ` , A , ` --stat` 1 )103 Format ( 1 ` Logical*1 ` , A , ` --fired` 1 )104 Format ( 1 `C` 1 )CGo To 2C201 ContinueCC..Make declaration code for action rulesCC First = .True.252 ContinueCC..Read A ruleCCall Read --action --rule --params ( First , No --more )If ( No --more ) Go To 251CC..Write out FORTRAN declarationsCCall Str$trim ( Ac --rule --name , Ac --rule --name , Len )Write ( Code --lun , 262 ) Ac --rule --name(1:len)262 Format (1 ` Logical*1 ` , A , ` --fired` , / , 1 `C` 1 )C Go To 252C 251 ContinueCCC...Now Write Initialization codeCWrite ( Code --lun , 401 ) Subroutine --name (1:Srlen)401 Format ( 1 `C` , / , 1 `C Initialize the status values.` , / , 1 `C` , / , 1 ` Van --status = Vss$ --from --ascii --time ( " " , Now )` , / 1 ` Van --status = Vss$ --to --ascii --time ( Now , C --Now )` , / , 1 ` Code(1) = 4 1 ` Code(2) = jpi$ --mode` , / , 1 ` Itemlist(2) = %loc(Mode)` , / , 1 ` Itemlist(3) = %loc(Len` , / , 1 ` Itemlist(4) = o` , / , 1 ` sys --status = sys$getjpiw ( ,,,Itemlist,,,)` , / , 1 `d Write(6,901) C --now` , / , 1 `901 Format ( / , " Running ` , A , ` at " , A )`, / , 1 `C` 1 )CC....Initialize variable rules - This will set logical flags false andC retrieve the necessary data for the rule.C First = .True. 402 ContinueCCC..Read A ruleC Call Read --var --rule --params ( First , No --more ) If ( No --more ) Go To 420C Call Str$trim ( Rule --name , Rule --name , Len ) Write ( Code --lun , 403 ) ( Rule --name(1:Len) , J =1,4 ) 403 Format ( 1 `C` , / , 1 `C....` , A , ` rule initialization` , / , 1 `C` , / , 1 ` ` , A , ` --astat = Unknown` , / ,1 ` ` , A , ` --stat = Unknown` , / ,1 ` ` , A , ` --fired = .False.` )CIf ( Ret --meth .eq. Current --val ) Then Write ( code --lun , 404 ) Var --num , (Rule --name(1:len),J=1,2)404 Format (1 ` Call Get --cur --data ( ` , I4 , ` , ` , A , ` --value , `` --age)`1 )Else If ( Ret --meth .eq. Discrete --avg ) Then Write ( code --lun , 405 ) Ret --time , Var --n(Rule --name(1:len), J=1,2)405 Format (1 `C` , / ,1 ` then = Now + ` ,I12 , / ,1 ` Call Get --disc --avg --data ( ` , I4 , ` , ` , A , ` --valueA,` --age , Then , Now )`1 )Else If ( Ret --meth .eq. Time --wt --avg ) Then Write ( code --lun , 406 ) Ret --time , Var --n(Rule --name(1:len),J=1,2)406 Format (1 `C` , / ,1 ` Then = Now + ` , I12 , / ,1 ` Call Get --time --wt --avg --data ( ` , I4 , ` , ` , A , ` --val, A, ` --age , Then , Now )`1 )Else If ( Ret --meth .eq. Sec --last --vant --point ) Then Write ( code --lun , 411 ) Var --num ,1 Rule --name(1:len)411 Format (1 `C` , / ,1 ` Call Get --sec --last --vant --point ( ` , I4 , ` , ` , A , `, Itime --stamp )`1 )Else If (Ret --meth .eq. ACS --ff --delta ) Then Write ( code --lun , 407 ) Var --num , Rule --name(1:len)407 Format (1 `C` , / ,1 ` ACS --status = ACS --get, --FF --delta ( ` , I4 , ` , ` , A , `)`1 )Else If ( Ret --meth .eq. ACS --fb --error ) Then Write ( code --lun , 408 ) Var --num , Rule --name(1:len)408 Format (1 `C` , / ,1 ` ACS --status = ACS --get --fb --error ( ` , I4 , ` , ` , A , `)`1 )Else If ( Ret --meth .eq. PCS --DMT --loop --goal ) Then Write ( code --lun , 409 ) Var --num , Rule --name(1:len)409 Format (1 `C` , / ,1 ` ACS --status = ACS --get --PCS --goal ( "DMT " , ` ,1 I , ` , ` , A , ` --value )`1)Else If ( Ret --meth .eq. PCS --TPA --loop --goal ) Then Write ( code --lun , 410 ) Var --num , Rule --name(1:len)410 Format (1 `C` , / ,1 ` ACS --status = ACS --get --PCS --goal ( "TPA " , ` ,1 I , ` , ` , A , ` --value )`1 )Else Write( Code --lun , * ) `C....Bad retrieval method` End IfC Write ( Code --lun , 510 ) (Rule --name(1:len),J=1,2)510 Format ( 1 `d Write(6,*) " ` , A , ` --value = " , ` , A , ` --value`C Go To 402C420 ContinueCC....Initialize calculation rulesCCall Init --calc --rules CC....Initialize analysis rulesCLast --cond = ` `First = .True.440 ContinueCCC..Read A ruleCCall Read --anal --rule --params ( First , No --more )If ( No --more ) Go To 450C Call Str$trim ( An --cond --name , An --cond --name , Len ) Call Str$trim ( An --rule --name , An --rule --name , Ilen ) Write ( Code --lun , 441 ) ( An --rule --name(1:ILen) , J =1,2 ) If ( An --cond --name .eq. Last --cond ) Go To 440 Last --cond = An --cond --name Write ( Code --lun , 442 ) ( An --cond --name(1:Len) , J =1,1 ) 441 Format ( 1 `C` , / , 1 `C....` , A , ` rule initialization` , / , 1 `C` , / , 1 ` ` , A , ` --fired = .False.` ) 442 Format ( 1 ` ` , A , ` --stat = Unknown` )C Go To 440C 450 ContinueCC....Initialize action rulesC First = .True.460 ContinueCCC..Read A ruleC Call Read --action --rule --params ( First , No --more ) If ( No --more ) Go To 490C Call Str$trim ( Ac --rule --name , Ac --rule --name , Len ) Write ( Code --lun , 461 ) ( Ac --rule --name(1:Len) , J =1,2 ) 461 Format ( 1 `C` , / , 1 `C....` , A , ` rule initialization` , / , 1 `C` , / , 1 ` ` , A , ` --fired = .False.` )C Go To 460 490 ContinueC 500 ContinueCC...Write the rule codeC Write ( Code --lun , 501 )501 Format ( 1 `C` , / , 1 ` 1 Continue` , / , 1 `C` , / , 1 ` This --pass --fires = 0` , / , 1 `C` 1 )CCC...Write out variable rule codeC First = .True.C 502 ContinueCC..Read A ruleC Call Read --var --rule --params ( First , No --more ) If ( No --more ) Go To 600C Call Str$trim ( Rule --name , Rule --name , Len )C If ( Age --limit .eq. Empty ) Age --limit = -365*24*60*60C Write ( Code --lun , 299 ) ( Rule --name(1:len),J=1,3) , Abs(Age -- 1 ( Rule --name(1:len),J=1,2)299 Format ( 1 `C` , / , 1 `C....` , A , ` Rules ` , / , 1 `C` , / , 1 ` If ( ` , / 1 ` 1 ( ` , A , ` --astat .eq. Unknown ) .and. ` , / , 1 ` 1 ( ` , A , ` --age .le. ` , I, ` ) ` , / , 1 ` 1 ) Then ` , / , 1 ` ` , A , ` -- astat = OK ` , / , 1 `d Write(6,*) ``` , A , ` --age is OK.``` , / , 1 ` This --pass --fires = This --pass --fires + 1` , / , 1 ` End If` 1 )C Write ( Code --lun ,Fmt=298 ) ( Rule --name(1:len),J=1Abs(Age --limit) , 1 ( Rule --name(1:len),J=1,2)298 Format ( 1 `C` , / , 1 ` If ( ` , / , 1 ` 1 ( ` , A , ` --astat .eq. Unknown ) .and. ` , / , 1 ` 1 ( ` , A , ` --age .gt. ` , I , ` ) ` , / , 1 ` 1 ) Then ` , / , 1 ` ` , A , ` --astat = Too --old` , / , 1 `d Write(6,*) ``` , A , ` --age is Too --old.``` , / , 1 ` This --pass --fires = This --pass --fires + 1` , / , 1 ` End If` 1 )C Write( code --lun , 505 ) (Rule --name(1:len),J=1,3) , Log --op1 ,` 1 Rule --name(1:len) , Status1 , Rule --name(1:len), 1 Status1 , Rule --name(1:len)505 Format ( 1 `C` , / ,1` If ( ` , / ,1 ` 1 ( .not. ` , A , ` --fired ) .and. ` , / ,1 ` 1 ( ` , A , ` --astat .eq. OK ) .and. ` , / ,1 ` 1 ( ` , A , ` --value ` , A4 , ` ` , F12,5 , ` ) ` ,1 ` 1 ) Then ` , / ,1 ` ` , A , ` --stat = ```, A25 , ```` , / ,1 `d Write(6,*) ``` , A , ` --stat is ` , A , ```` , / ,1 ` ` , A , ` --fired = .True.` , / ,1 ` This --pass --fires = This --pass --fires + 1` , / ,1 ` End If`1 )C Write( code --1un , 506 ) (Rule --name(1:len),J=1,3) , Log --op8 ,` 1 Rule --name(1:len) , Status8 , Rule --name(1:len) , 1 Status8 , Rule --name(1:len)506 Format ( 1 `C` , / , 1 ` If ( ` , / , 1 ` 1 ( .not. ` , A , ` --fired ) .and. ` , / , 1 ` 1 ( ` , A , ` --astat .eq. OK ) .and. ` , / , 1 ` 1 ( ` , A , ` --value ` , A4 , ` ` , F12.5 , ` ) ` , 1 ` 1 ) Then ` , / , 1 ` ` , A , ` --stat = ```, A25 ,```` , / , 1 `d Write(6,*) ``` , A , ` --stat is ` , A , ```` , / , 1 ` ` , A , ` --fired = .True. ` , / , 1 ` This --pass --fires = This --pass --fires + 1` , / , 1 ` End If` 1 )C If ( Status2 .ne. ` ` ) ThenC Write( code --lun , 508 ) (Rule --name(1:len),J=1,3) , Log --op2 ,` 1 Rule --name(1:len) , Log --op3 , Limit3 , 1 Rule --name(1:len) , Status2 , Rule --name(1:len) , 1 Status2 , Rule --name(1:len)508 Format ( 1 `C` , / , 1 ` If ( ` , / , 1 ` 1 ( .not. ` , A , ` --fired ) .and. ` , / , 1 ` 1 ( ` , A , ` --astat .eq. OK ) .and. ` , / , 1 ` 1 ( ` , A , ` --value ` , A4 , ` ` , F12.5 , ` ) .and` 1 ` 1 ( ` , A , ` --value ` , A4 , ` ` , F12.5 , ` )` , 1 ` 1 ) Then ` , / , 1 ` ` , A , ` --stat = ```, A25 ,```` , / , 1 `d Write(6,*) ``` , A, ` --stat is ` , A , ```` , / 1 ' ` , A , ` --fired = .True. ` , / , 1 ` This --pass --fires = This --fires + 1 ` , / , 1 ` End If` 1 )End IfC If ( Status4 .ne. ` ` ) ThenC Write( code --lun , 509 ) (Rule --name(1:len),J=1,3) , Log --op4 ,` 1 Rule --name(1:len) , Log --op5 , Limit5 , 1 Rule --name(1:len) , Status4 , Rule --name(1:len) , 1 Status4 , Rule --name(1:len)509 Format ( 1 `C` , / , 1 ` If ( ` , / , 1 ` 1 ( .not. ` , A , ` --fired ) .and. ` , / , 1 ` 1 ( ` , A , ` --astat .eq. OK ) .and. ` , / , 1 ` 1 ( `, A , ` --value ` , A4 , ` ` , F12.5 , ` ) .and` 1 ` 1 ( ` , A , ` --value ` , A4 , ` ` , F12.5 , ` ) ` , 1 ` 1 ) Then ` , / , 1 ` ` , A , ` --stat = ```, A25 , ```` , / , 1 `d Write(6,*) ``` , A , ` --stat is ` , A , ```` , / , 1 ` ` , A , ` --fired = .True. ` , / , 1 ` This --pass --fires = This --pass --fires + 1` , / , 1 ` End If` 1 ) End IfC If ( Status6 .ne. ` ` ) ThenC Write( code --lun , 511 ) (Rule --name(1:len),J=1,3) , Log --op6 ,` 1 Rule --name(1:len) , Log --op7 , Limit7 , 1 Rule --name(1:len) , Status6 , Rule --name(1:len) , 1 Status6 , Rule --name(1:len)511 Format ( 1 `C` , / , 1 ` If ( ` , / , 1 ` 1 ( .not. ` , A , ` --fired ) .and. ` , / , 1 ` 1 ( ` , A , ` --astat .eq. OK ) .and. ` , / , 1 ` 1 ( ` , A , ` --value ` , A4 , ` ` , F12.5 , ` ) .and` 1` 1 ( ` , A , ` --value ` , A4 , ` ` , F12.5 , ` ) ` , 1 ` 1 ) Then ` , / , 1 ` ` , A , ` --stat = ```, A25 , ```` , / , 1 `d Write(6,*) ``` , A , ` --stat is ` , A , ```` , / , 1 ` ` , A , ` -- fired = .True. ` , / , 1 ` This --pass --fires = This --pass --fires + 1` , / , 1 ` End If` 1 ) End IfC Go To 502C600 ContinueCC...Write out calculation rule codeCCall Write --calc --rulesCC...Write out analysis rule codeCFirst = .True.C602 ContinueCC..Read A ruleC Call Read --anal --rule --params ( First , No --more ) If ( No --more ) Go To 700CC Call Str$trim ( An --cond --name , An --cond --name , Len ) Call Str$trim ( An --rule --name , An --rule --name , ILen ) Write ( Code --lun , 699 ) (An --rule --name(1:llen),j=1,2)699 Format ( 1 `C` , / , 1 `C....` , A , ` Rules ` , / , 1 `C` , / , 1 ` If ( ` , / , 1 ` 1 ( .not. ` , A , ` --fired ) .and. ` 1 )CIf ( An --rule1 .ne. ` ` ) Then Call Str$trim ( An --rule1 , Len )C If ( An --not1 .eq. `.NOT.` ) Then Write( code --lun , 1001 ) An --rule1(1<len) End If1001 Format ( 1 ` 1 ( .not. (` , A , ` --stat .EQ. Unknown ) ) .and.` 1 ) Write( code --lun , 608 ) An --not1 , An --rule1(1:len) , 1 An --status1608 Format ( 1 ` 1 ( ` , A , ` ( ` , A , ` --stat .EQ. ``` , A , `.and.` 1 ) End IfCIf ( An --rule2 .ne. ` ` ) Then Call Str$trim ( An --rule2 , An --rule2 , Len )C If ( An --not2 .eq. `.NOT.` ) Then Write( code --lun , 1001 ) An --rule2(1:len) End If Write( code --lun , 609 ) An --not2 , An --rule2(1:len) , 1 An --status2609 Format ( 1 ` 1 ( ` , A , ` (` , A , ` --stat .EQ. ``` , A , `.and.` 1 ) End IfCIf ( An --rule3 .ne. ` Call Str$trim ( An --rule3 , An --rule3 , Len )C If ( An --not3 .eq. `.NOT.` ) Then Write( code --lun , 1001 ) An --rule3(1:len) End If Write( code --lun , 610 ) An --not3 , An --rule3(1:len) , 1 An --status3610 Format ( 1 ` 1 ( ` , A , ` ( ` , A , ` --stat .EQ. ``` , A , `.and.` 1 ) End IfCIf ( An --rule4 .ne. ` ` ) Then Call Str$trim ( An --rule4 , An --rule4 , Len )C If ( An --not4 .eq. `.NOT.` ) Then Write( code --lun , 1001 ) An --rule4(1:len) End If Write( code --lun, 611 ) An --not4 , An --rule4(1:len) , 1 An --status4611 Format ( 1 ` 1 ( ` , A , ` ( ` , A , ` --stat .EQ. ```, A , `.and.` 1 ) End IfCIf ( An --rule5 .ne. ` ` ) Then Call Str$trim ( An --rule5 , An --rule5 , Len )C If ( An --not5 .eq. `.NOT.` ) Then Write( code --lun , 1001 ) An --rule5(1:len) End If Write( code --lun , 612 ) An --not5 , An --rule5(1:len) , 1 An --status5612 Format ( 1 ` 1 ( ` , A , ` ( ` , A , ` -- stat .EQ. ``` , A , `.and.` 1 ) End IfC Call Str$trim ( An --cond --name , An --cond --name , Len ) Write ( Code --lun , 613 ) 1 (An --cond --name(1:len),j=1,1) , An --end --status , 1 (An --cond --name(1:len),j=1,1) , An --end --status , 1 (An --rule --name(1:Ilen),j=1,1)613 Format ( 1 ` 1 ( .True. ) ` , / , 1 ` 1 ) Then ` , / ,1 ` ` , A, ` --stat = ```, A25 , ```` , / ,1 `d Write(6,*) ``` , A , ` --stat is ` , A , ```` , / , This --pass --fires = This --pass --fires + 1` , / ,1 ` End If`1 )CGo To 602C700 ContinueCCC...Write out action rule codeC First = .True.C 702 ContinueCC..Read A ruleC Call Read --action --rule --params ( First , No --more ) If ( No --more ) Go To 800CC Call Str$trim ( Ac --rule -- name , Ac --rule --name , Len ) Write ( Code --lun , 799 ) (Ac --rule --name(1:len),j=1,2) 799 Format ( 1 `C` , / , 1 `C....` , A , ` Rules ` , / , 1 `C` , / , 1 ` If ( ` , / , 1 ` 1 ( .not. ` , A , ` --fired ) .and. ` 1 )C Call Str$trim ( Ac --rule1 , Ac --rule1 , Len )C Write( code --lun , 708 ) Ac --rule1(1:len) , 1 Ac --status1708 Format ( 1 ` 1 ( ` , ` ( ` , A , ` --stat .EQ. ``` , A , ``` ) ) ` 1 )CC Call Str$trim ( Ac --rule --name , Ac --rule --name , Len ) Write ( Code --lun , 713 ) (Ac --rule --name(1:len),j=1,2)713 Format ( 1 ` 1 ) Then ` , / ,1 `d Write(6,*) "Doing action rule ` , A , ```` , / ,1 ` ` , A , ` --fired = .True.` , / ,1 ` This --pass --fires = This --pass --fires + 1`1 )CCall Str$trim ( Ac --data --line , Ac --data --line , Len )If ( Iac --type .eq. Exec --fort --statement ) Then Write ( code --lun , 714 ) Ac --data -- line(1:Len)714 Format (1 ` ` , A1 )Else If ( Iac --type .eq. Exec --dcl --precedure ) Then Subprocess --name(L --sp:14) = Ac --rule --name Call Str$trim ( Subprocess --name , Subprocess --name , ILen ) Write ( code --lun , 715 ) Ac --data --line(1:Len) ,1 Subprocess --name(1:Ilen)715 Format (1 ` Call Lib$spawn ("@` , A , ```,,,, ``` , A , ``` ,,,,,1 )Else If ( Iac --type .eq. Send --vaxmail --msg ) Then Call Str$trim ( Ac --rule --name , Ac --rule --name , Len ) Call Str$trim ( Directory , Directory , L --dir ) Subprocess --name(L --sp:14) = Ac --rule --name Call Str$trim ( Subprocess --name , Subprocess --name , ILen ) Write(Code -- lun , 788 )788 Format (1 ` If ( Mode .eq. Jpi$k --other ) Then`1 ) Write ( code --lun , 718 ) Directory(1:L --dir) ,1 Ac --rule --name(1:len) ,1 Subprocess --name(1:Ilen)718 Format (1 ` Call Lib$spawn ( "@` , A , A , `.mailmsg",,,,``` , A,,,,,,,)` 1 ) Write(Code --lun , 787 )787 Format (1 ` Else if ( Mode .eq. Jpi$k --interactive ) Then`1 ) Write ( Code --lun , 789 ) Directory(1:L --dir) ,1 Ac --rule --name(1:len) , Next --label, Next --label Next --label = Next --label + 1789 Format (1 ` Open( 11,File=``` , A , A , ` . mailmsg`` ,Status="old"1 ` Do J = 1,3 ` ,/,1 ` Read ( 11 , "(A)" ) Line` ,/,1 ` End Do` ,/,1 ` Do J = 1,60` ,/,1 ` Read (11 , "(A)" , End = `, I4 , ` ) Line ` ,/,1 ` Write(6,*) Line ` ,/,1 ` End Do` ,/,1 I4 ,` Continue` ,/,1 ` Close ( 11 )1 ) Write(Code --lun , 786 )786 Format (1 ` End If`1 )CElse Write ( code --lun , 716 )716 Format (1 ` Write(6,*) "Bad Action type. "`1 )End IfC Write ( Code --lun , 717 )717 Format ( 1 ` End If` 1 )C Go To 702C 800 ContinueC Write( Code --lun , 9998 )9998 Format ( 1 `d Write(6,*) This --pass --fires," rules fired this pass.`` 1 ` If ( This --pass --fires .gt. 0 ) Go To 1` , / , 1 `C` , / , 1 ` Return` , / , 1 ` 1 ) Call Fdv$Putl(` Generating Expert System code.... Done.`) Return End__________________________________________________________________________
Copyright (c) 1987 E.I. duPont de Nemours & Co., all rights reserved.
Thus, steps such as those listed above will produce (in this example) FORTRAN source code which defines an expert system including rules as defined by the user. This source code can then be compiled and linked, as described above, to provide an expert procedure which is callable at run-time. This expert procedure is tied into the supervisor procedure, as described above, by inserting an appropriate call into the user program section of one of the blocks in the supervisor procedure. Thus, the expert procedure can be called under specific circumstances (e.g. if selection among several possible manipulated variables must be made), or may optionally be called on every pass of the base cycle procedure, or at fixed time intervals, or according to any of the other options set forth above.
As will be recognized by those skilled in the art, the innovative concepts described in the present application can be modified and varied over a tremendous range of applications, and accordingly their scope is not limited except by the allowed claims.
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An expert system wherein the rules are of three classes: (1) retrieval rules, which each associate one of several attributes to an object in accordance with the values of inputs; (2) analysis rules, which selectively associate an attribute with an object, and which are somewhat analogous to the natural-language inference rules which would be used in communications between domain experts; and (3) action rules, which selectively carry out the output and control actuation options, based on the attributes associated with objects by the other rules.
Preferably only the action rules can enable execution of an external command procedure. Preferably each of each of the action rules requires no logical operations other than a test for association between an attribute and an object. Preferably none of the action rules can associate an attribute with an object. Preferably only the retrieval rules include numeric operations.
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CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of U.S. application Ser. No. 13/955,149 filed on Jul. 31, 2013 and entitled “METHOD OF MANUFACTURING ELECTRONIC PACKAGE MODULE”, now in condition for allowance.
BACKGROUND
1. Field of the Invention
The instant disclosure relates to an electronic module and method of making the same; in particular, to an electronic module having selective molding and method making the same.
2. Description of Related Art
Conventional electronic module includes a plurality of electronic components disposed on a circuit board. In addition, the electronic component modules may include molding material to encapsulate the electronic components for protection.
However, some electronic components like connectors or optoelectronics are not suitable for encapsulation, for example, the CMOS image sensor (CIS), charge-coupled device (CCD), and light emitting diode (LED). In order to protect some electronic components and remain the function of other components that are not suitable for encapsulation, a “partial molding” is then developed.
Conventional “partial molding” is achieved by mold chase, and the molding material is added to form the molding member. However, because of fluid adhesion, the molding material tends to form air bubbles or void at the mold cavity or the gap between the components and the circuit board. The air bubbles or the voids with moisture and in the following heating process they may cause “popcorn” issue which leads to low yield rate. Furthermore, after molding is completed by the mold chase, the mold chase has to be removed. For removing the mold chase, a draft angle has to be preserved when designing the mold chase. Typically, the acute angle between the mold and the circuit board is approximately 70 degree which reduces the overall usage of the printed circuit board. Moreover, whenever there is a different configuration, such as irregular shape of the molding, the mold chase has to be redesigned. Therefore, the cost is increased and the design consideration of mold chase becomes more complicated.
BRIEF SUMMARY OF THE INVENTION
The instant disclosure provides an electronic module and method of making the same for selective molding electronic components.
According to one embodiment of the instant disclosure, the method includes: providing a circuit substrate. The circuit substrate includes a first surface, at least one first ground pad and a first predetermined area disposed on the first surface. Then, a first tape is formed onto the first predetermined area. Next, at least one electronic component is disposed outside the first predetermined area. After then, a first molding member is formed. The first molding member covers the first tape and the electronic components. Subsequently, the first molding member and the first tape above the first predetermined area are removed.
In the step of forming the tape on the predetermined area, a tape is attached on the entire circuit substrate. Then, laser is used to trench the tape above the ground pad. Subsequently, the tape outside the first predetermined area is removed, such that in the predetermined area, the tape remains.
In the step of removing the molding member, laser may be used to trench the molding member above the ground pad that surrounds the predetermined area.
In the step of removing the molding member, laser may be used to trim the molding member above the predetermined area.
In the step of removing the tape above the predetermined area, heating may be used to facilitate the process.
The tape may be UV tape. In the step of removing the tape above the predetermined area, UV light may be used to shine on the tape and removed thereby.
The method of manufacturing the electronic module may further includes disposing the optoelectronic, connector or the like that are not suitable to be encapsulated on the predetermined area. According to an embodiment, after the removal of the tape, a mask layer is formed within the predetermined area and not covers the ground pad, and further formed the EMI shielding layer entirely and electrically connected to the ground pad. Then the mask layer is removed, and the optoelectronic is disposed on the predetermined area. After laser trenches the molding member above the ground pad, the entire area is formed with EMI shielding layer. The EMI shielding layer and the ground pad are electrically connected, and the tape in the predetermined area is then removed. The optoelectronic is subsequently disposed on the predetermined area.
The circuit substrate may further include side ground pads, and the EMI shielding layer and the side ground pad are electrically connected.
The electronic module of the instant disclosure may further include a circuit substrate, electronic components, molding members, an EMI shielding layer, optoelectronics and side ground pads. The circuit substrate includes a surface, ground pad and a predetermined area. The predetermined area and the ground pad are disposed on the surface. The electronic components are disposed on the surface outside the predetermined area. The molding member encapsulates the electronic components and each side of the molding member and the surface form an angle between 85 and 90 degrees. The EMI shielding layer covers the molding member, and it is electronically connected to the ground pad. The optoelectronics are disposed on the surface of the predetermined area. The side ground pad is disposed on a side of the circuit substrate, and the EMI shielding layer is electrically connected to the side ground pad.
By the abovementioned arrangement, the method of manufacturing electronic module can undergo selective molding without complex molds or procedure. The area that requires molding are formed with molding member and metal coating, such that electromagnetic interference (EMI) is avoided, and the optoelectronics are less likely to be affected by the molding members.
In order to further understand the instant disclosure, the following embodiments are provided along with illustrations to facilitate the appreciation of the instant disclosure; however, the appended drawings are merely provided for reference and illustration, without any intention to be used for limiting the scope of the instant disclosure.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIGS. 1A-1E are schematic views showing the steps of manufacturing electronic module in accordance with an embodiment of the instant disclosure;
FIG. 2 is a top view of an electronic module with an irregular area formed by a method of manufacturing electronic module in accordance with an embodiment of the instant disclosure.
FIGS. 3A-3E are cross-sectional views of the steps of forming electronic module with optoelectronics in an predetermined area in accordance with an embodiment of the instant disclosure;
FIGS. 4A-4D are cross-sectional views of the steps of forming electronic module with optoelectronics in an predetermined area in accordance with another embodiment of the instant disclosure;
FIG. 5 is a cross-sectional view of an electronic module including side ground pads in accordance with an embodiment of the instant disclosure; and
FIGS. 6A-6I are cross-sectional views showing a method for manufacturing electronic module implementing on a two-sided molding in accordance with an embodiment of the instant disclosure.
DETAILED DESCRIPTION OF THE INVENTION
The aforementioned illustrations and following detailed descriptions are exemplary for the purpose of further explaining the scope of the instant disclosure. Other objectives and advantages related to the instant disclosure will be illustrated in the subsequent descriptions and appended drawings.
Please refer to FIGS. 1A-1E . FIGS. 1A, 1C and 1E are cross-sectional view of a method of manufacturing electronic module in accordance with an embodiment. FIGS. 1B and 1D are top view of the method of manufacturing electronic module of the embodiment.
In this embodiment, please refer to FIGS. 1A and 1B . The method of manufacturing electronic module of the instant disclosure includes, firstly, preparing a circuit substrate 11 . The circuit substrate 11 has a surface 12 , a predetermined area 101 on the surface 12 and ground pad 111 . The position of the ground pad 111 can be used to define the predetermined area and the non-predetermined area. In the present embodiment, the ground pad 111 surrounds the predetermined area, and in another embodiment, the width of the ground pad 111 is 200 μm, but the instant disclosure is not limited thereto. The position, shape and dimension of the ground pad 111 are subject to change for different requirement.
Firstly of all, in order to form tape within the predetermined area, a suitable sized tape can be attached to the predetermined area 101 . Alternatively, a large piece of tape can be attached to the entire circuit substrate 11 , and laser is used to trench the tape to the peripheral region of the predetermined area, and then the partial tape outside the predetermined area 101 is removed, such that tape 13 is only present within the predetermined area 101 .
The electronic component 21 is disposed on the surface 12 outside the predetermined area 101 . It can be disposed by surface mount technology (SMT), and the electronic component 21 may be other elements other than optoelectronic, such as all kinds of active, passive components and the instant disclosure is not limited thereto. The optoelectronic in this specification refers to any components that are not suitable to be encapsulated by molding member, for example, CMOS image sensor, CCD, light emitting diode, connector, insertion hole, receptacle or the like. In addition, components that are suitable to be encapsulated are referred to as electronic components.
Please refer to FIG. 2 . FIG. 2 is a top view of an electronic module with an irregular area formed by a method of manufacturing electronic module in accordance with an embodiment of the instant disclosure. The predetermined area 102 in FIG. 2 is irregular. The predetermined area is not limited by number, area size or shape. The predetermined area is used for locating optoelectronics, connector or the like that are not suitable to be encapsulated by the molding member 15 in the following process. The following implementation is adaptable to the predetermined areas 101 and 102 .
After the abovementioned step shown in FIGS. 1A and 1B , such as the step of forming tape within the predetermined area and the step of disposing at least one electronic component 21 , the molding member 15 is formed on the entire circuit substrate 11 . The molding member 15 covers the tape 13 along with the circuit substrate 11 and the electronic components 21 outside the predetermined area 101 and ground pad 111 . The formation of the molding member 15 is achieved by transfer molding or injection molding. The coverage of the tape 13 may overlap the ground pad 111 or immediately adjacent to the ground pad 111 without overlapping, and the instant disclosure is not limited thereto.
Please refer to FIGS. 1C and 1D . After the formation of molding member 15 , laser is used to trench around the peripheral region of the predetermined area 101 . In other words, a trench is cut along the ground 111 . In an embodiment, the width of the trench is approximately 100 μm. The ground pad 111 is a metal layer, and the main material of the molding member 15 may include resin. Because of the different laser absorption level between the ground pad 111 and molding member 15 , the ground pad 111 may act as a stop for laser cutting. However, the instant disclosure is not limited to this approach, and any means that cuts the molding member 15 alone and leaves the circuit substrate 11 is acceptable. For example, contour cutting may also be used to trench the molding member 15 . It should be noted that in the instant disclosure, laser cutting is used, and the molding member does not need to reserve for a draft angle (e,g, approximately 20 degree). Therefore, after trenching, the side wall of the molding member 15 and the surface 12 form an angle α ranging between 85 and 90 degree. Compared to the conventional electronic module, the angle α is closer to 90 degree.
If the tape is a thin film, for example, thickness ranging between 20 and 50 micrometer (μm), when the tape 13 is removed, the molding member 15 remains on the circuit substrate 11 outside the predetermined area. The tape 13 may be heat tape or UV tape. If the tape is a heat tape, it can be removed by heating. In an embodiment, it is heated to 175° C., and the tape is removed by any pickup device. If the tape is a UV tape, the tape can be removed by shining UV light, and the instant disclosure is not limited to these two types of tapes.
In another embodiment of the instant disclosure, the tape is a thick film, for example, thickness being 0.2 mm. After laser trenches the molding member 15 on the predetermined area, laser is used to trim the molding member 15 on the predetermined area (i.e., the molding member 15 above the tape 13 ). In other words, after the molding member 15 on the predetermined area 101 is removed, the tape 13 is then removed, such that only the molding member 15 remains on the circuit substrate 11 outside the predetermined area 101 .
In another embodiment of the instant disclosure, the molding member 15 outside the predetermined area 101 covers with the EMI shielding layer 19 and is electrically connected to the ground pad 111 , and the optoelectronic 22 is disposed on the predetermined area 101 .
Please refer to FIGS. 3A to 3E showing the processes and corresponding cross-sectional views of forming electronic module with the optoelectronic 22 within the predetermined area 101 . In the instant embodiment, after the tape 13 is removed (as shown in FIG. 3A ), a mask layer 18 is disposed on the surface 12 within the predetermined area 101 and does not cover the ground (as shown in FIG. 3B ). The material of the mask layer 18 is not limited as long as it can be easily removed. Subsequently, an entire EMI shielding layer 19 is formed (as shown in FIG. 3C ). The EMI shielding layer 19 may be formed by spray coating, electroless plating or sputtering, and the instant disclosure is not limited thereto as long as the EMI shielding layer 19 and the ground pad 111 keep electrical connection. In this regard, once the mask layer 18 is removed, the EMI shielding layer 19 covers the molding member 15 outside the predetermined area 101 and is electrically connected to ground pad 111 (as shown in FIG. 3D ), such that EMI shielding function can be offered to the electronic component 21 . Then, the optoelectronic 22 is disposed within the predetermined area 101 (as shown in FIG. 3E ), the optoelectronic 22 may be disposed by surface mount technology (SMT), and the instant disclosure is not limited thereto. Accordingly, the optoelectronic 22 is not encapsulated by the molding member, and the optoelectronic 22 is free from electromagnetic interference (EMI).
In another embodiment of the instant disclosure, please refer to FIGS. 4A to 4D . FIGS. 4A to 4D show the processes and corresponding cross-sectional views of forming electronic module with optoelectronic 22 within the predetermined area 101 . In the instant embodiment, after laser trenches the molding member 15 surrounding the predetermined area 101 (as shown in FIG. 4A ), the entire EMI shielding layer 19 is formed (as shown in FIG. 4B ). The formation of the EMI shielding layer 19 is identical as previously mentioned. The EMI shielding layer 19 should be electrically connected to the ground pad 111 . Next, the tape 13 is removed, and the molding member 15 outside the predetermined area 101 is covered with the EMI shielding layer 19 and is electrically connected to the ground pad 111 (as shown in FIG. 4C ), such that EMI shielding function can be provided. Then, the optoelectronic 22 is disposed within the predetermined area 101 (as shown in FIG. 4D ). In practical, in the situations such as the distance between each molding member 15 or the height of the molding member 15 will be result in electrical disconnection of EMI shielding layer 19 and ground pad 111 , the embodiment as shown in FIGS. 3A to 3E could be used to in place of directly forms the EMI shielding layer 19 as shown in FIGS. 4A to 4B .
In addition, for increasing the effectiveness of the protection against electromagnetic interference, the electronic module may further include at least one side ground pad 112 disposed on a side of the circuit substrate 11 and electrically connected to EMI shielding layer 19 as shown in FIG. 5 .
The instant disclosure also provides a method of manufacturing double-sided electronic module by using the aforementioned process. Most of the process detail can be referred back to the previous embodiments. Please refer to FIGS. 6A to 6I . In FIG. 6A , the electronic component 41 is disposed on a first surface of the circuit substrate 31 outside the predetermined area. The tape 33 is attached within the predetermined area. The ground pad 311 surrounds the predetermined area, and the side ground pad 312 is disposed around the side of the substrate 31 . If the height of electronic component 41 is relatively shorter, the tape 33 attached to the first surface can be a thicker tape, and its thickness may be slightly higher than the electronic component 41 .
Subsequently, the first surface of the circuit substrate 31 is formed with the molding member 35 . Because the tape 33 is thicker, the height of the molding member 35 is approximately the same as the tape 33 , such that the molding member 35 can completely encapsulate the electronic component 41 , as shown in FIG. 6B . In addition, because the height of the molding member 35 is the same as the tape 33 , in the following formation of the EMI shielding layer 39 , the tape does not need to be removed and sputtering can be performed straight afterwards.
Then, the molding member 35 formed on the first surface of the circuit substrate 31 is trenched, as shown in FIG. 6C . For the convenience of the following formation of the EMI shielding layer 39 , the trench is wider for easier coating.
After that, the trenched molding member 35 on the first surface of the circuit substrate 31 undergoes coating and is covered with a layer of ink 37 , as shown in FIG. 6D . The ink 37 serves to prevent any contamination from dust or foreign particles occurring to where it covers. The ink 37 can be washed off by chemical solvent, and the particles thereon can be rinsed off at the same time. The layer underneath the ink layer is therefore clean.
Please refer to FIG. 6E . The circuit substrate 31 is turned over to the other side, and starts to mold the second surface of the circuit substrate 31 . The second surface is opposite to the first surface. The tape 53 is attached to the predetermined area on the second surface. In the embodiment, the predetermined area on the second surface surrounds the non-predetermined area. However, the shape of the predetermined area is not limited to the present disclosure. The ground pad 511 can be disposed around the non-predetermined area to act as a stop for laser cutting, in other words, the ground pad 511 is located between the predetermined area and the non-predetermined area. In this embodiment, the height of electronic component 61 disposed outside the predetermined area of the second surface relatively higher than that of electronic component 41 on the first surface, so that a thinner tape 53 could be used at the second surface for attaching on predetermined area. It should be noted that in the instant embodiment, two sides of the circuit substrate 31 (i.e. the first and second surface) are used to describe a preferable implementation, and the instant disclosure is not limited thereto. The height of the electronic components and the position of the predetermined area are not dependent to each other. The combination of the height of the electronic component and the thickness of the tape is decided in relation to a more convenient process, and it may be subject to change.
After the electronic component 61 is disposed on the second surface outside the predetermined area (i.e. the non-predetermined area), the molding member 55 can be formed as shown in FIG. 6F . Subsequently, the tape 53 and the molding member 55 are removed, and the ink 57 is formed on the predetermined above the second surface, as shown in FIG. 6G .
Furthermore, the entire circuit substrate can undergo the processing of EMI shielding layer 59 and then be cut into form individual modules. Alternatively, the entire circuit substrate can undergo cutting to form individual modules first and then processing the EMI shielding layer 59 , such that the exterior of each individual module is formed with the EMI shielding layer 59 , as shown in FIG. 6H .
Following that, the ink 37 , 57 are washed off, and the tape 33 is removed. The resulting circuit substrate 31 has selective molding at two sides and each side has complete EMI shielding layer 39 , 59 respectively. Finally, the optoelectronic 62 is disposed on the predetermined area and the electronic module is complete, as shown in FIG. 6I .
It should be noted that the two-sided molding does not intend to limit the instant disclosure. If the predetermined areas of the two sides are both at the central region, a complete electromagnetic mask layer can be shared between the two sides. That is to say, the ink 37 and the EMI shielding layer 59 can be omitted. More specifically, the substrate undergoes the process up to the step as shown in FIG. 6C , and the EMI shielding layer 39 is formed to cover the entire substrate to simplify the process.
The descriptions illustrated supra set forth simply the preferred embodiments of the instant disclosure; however, the characteristics of the instant disclosure are by no means restricted thereto. All changes, alternations, or modifications conveniently considered by those skilled in the art are deemed to be encompassed within the scope of the instant disclosure delineated by the following claims.
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A method of manufacturing electronic module is provided. The method can perform selective partial molding by forming the tapes in a predetermined area on the circuit substrate, setting electronic components out the predetermined area on the circuit substrate, forming the molding member encapsulating the whole circuit substrate and removing the tapes along of the molding member thereon. Following, forming an EMI shielding layer on the molding member and setting optoelectronics in the predetermined area on the circuit substrate could protect the electronic components from electromagnetic disturbance and avoid the optoelectronics being encapsulated.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of my copending application Ser. No. 06/551,914, pending 350 filed Nov. 15, 1983 and my co-pending Appln. Ser. No. 06/551,913, filed Nov. 15, 1983.
BACKGROUND OF THE INVENTION
The manufacture of microchips and some other industrial products has created a necessity for an extreme degree of cleanliness in manufacturing facilities, commonly called clean rooms. As a result of these cleanliness requirements, Federal standards have been promulgated and must be strictly complied with by the industries involved. Current Federal Standard No. 209B pertaining to classes of room cleanliness establishes three classes of clean rooms, Class 100 being the strictest of these classes. Class 100 specifies that only 100 particles of 0.5 micron size or larger are allowed per cubic foot of air in the clean room. The standard does not pertain to merely an average foot of air but to any cubic foot, at any time. Suggested air velocities are also listed for each class under Federal Standard No. 209B.
A main object of the present invention is to fully comply with and substantially exceed the requirements of Class 100 under Federal Standard No. 209B, in connection with upholstered furniture for clean room use, such as chairs, stools and other seat structures.
Presently, no conventional upholstered furniture or wooden furniture can be tolerated in clean rooms because of the micro particles expelled by them into the environment during normal usage. Such furniture falls far short of even the most liberal class under Federal Standard No. 209B, namely Class 100,000. Metal furniture, such as furniture made entirely of stainless steel, can meet the Federal standards but such furniture becomes so uncomfortable during long usage as to be intolerable, and does not represent a complete solution to the problem.
A further object of the present invention is to provide comfortable upholstered furniture, including various types of seats for clean room usage which fully comply with and exceed the cleanliness requirements under Federal standards of self-imposed industrial standards.
Another and more specific object of the invention is to provide an upholstered seat or other upholstered body supporting surface having a yielding cushion, a hard support base for the cushion and hermetically sealed air-impermeable coverings for the cushion and support base; there being a flexible expandable and collapsible air-impermeable vessel in communication with the interior of the cushion and closed to the atmosphere.
Other features and advantages of the invention will become apparent to those skilled in the art during the course of the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an upholstered clean room chair according to the invention.
FIG. 2 is an enlarged bottom plan view of the seat portion of the chair, partly in cross-section and partly broken away.
FIG. 3 is a vertical section taken on line 3--3 of FIG. 2, parts in elevation.
FIG. 4 is an enlarged fragmentary vertical section taken on line 4--4 of FIG. 2.
DETAILED DESCRIPTION
Referring to the drawings in detail, wherein like numerals designate like parts, a typical upholstered clean room technician's chair 10 according to the present invention is shown in FIG. 1. The invention is also applicable to other types of clean room upholstered furniture including stools, benches and the like. The chair 10 includes a metal pedestal 11, an upholstered seat 12 constructed in accordance with the invention, and an appropriate backrest 13. In some cases, the subject matter of the invention can also be embodied in the backrest or other upholstered body supporting surface of furniture.
In accordance with the invention, the upholstered seat 12 comprises a rigid preferably contoured base panel 14 formed of wood or the like, on the upper surface of which is mounted a resilient cushion 15 formed of foam rubber or foam plastics material. An air-impermeable preferably vinyl top cover section 16 entirely encloses the seat cushion 15 above the rigid panel member 14 and has its marginal portion 17 folded inwardly beneath the panel member 14 and attached thereto by a first line of staples 18.
A lower air-impermeable preferably vinyl seat cover section 19 extends beneath the base panel 14 and between it and a top mounting flange 20 of the pedestal 11. The marginal portion of the cover section 19 is folded upon itself to provide a double thickness margin 21 for the lower over section and this double thickness margin is secured directly to the bottom of the marginal portion 17 by a second line of staples 22. Screws 23 are employed to secure the pedestal flange 20 to the base panel 14 rigidly.
To render the upholstered seat structure thus far described completely air-tight, continuous adhesive sealant 24 is applied around the margin of the double thickness portion 21 of the lower cover section 19 and between the portions 21 and 17 in the region of the staples 22, as best shown in FIG. 4. The screws 23 are also dipped in adhesive solvent before application to the flange 20 and base panel 14.
In accordance with the principal feature of the invention, a bellows 25 formed of rubber or rubber-like material is mounted in communication with the interior of the upholstered seat 12 in such a manner that the air contained in the seat cushion 15 can be expelled into the bellows when the upholstered seat is compressed, and the same air within the bellows is inducted into the seat cushion as the upholstered seat is relieved of its load and expands. The upholstered seat and bellows are completely sealed relative to the outside atmosphere so that no atmospheric air can enter the bellows or upholstered seat and no air contained in the seat and bellows can be expelled to the atmosphere. This completely eliminates pollution of the clean room atmosphere by the air contained within the upholstered furniture during its usage in a clean room.
The bellows which may be circular in cross section or a different shape, if preferred, is spaced forwardly of the pedestal 11 and located substantially flush with the front edge of the seat 12 at its transverse center. The base panel 14 adjacent to the bellows has an opening 26 through which air flows from the upholstered seat into the bellows and vice-versa. The lower vinyl cover section 19 has a registering opening 27 and the top wall 28 of the bellows 25 also has a registering opening 29. A compressible ring gasket 30 and rigid ring 31 are placed below the bellows top wall 28 with their bores in registry with the openings 26, 27 and 29. These elements 30 and 31 are disposed inside of the air-impermeable bellows.
Bellows attaching screws 32 dipped in adhesive sealant 33 are placed through the ring 31, gasket 30, bellows top wall 28, lower cover section 19 and into the rigid base panel 14. The previously-described sealant 24 is also disposed between the bellows top wall 28 and lower cover section 19, as best shown in FIG. 4. The upholstered seat and bellows assembly is thus completely hermetically sealed.
The lower end wall 34 of the bellows 25 is closed by a disc 35 of rubber installed after completion of the assembly. This closure disc is also sealed by adhesive sealant 36.
It should now be apparent that the bellows 25 forms a flexible expandable and collapsible vessel sealed from the ambient atmosphere and always in open communication with the interior of the air-impermeable upholstered seat. Thus, whenever the seat is compressed by a user, the air contained therein is expelled into the bellows 25, and later, when the seat is relieved of its load and returns to its normal shape, the air previously expelled into the bellows is returned into the seat 12. This action takes place with absolutely no contamination of the clean room atmosphere.
The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention, in the use of such terms and expressions, of excluding any equivalents of the features shown and described or portions thereof but is is recognized that various modifications are possible within the scope of the invention claimed.
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To assist in maintaining the high degree of cleanliness required by Federal standards in industrial clean rooms, an upholstered seat is provided having an attached bellows which receives air from the seat when the seat is compressed and from which air is returned to the seat as the seat expands. There is no escape of air from the seat and bellows to the atmosphere and no induction of air from the atmosphere to the seat or bellows.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to provisional application No. 60/285,001, filed Apr. 19, 2001, “Periphyton Filtration Pretreatment System and Method.”
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to systems and method for improving water quality, and, more particularly, to such systems and methods for bioremediating water with an attached algal colony, and, most particularly, to treating water against undesired toxins, microorganisms, and other water-borne pollutants in concert with an attached algal colony.
[0004] 2. Description of Related Art
[0005] Algae comprise a group of plants, existing in approximately 18,000 different species, whose primary nutrients include carbon, nitrogen, and phosphorus, as well as a suite of micronutrients essential to plant growth.
[0006] The removal of contaminants from wastewater and ground water has become an important problem in restoring ecological balance to polluted areas. It is known that some algal species are capable of absorbing heavy metals into their cell walls, thus reducing their toxic effects on the environment. Algae can also take up nutrients and micronutrients that may be present in overabundance, such as phosphorus, potassium, nitrogen, iron, aluminum, and calcium, and can thus be utilized to remediate an ecosystem. Such remediation can occur when water flows over stationary algae, also absorbing carbon dioxide and releasing oxygen in the process as a result of respiration and photosynthesis. Further, the water passing over the PF experiences an increase in pH owing to the removal of carbon. The filtration can occur through adsorption, absorption, physical trapping, and other more complex means.
[0007] A system used to effect this uptake is known as a periphyton filter, the periphyton comprising a culture of a family of fresh, brackish, and/or salt-water aquatic plants known as attached microalgae. Unlike such organisms as free-floating plankton, benthos or attached algae is stationary community of epiphytes that will grow on a wide variety of surfaces. When occurring in the path of flowing water, the stationary algae remove nutrients and other compounds from the passing water, while absorbing CO 2 and releasing O 2 as a result of respiration and photosynthesis. Once a colony is established, roots or holdfasts cover the culture surface. If the plant bodies are harvested, leaving the roots behind, the nutrients and other pollutants contained in the plant bodies are removed from the water, causing a natural filtration effect.
[0008] A further advantage to this technique is that the enriched algae can be harvested and used as fish or animal feed, which serves to return the nutrients to the food chain.
[0009] Periphyton filters (PF) have the potential for use in a variety of applications. For example, the turf can be used to replace biological or bacteriological filters in aquaria. As mentioned, natural periphyton can be used to remove nutrients and other contaminants from polluted waters. In addition, by harvesting the algal mass, various processes can be used to produce a biomass energy source such as methane or ethanol, fertilizer, a human or animal food additive or supplement, cosmetics, or pharmaceuticals.
[0010] The high productivity of the algae in a fibrous form has also yielded uses in the paper and paper products industry, as the harvested algae are stronger and easier to process than wood fiber. This capability has resulted in a sustainable method of managing human impact on aquatic ecosystems.
[0011] Periphyton filters behave differently in water with varying location, speciation, chemical characteristics, and other parameters. Experience in situ has in some cases resulted in weak or poor productivity owing to low concentrations of available nutrients. It has been shown that if a fraction of the primary nutrients are not available, then the periphyton filters struggle to develop the critical mass necessary to invoke a substantial precipitation and physical trapping capability and concurrent filtration characteristics. In particular, the presence of microinvertebrates and their eggs can compromise the success of a periphyton filtration system by consuming desirable periphyton and by eating the root or holdfast of the algal filament.
[0012] Toxic cyanobacteria pose a particularly formidable set of filtration challenges in that the toxins are very persistent in the environment and can exist both inside and outside the algal cell. It is known to treat toxin-containing water with ozone because of its strong oxidizing effect when mixed in water; however, the nutrients in ozonated water become available and are reconsumed by the toxic algae.
[0013] Studies in algal turf production are known in the art. Algal turf techniques have been disclosed in Adey's U.S. Pat. No. 4,333,263, and the present inventor's U.S. Pat. Nos. 5,131,820, 5,527,456, 5,573,669, 5,591,341, 5,846,423, and 5,985,147, the disclosures of which are incorporated herein by reference.
SUMMARY OF THE INVENTION
[0014] It is therefore an object of the present invention to provide a system and method for pretreating and/or post-treating water in concert with a periphyton filtration bed.
[0015] It is another object to provide such a system and method for reducing a population of undesirable microinvertebrates in a periphyton filtration bed.
[0016] It is an additional object to provide such a system and method for reducing or eliminating toxins from inflow water as well as a toxicity level of harvested algal mass.
[0017] These objects and others are attained with the system and method of the present invention. The system comprises means for adding a strong oxidizer to the influent, and, in some cases, to the effluent. A particular embodiment comprises ozonating the water.
[0018] The method of treating water comprises the steps of exposing water desired to be treated to ozone in sufficient quantity to reduce a concentration of undesired microorganisms therein and flowing the water over a colony of attached algae to remove undesired matter therefrom, such as, but not intended to be limited to, nutrients.
[0019] The features that characterize the invention, both as to organization and method of operation, together with further objects and advantages thereof, will be better understood from the following description used in conjunction with the accompanying drawing. It is to be expressly understood that the drawing is for the purpose of illustration and description and is not intended as a definition of the limits of the invention. These and other objects attained, and advantages offered, by the present invention will become more fully apparent as the description that now follows is read in conjunction with the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
[0020] [0020]FIG. 1 is a schematic illustration of a first embodiment of the invention.
[0021] [0021]FIG. 2 is a schematic illustration of a second embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] A description of the preferred embodiments of the present invention will now be presented with reference to FIGS. 1 and 2.
[0023] It is known to use ozone to treat water because of the properties of the unstable O 3 molecule, which is a strong oxidizer. Ozone is typically generated, for example, by ultraviolet radiation or corona discharge. Since ozone is a gas, it must be dissolved or broken into small bubbles to optimize contact with the target microorganisms in the influent and, in some cases, the effluent. An optimal residence time should be achieved in the water to be treated to maximize particle contact. This may be achieved, for example, with a mixing chamber or a mixing pump.
[0024] If the location of the periphyton filter is at some distance from the water to be treated, mixing may occur, for example, downstream and generally adjacent a supply pump or pipe entrance, with a single or multiple static mixers agitating the water/ozone combination. The residence time is then equal to the travel time to the periphyton filter, which can be tested for sufficiency of contact time. In addition, further static mixers and ozone injection points may be positioned along the pathway to the periphyton filter to increase effectiveness and efficiency.
[0025] In an alternate embodiment a covered pond may be used, such a pond cover having an ozone destruct port at the highest location to catch ozone prior to escaping into the atmosphere. A subsurface “well-style” tank may be used to increase contact time, such a tank having a high-pressure ozone injection at its bottom for optimal dispersion of ozone into the water column.
[0026] The present invention provides the following benefits:
[0027] Ozone breaks up planktonic algae, bacteria, and other organically bound particles in lake water, thereby making nutrients available for use and concurrent growth of the periphyton.
[0028] After the nutrients are available and removed by the periphyton, the water can be returned to the water body from which it came, or to another water body, in a state that will limit the ability of toxic algae to regrow, thereby effecting remediation.
[0029] Ozone destroys certain toxic compounds found in cyanobacteria (blue-green algae) recently found to be dangerous to humans and other animals. These toxic compounds, as well as nontoxic compounds, are then available to be taken up by filamentous algae grown for industrial use, such as in the paper products industry
[0030] Ozone destroys both microinvertebrates and their eggs, which often settle, hatch, and grow as they consume desirable periphyton, thus reducing the effectiveness of filtration.
[0031] Other devices to be used alone or in conjunction with ozone to enhance performance are plasma sparkers and ultraviolet light treatment systems, such as are known in the art.
[0032] Two embodiments of the present invention are illustrated schematically in FIGS. 1 and 2. In the first embodiment (FIG. 1) of the system 10 water is shown being taken in from deep water 11 , shallow water 12 , or a tributary 13 byway of pipes 14 and pumps 15 - 17 , respectively. An ozone generator 18 provides ozone to an ozone injection apparatus 19 so that the water desired to be treated can be contacted with ozone in chamber 20 . Alternately, as mentioned above, a submersible plasma sparker may be used. Ozonated water is carried via transfer piping 21 to a distribution manifold 22 , which distributes the water to the inlet end 23 of a periphyton bed 24 , which is tilted to permit the water to flow downward to the outlet end 25 . The treated water is then collected into a transfer pipe system 26 , and is then either returned to a waterway 27 or transferred to a drinking water treatment system 28 of ground water aquifers 29 .
[0033] In the second embodiment (FIG. 2) of the system 30 , inflowing water 31 is pumped into ozone distribution piping 32 , into which is also injected ozone from an ozone generator 33 . Prior to exposure to ozone, the water may be exposed to at least one of ultraviolet radiation and acoustic energy 43 . Following passage through an ozone injection diffuser 34 , the water proceeds via transfer piping 35 into multiple ozone contact chambers 36 . Three are shown here, but this is not intended as a limitation. When fully ozonated, the water exits via discharge piping 37 .
[0034] In either of the above-described embodiments, an additional step may be taken of adding a pesticide to the algal colony for controlling insects. The pesticide may be selected, for example, from a group consisting of an insecticide, a pyrethroid, or a natural pyrethrum, although these are not intended as limitations.
[0035] In a particular embodiment, the pesticide may comprise bacillus therengensus isralioans (BTI). A further element of either of the systems 10 , 30 , shown in FIG. 1, comprises a BTI culturing system 40 , wherein BTI is substantially continuously cultured, or cultured as needed, and a continuous drip of BTI is provided via line 41 leading to drip hose 42 adjacent the inlet 23 of the periphyton bed 24 .
[0036] As an additional or alternative embodiment, further systems and methods are envisioned for detoxifying one or more elements of the system 10 , 30 . As an example (FIG. 1), the algal colony 24 may be harvested by means known in the art from its base 44 , and a pesticide P may be added to the harvested algae to form a mixture 24 ′. This mixture 24 ′ is exposed to sunlight or other means to provide detoxification and then ground to form a mulch 24 ″. Such a mulch may then be used atop the base 44 to form a subsequent algal colony 24 . The pesticide may be selected from a group consisting of natural pyrethrum, natural pepper, garlic, elder, and lemon sage, although these are not intended as limitations.
[0037] Further, the algal colony 24 may be harvested by means known in the art, and pesticide P may be added to the base 44 wherein water is not flowing, and allowed to detoxify the base 44 . Following sufficient time for detoxification, an agonist may be added, such as an alkaline solution, to detoxify the pesticide prior to restarting water flow over the algal colony 24 . In this case, the pesticide may comprise at least one of a synthetic pyrethroid or a natural pyrethrum.
[0038] It may be appreciated by one skilled in the art that additional embodiments may be contemplated, including alternate methods of introducing ozone and the use of alternate oxidizing agents to the treatment water.
[0039] In the foregoing description, certain terms have been used for brevity, clarity, and understanding, but no unnecessary limitations are to be implied therefrom beyond the requirements of the prior art, because such words are used for description purposes herein and are intended to be broadly construed. Moreover, the embodiments of the apparatus illustrated and described herein are by way of example, and the scope of the invention is not limited to the exact details of construction.
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Periphyton filtration is a known method for performing bioremediation of polluted water, removing nutrients from the influent on which the attached algae thrive. The present system improves upon this method by adding a strong oxidizer to the influent, and, in some cases, to the effluent, to make organically bound nutrients available to a target culture of periphyton or aquatic plants to reduce the population of undesirable microinvertebrates, to make organically bound nutrients available to the periphyton, and to reduce the level of toxic compounds. A particular embodiment comprises ozonating the water. A pesticide may be added to control insect populations.
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BACKGROUND OF THE INVENTION
[0001] This invention relates to the field of sub-floor systems for balcony, patio or terrace of homes and roof.
Prior Art
[0002] Our research among patents revealed some systems that caught our attention:
[0003] CA 1,225,252 is a floor with twin cells to protect electric wire.
[0004] CA 2,340,371 is an evacuation drain for plumbing installed within a building.
[0005] U.S. Pat. No. 6,539,681 is a spacing for a hollow floor which supports piping for heating or air-conditioning.
[0006] EPO JP20000320034 is a sheet looking like a net for preventing infestation of termites.
OBJECTS AND ADVANTAGES
[0007] The general objective of this invention is to permit building galleries with openwork planks to shy from rain and snow, for storing objects and protecting a structure against water.
[0008] A specific objective is to prevent rainwater from being introduced and remain caught between the boards and the wooden structures which constitute the coating and the braces of a patio or a balcony. This invention allows the draining and the water running off far from the structures composing a patio, a balcony or a terrace.
[0009] Another objective is to allow an arrangement under a patio including humps and valleys positioned such that the rainwater will not run any more between the boards so as to maintain dry the lower part of a patio.
BRIEF DESCRIPTION OF DRAWING FIGURES
[0010] FIG. 1 is a side view of an under-plank
[0011] FIGS. 2A and 2B are cut views according to line 2 - 2 of FIG.4
[0012] FIG. 3A is a perspective view of an under-plank sheet
[0013] FIG. 3B is a perspective view of a wood board
[0014] FIG. 4 is a side view of a patio juxtaposed with a building support
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0015] In the following description and in the accompanying drawings, the numeral numbers refer to identical parts in the various Figures.
[0016] FIG. 1 shows by an arrow a side view of an under-plank 20 , a sloping section 23 surrounded by an accentuated left crest 26 , central crest 27 and widened crest 35 ; on which water slips before arriving in the various zones of drainage of water 22 , 22 ′. Zones of screwing 24 , 24 ′ correspond to a zone where the screws of a deck board will be most effective when piercing the under-plank 20 , between boards 30 which constitute a coating of a patio and beams 44 . The zones of screwing 24 are defined in widened zones of screwing 38 and abrupt zones of screwing 42 . An accentuated crest 26 is encased in an accentuated crest 28 which has an edge 48 of a connection zone 41 in order to allow the connection of another under-plank 20 to the following and to maintain the sealing between them. An overlap zone is according to the spacing between boards of the patio. A typical variation is 0 to ½ inch.
[0017] FIG. 2A Defines water flow direction first vertically along a screw or between two boards then along a slope and finally away from an observer and longitudinally of the board 30 . FIG. 2 shows a side view of the assembly of a sub floor sheet 20 maintained in place with screws 32 between wood boards 30 of the coating of the patio and beams 44 . Screws 32 , 32 ′ are placed close to crests 35 and 26 , but preferably in the widened zones of screwing 38 , 38 ′ because the water infiltrated through the holes made by screws 32 will run out by slipping along the crests 35 and 26 in the zones of evacuation 22 , 22 ′. There are indeed a broader zone of screwing 25 on the crest 27 which allows screwing and the drainage of water, but it is necessary to take care not to screw too close to the zones of evacuation 22 , 22 ′ because water would then be retained at the place where the screw would be entering a metal shield. It is better to target the widened zone of screwing 38 which gives more play. Water infiltrating through a hole made in a deck board sub floor sheet 20 runs between the zones of evacuation 22 , 22 ′ which are in the direction of the relief of these zones. The dotted arrows show the direction water can follow while running out on or between boards 30 of the covering of the patio before being evacuated by the zones of drainage of water 22 , 22 ′ or by the flat bottom 40 of the zone of connection 41 .
[0018] FIG. 2B shows a side view of the assembly of an under-plank 20 wherein boards 30 are closer than those of FIG. 2A to provide adjustment between similar boards 30 laid out on FIG. 2A .
[0019] FIG. 3A shows an under-plank 20 which is corrugated, an under-plank strip appears rolled over itself several times such as for a grass roll.
[0020] FIG. 3B shows a deck wood board 30 .
[0021] FIG. 4 shows a patio 46 juxtaposed at a building 58 with a slope 50 such as ¼ inch per foot in length in order to allow the drainage of water in the direction opposed to that of the building.
Applications
[0022] The applications of this invention relate to the protection of a patio, a balcony or a terrace deck board; a tight sub-floor for patio is a semi-rigid under-plank of corrugated polymeric installed between beams and transverse boards constituting the covering of the patio. The corrugated under-plank has a design of crests and dips, crests widened to make possible to receive of screws and dips where there will be no perforation of screwing, to allow the water run-off in order to protect the wood structures of patios, balconies or terraces against moisture causing their premature rot.
SUMMARY OF THE INVENTION
[0023] A corrugated semi-rigid under-plank intended to be used between a board 30 and a structure element 44 , the under-plank having a number of crests 26 , 27 , 28 , 35 among which a group of widened crests 26 , 35 intended to provide a spacing to receive screws 32 , 32 ′ in a zone of screwing 24 , 24 ′, and a flat upper zone 27 of screwing intended to receive a screw 27 ′ fixed upwardly.
[0024] The under-plank has a number of dips 22 , 22 ′, 40 to provide support over the structure element 44 , and to provide means of drainage of a liquid found on a surface of the board 30 .
[0025] Water infiltrating around screws result in a flow of water along a slope 23 , 23 ′ towards the dips 22 , 22 ′ called zones of drainage,
[0026] The under-plank may be placed between two rows of boards, a top row a covering may be a floor, a patio, a balcony, a terrace, or a roof. The under-plank may be placed between two rows of boards, the lower row being beams or foundations of a floor, a patio, a balcony, or a terrace.
[0027] The under-plank may be a roof.
[0028] The under-plank being corrugated according to the higher and lower crests and whose top and base are all at corresponding height, each crest being a point of support.
[0029] The under-plank being sufficiently rigid in order to maintain its form during the screwing and when a significant load will be deposited on it in addition to the people who will circulate and objects which will be deposited on a first rank of boards defined as covering, the form also need to be maintained between the beams in order to preserve the functions of a sub floor.
[0030] The under-plank whose zones of drainage of water 22 , 22 ′, 40 are intended to provide a means of drainage of rain, water coming from snow melt or water washing accumulating in a natural or artificial way.
[0031] The under-plank consisting of an impermeable material to water, the absence of porosity jams the passage of liquid through the under-plank.
[0032] The under-plank consisting of a material which does not deteriorate upon moisture, solar radiation and freezing and thaw.
[0033] The under-plank is made according to a central axis on in each side of the axis the crests are distributed symmetrically.
[0034] The under-plank is formed of crests laid out symmetrically, which implies the disposition according to a regular spacing of boards 30 which constitutes the covering of a patio, in order to allow a screwing in the zones of screwing 24 , 24 ′ of the under-plank.
[0035] The under-plank whose crests have a sufficient height to allow the flow of water when it rains abundantly.
[0036] The under-plank whose lower crests correspond to zones of drainage of water 22 , 22 ′.
[0037] The connection zone 41 having a flat dip 40 , which is also a zone of drainage, terminated on a terminating edge 48 which matches a forward edge 36 of a second under-plank in order to allow the alignment of several under-plank 20 and the sealing of a sub floor.
[0038] The connection zone 41 allowing a variation in the adjustment of the under-planks thereby making possible adjusting boards for the covering of a patio laid out above the flat dip 40 of the connection zone 41 .
[0039] The under-plank whose higher crests are indicated according to the shape of their slope; accentuated left crests 26 , central 27 and the widened crests 35 .
[0040] The under-plank whose zones of screwing 24 , 24 ′ correspond to spaces on both sides of higher crests.
[0041] The under-plank whose zones of screwing of the widened crests 26 , 35 are indicated according to the extent of the available zone for screwing; widened zone of screwing 38 , 38 ′, and the abrupt zone of screwing 42 , 42 ′ narrower than the wide zone of screwing.
[0042] The under-plank whose widened zones of screwing 38 and the abrupt zones of screwing 42 have a slope of at least 2 degrees which permit water to run out than instead of remain imprisoned between boards 30 of covering and the under-plank 20 .
[0043] The corrugated under-plank is not necessarily rigid in composition so as to permit the wrapping thereof into a four foot diameter bundle for extension to one hundred feet. The board means may be a coating or a paste or fibreglass spread over the top surface of the under-plank for providing a roof surface without any top board element. The sloping sections may be provided with a clip arrangement to be maintained together. The number of crests 26 , 27 , 28 , 35 and dips 22 , 22 ′ providing support over structural elements 44 , a number of sloping sections 23 to provide a spacing to receive screws 32 , 32 ′ in a so-called zone of screwing 24 , 24 ′, sloping sections to provide means of drainage of a liquid found on a surface of a board 30 and around the screws, the zone of screwing being limited to the sloping sections, water infiltrating around screws, during screwing and afterwards, resulting in a flow of water towards the dips 22 , 22 ′ and resulting in a zone of drainage.
[0044] It is to be clearly understood that the instant description with reference to the annexed drawing is made in an indicative manner and that the preferred embodiments described herein are meant in no way to limit further embodiments realizable within the scope of the invention. The matter which is claimed as being inventive and new is limited only by the following claims.
PARTS
[0000]
20 —Under-plank
22 —Zone of drainage of water
23 , 23 ′—Sloping sections
24 —Zone of screwing
25 —Boarder of screwing
26 —left accentuated Crest
27 —Central crest
27 ′—Screw fixed upwardly
38 —Edge
35 —Right accentuated Crest
30 —Board
32 —Screw
35 —Right widened Crest
36 —Forward edge
38 —Widened Zone of screwing
40 —Flat bottom of the connection zone 41
41 —Connection zone
42 —Abrupt Zone of screwing
44 —Structural element
46 —Patio
48 —Terminating edge
50 —Slope
52 —Beam
54 —Support
58 —Support building
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The present invention relates to a watertight sub-floor system for balcony or roof, in the form of a semi-rigid rollable plank of corrugated polymeric type installed in juxtaposition to form a waterproof flooring between boards and beams. Under-plank are unwrapped and cut at a desired length to avoid transverse junction with respect to water flow. Under-planks overlap parallel to water flow without loss of sealing. The corrugated under-plank has a design of crests and dips, crests widened and sloping to make possible the receiving of screws from deck board, thereby permitting the descent of water trickling from around the damaging screwing of the under-plank, and dips which bear no perforations from screwing and merely allow water to run off to protect wood structures of patios, balconies or terraces against moisture causing premature rot and to protect objects (bike, mowers . . . ) under a deck.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present invention claims the benefit of the filing date of U.S. Provisional Patent Application Ser. No. 60/186,245 filed Mar. 1, 2000.
FIELD OF THE INVENTION
[0002] The present invention relates generally to an antenna for transmitting to and receiving signals from one or more transmitting and receiving sources such as satellites, wherein the received signals are dual-polarized such that they simultaneously contain two components of different polarizations such as two different linearly polarized components on orthogonal planes, or right-hand and left-hand circularly polarized components.
BACKGROUND OF THE INVENTION
[0003] In recent years, there has been a significant increase in the amount and types of information that is transmitted via satellite communication. For instance, satellites now transmit telephone signals, television signals, internet data, etc. Due to the expanded use of satellites for data communication, there has also been an associated increase in the number of satellites placed in orbit about the earth. For instance, there are currently satellites that are dedicated to transmission of not only television signals in general, but are dedicated to transmission of only certain types of programming, such as movie channels, foreign language channels, local channel programming, or high definition television signals. Satellites have also been deployed for the transmission of internet signals for some internet providers.
[0004] As the use of satellite communications continues to increase, there is a general trend toward more widespread use of satellite antennas by private individuals and commercial and governmental users. For these types of applications, cost and aesthetics are major concerns in the design of antennas. Providing a low cost, compact, and aesthetically pleasing antenna, however, presents design challenges.
[0005] One such challenge is reducing the overall size of an antenna while at the same time providing increased functionality required by changes in the way data communications with satellites are conducted. More particularly, there is a trend in satellite communications toward greater and greater utilization of “frequency reuse” so that increasing amounts of information can be transmitted and received within a given frequency band. Frequency reuse refers to a method of increasing the throughput of information in a frequency band by dual-polarizing a transmitted signal such that the signal contains two components of different polarizations. For instance, two components can be linearly polarized in two different planes, typically orthogonal to each other and usually referred to as “vertical” and “horizontal” planes. Alternatively, both right-hand and left-hand circularly polarized components can be contained in the same signal. In either case, each component is encoded with information, such that about half of the transmitted information is carried in one polarization component and the other half is carried in the other polarization component. Traditionally, in the satellite antenna industry, such dual-polarized signals containing vertical and horizontal linearly polarized components have been received by a transmit/receive (T/R) feed and passed through an ortho-mode transducer (OMT), which is essentially a Y junction that channels transmitted signals from a transmitter of the antenna to the T/R feed, and channels received signals received by the T/R feed to a receive side of the antenna. The receive side of the antenna traditionally has included a diplexer for separating the vertical polarization component of the received signal from the horizontal component thereof. Downstream of the diplexer, a pair of rectangular waveguide/filter elements have traditionally been used for separately filtering the vertical and horizontal components of the received signal so as to prevent signals transmitted by the transmitter of the antenna from propagating down the receive side of the antenna to the antenna's receiver. After the vertical and horizontal components are separately filtered, they are typically recombined in a recombiner, and are then passed to further electronics for processing before being passed to the antenna's receiver. Thus, the conventional antenna capable of handling dual-polarized signals has required a diplexer, two separate filter elements, and a recombiner. All of these components can add to the cost and overall size of the antenna.
SUMMARY OF THE INVENTION
[0006] The present invention addresses the above-noted needs by providing an apparatus for receiving signals from and transmitting signals to a source such as a satellite, in which the traditionally used diplexer, separate vertical and horizontal filters, and recombiner are replaced by a considerably simplified system for handling dual-polarized received signals. In accordance with one preferred embodiment of the invention, the apparatus comprises a transmit/receive feed operable to transmit signals to and receive signals from a source, a waveguide assembly coupled with the transmit/receive feed for propagating transmitted and received signals to and from the transmit/receive feed, and a receive isolation filter coupled with the waveguide assembly and operable to filter the dual-polarized received signals without separating the two components thereof and to provide the filtered dual-polarized received signals to a receiver so as to isolate the receiver from signals transmitted by the transmit/receive feed. Thus, both components of the received signals are filtered simultaneously along the same path of propagation, eliminating the need to split the components along separate paths, separately filter them, and then recombine them as in prior antennas. The receive isolation filter, also referred to herein as a dual-mode filter, can filter signals containing two orthogonal linearly polarized components, and can also filter signals containing right-hand and left-hand circularly polarized signals.
[0007] The apparatus in accordance with the invention preferably forms a part of an antenna for receiving signals from and transmitting signals to a satellite. In a preferred embodiment, the receive isolation filter defines multiple internal cavities of different dimensions. In order to simultaneously filter two orthogonal components of the dual-polarized received signals, the receive isolation filter preferably defines an internal waveguide passage that has 90° rotational symmetry about its longitudinal axis. By “90° rotational symmetry” is meant that a cross-section through the passage along a first plane, such as the plane of one of the polarization components and containing the longitudinal axis of the passage, is substantially identical to a cross-section through the passage along a second plane orthogonal the first plane and also containing the longitudinal axis. Thus, the passage appears the same to each of the polarization components, whether the components comprise two orthogonal linearly polarized components or right-hand and left-hand circularly polarized components. In other words, the filter is polarization-independent. Various internal cross-sectional shapes having such 90° rotational symmetry can be used for the filter, including but not limited to circular cylindrical passages or square passages. In a preferred embodiment, the receive isolation filter has a circular internal cross-section. More particularly, in a preferred embodiment the receive isolation filter comprises a plurality of sequentially arranged circular cylindrical cavities of different internal diameters and volumes.
[0008] The apparatus can be incorporated in an antenna for communications with two different sources such that the antenna transmits to and receives from a first source and only receives from a second source. In this case, the apparatus also includes a second feed operable to receive signals from the second source, and a second receive isolation filter operable to filter the received signals from the second feed so as to isolate the antenna's receiver from signals transmitted by the transmit/receive feed. Of course, if the signals received by the second feed are dual-polarized signals, then the second receive isolation filter can be a dual-mode filter similar in concept to that used with the transmit/receive feed.
[0009] Antennas in accordance with the invention can also include additional feeds for communicating with additional sources such as satellites, if desired.
[0010] The invention thus simplifies the design and manufacturing of an antenna for satellite communications via dual-polarized signals, and enables the filtering and waveguide elements of the antenna to be made more compact in size and lower in cost compared with prior antennas employing separate filtering of the two components of the dual-polarized signals.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The above and other objects, features, and advantages of the invention will become more apparent from the following description of certain preferred embodiments thereof, when taken in conjunction with the accompanying drawings in which:
[0012] [0012]FIG. 1 is a perspective view of an antenna in accordance with one embodiment of the invention;
[0013] [0013]FIG. 2 is a perspective view of an assembly of the antenna including feeds, waveguide elements, filtering elements, and other components;
[0014] [0014]FIG. 3 is a perspective view of a portion of the assembly of FIG. 2;
[0015] [0015]FIG. 4 is a sectioned view, in perspective, of a receive isolation filter in accordance with an embodiment of the invention; and
[0016] [0016]FIG. 5 is a plot of frequency response for the receive isolation filter in accordance with one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0017] 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.
[0018] [0018]FIG. 1 shows an antenna 10 in accordance with one preferred embodiment of the invention. The antenna 10 includes a reflector 20 that has a concave shape for reflecting signals inbound from a transmitting source such as a satellite such that the reflected signals are focused at a focal point spaced from the concave surface of the reflector. Located at or in close proximity to the focal point of the reflector are a transmit/receive (T/R) feed 22 and a plurality of additional feeds 24 , 26 , and 28 . The feed 24 in this particular embodiment comprises a receive feed that receives signals but is not designed to transmit signals. The T/R feed 22 advantageously comprises a corrugated feed.
[0019] With reference to FIGS. 2 - 4 , the feeds 22 and 24 and associated components are shown in greater detail. The T/R feed 22 receives signals transmitted by a source and reflected from the reflector of the antenna, and directs the received signals via a waveguide assembly to further components of the antenna. More particularly, the feed 22 directs the received signals into a main port 30 a (FIG. 4) of a Y junction device 30 , such as an ortho-mode transducer. The Y junction device 30 includes a receive outlet port 30 b to which is coupled a receive isolation filter 40 . Dual-polarized received signals that enter the main port 30 a of the Y junction device 30 propagate substantially unimpeded along a main waveguide portion of the Y junction device and exit the receive outlet port 30 b into the receive isolation filter 40 . The Y junction device 30 also includes a transmit port 30 c to which is coupled one end of a transmit waveguide 34 . The opposite end of the transmit waveguide 34 is coupled with a transmitter 50 of the antenna. Transmitted signals from the transmitter 50 are propagated along the transmit waveguide 34 into the transmit port 30 c of the Y junction device 30 and then are propagated substantially unimpeded along a waveguide portion of the Y junction device and out the main port 30 a to the T/R feed 22 , which transmits the signals toward the reflector of the antenna where the signals are reflected back toward a satellite or other destination.
[0020] The Y junction device 30 thus is operable to channel transmitted and received signals along separate paths such that transmitted signals from the transmitter are substantially prevented from passing out the receive port into the receive isolation filter 40 , and received signals from the T/R feed 22 that enter the main port 30 a of the Y junction device are substantially prevented from passing through the transmit port 30 c into the transmit waveguide 34 and thence to the transmitter 50 . However, the Y junction device generally cannot be completely effective in this separation of the transmitted and received signals. Accordingly, generally some attenuated transmitted signals will find their way through the receive port 30 b of the Y junction device. Although these signals may be attenuated relative to their original level, they can still be large in comparison with the levels of received signals. Therefore, filtering of the received signals is required, and is performed by the receive isolation filter 40 .
[0021] In accordance with the present invention, the received signals are dual-polarized, meaning that they contain two components that are polarized in two different ways. Typically the two components are polarized in two orthogonal planes, and are usually denoted by the terms “vertical” and “horizontal” components. Alternatively, the two components can be right-hand and left-hand circularly polarized. In contrast to prior antenna systems in which the two components are separated and then filtered by two separate filters, the present invention employs the receive isolation filter 40 , which filters both components without separating them. The receive isolation filter 40 is operable to filter the signals that pass into its input port such that signals within the frequency band corresponding to the dual-polarized received signals are passed with relatively little attenuation through the output port of the filter and are fed to a further component such as a low noise block (LNB) module 60 . However, signals within the frequency band of the transmitted signals from the transmitter 50 are substantially attenuated to a level substantially below that of the received signals.
[0022] [0022]FIG. 5 shows an exemplary frequency response plot for a receive isolation filter 40 in accordance with the present invention. In this example, the receive frequency band 42 is about 12.2 to 12.7 gigaHertz and the transmitting frequency band 44 is about 14.0 to 14.5 gigaHertz. The curve 46 represents the isolation of the filter, and exhibits an approximately zero dB isolation in the receive frequency band 42 , while providing an attenuation of at least about 60 dB in the transmit frequency band 44 . The curve 48 represents the return loss of the filter, and shows a return loss of about 20 dB in the receive frequency range and a return loss of about zero dB in the transmitting frequency range. Of course, the invention is not limited to any particular receive and transmit frequency bands. Those skilled in the art will recognize the frequency ranges referred to above as corresponding to the Ku-band; however, the invention can be used for other frequencies such as the Ka-band in which signals are received in the range of about 19.7 to 20.2 gigaHertz and are transmitted in the range of about 29.5 to 30.0 gigaHertz. To operate in the Ka-band, the configurations of various components of the antenna system would differ somewhat from their configurations in the Ku-band, but the general concepts of the invention would remain the same.
[0023] As noted previously, the receive isolation filter 40 comprises a dual-mode filter that filters both polarization components of the received signals without having to separate the components and separately filter them. This is accomplished in accordance with preferred embodiments of the invention by appropriately configuring the internal dimensions of the filter 40 so that the filter operates essentially independent of the polarization of the waves propagating through it. To this end, and with reference to FIG. 4, the filter 40 preferably has an internal waveguide passage 52 that has 90° rotational symmetry about its longitudinal axis. Thus, for example, if the plane on which the sectioned view of FIG. 4 is taken corresponds to the plane of a vertical polarization component of the received signal, the passage 52 is configured such that a plane section through the passage orthogonal to the plane of FIG. 4 and also containing the longitudinal axis of the passage, which would correspond to the plane of a horizontal polarization component, appears substantially identical. Various cross-sectional shapes having such 90° rotational symmetry are possible in accordance with the invention, including circular cylindrical passages, square passages, and others. The 90° rotational symmetry of the waveguide passage allows the filter 40 to act on both polarization components of the received signals in substantially the same manner. The filter works with right-hand and left-hand circularly polarized components as well.
[0024] Filtering of the signal is accomplished by configuring the internal waveguide passage 52 as a plurality of sequentially arranged cavities 54 , 55 , 56 , 57 , 58 having different volumes. The dimensions of the cavities are selected in accordance with the desired frequency response of the filter. The sizing of the cavities can be performed analytically by computer modeling (e.g., finite element modeling) and/or empirically by trial and error. The cavities 54 - 58 preferably comprise a series of circular cylindrical cavities arranged coaxially with respect to one another and having different diameters, and more particularly having alternately smaller and larger diameters. The cavities 54 , 56 , and 58 have relatively larger diameters and relatively shorter axial lengths while the cavities 55 and 57 have relatively smaller diameters and relatively greater axial lengths. Thus, the cavities have alternately smaller and larger length-to-diameter ratios. Advantageously, the cavities are not partitioned from one another with internal partitions as in some prior multi-cavity filters, which often include dielectric partitions having specially shaped waveguide apertures therethrough, and may also include internal probes for exciting certain resonant frequencies. Instead, the waveguide passage 52 comprises a continuous, undivided passage from the entrance to the outlet of the filter.
[0025] The filter 40 can be manufactured in various ways. Advantageously, the filter can be investment cast or die cast. Careful optimization of the cavity dimensions and careful fabrication of the mold to close tolerances enable the filter to be cast to its final shape. Hence, there is minimal labor involved in making the filter. Furthermore, the filter does not require tuning screws or the like for fine tuning the response of the filter, as in many prior cavity-type filters.
[0026] With reference primarily to FIGS. 2 and 3, the feed 24 in the illustrated embodiment comprises a receive-only feed that receives signals reflected from the reflector 20 . The feed 24 advantageously comprises a poly-rod formed of a dielectric material. In the illustrated embodiment, the feed 24 is employed for receiving dual-polarized signals containing both right-hand and left-hand circularly polarized components. Accordingly, a polarizer 40 ′ is employed behind the feed 24 . However, in the illustrated embodiment, filtering of the signals propagated by the feed 24 is performed within the associated low noise block 60 connected with the polarizer 40 ′. Of course, alternatively, the filtering could be performed by another dual-mode filter (not shown) similar in concept to the filter 40 used with the T/R feed 22 , in which case the filtered signals from the filter would be fed to the low noise block 60 . Of course, the feed 24 could alternatively be designed to receive dual-polarized signals containing both vertical and horizontal polarization components.
[0027] As already noted, the antenna 10 can include additional feeds 26 , 28 , if desired, for communicating with other satellites. Each feed 26 , 28 includes associated waveguide elements and can also include filtering elements, which are not described in detail herein for sake of brevity. Of course, one or both of the feeds 26 , 28 can employ a dual-mode filter similar to the filter 40 if dual-polarized signals are to be received by the feeds, or can employ more-conventional filters if non-dual-polarized signals are to be received.
[0028] Many modifications and other embodiments of the invention will come to mind to one skilled in the art to which this invention pertains having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the invention is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
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A transmitting and receiving apparatus comprises a transmit/receive feed operable to transmit signals to and receive signals from a source, a waveguide assembly coupled with the transmit/receive feed for propagating transmitted and received signals to and from the transmit/receive feed, and a receive isolation filter coupled with the waveguide assembly and operable to filter the dual-polarized received signals without separating the two components thereof and to provide the filtered dual-polarized received signals to a receiver so as to isolate the receiver from signals transmitted by the transmit/receive feed. Thus, both components of the received signals are filtered simultaneously along the same path of propagation, eliminating the need to split the components along separate paths, separately filter them, and then recombine them as in prior antennas.
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FIELD OF INVENTION
This invention is related to a manually adjustable fuel valve of a carburetor that supplies fuel to utility engines used as power sources for agricultural machinery, gardening machinery and light vehicles, and more particularly to a tamper resistant limit cap that facilitates control over the range in which the valve can be adjusted.
BACKGROUND OF THE INVENTION
The fuel flow of utility engine carburetors is a very small volume as compared to the fuel flow volume of a four-cycle automobile carburetor. Relatively big variations in fuel flow occur due to differences in dimensional accuracy and part quality within the carburetors. Also, engines that receive fuel via a carburetor have different individual performance characteristics. Therefore, adjustments are needed to correct fuel flow for each engine and each carburetor.
For the above reasons, a diaphragm or float type carburetor can adjust the fuel flow with a manual adjust valve by changing the effective area of passage to the main nozzle, the slow port, or the idle port, from the metering chamber. (U.S. Pat. No. 3,404,872, Japan 47-21848).
The manual adjust valves comprise a needle shaped design that changes the effective area of fuel passage proportionally to the rotation of a male screw that is installed within a female receptacle of the carburetor body. A valve head, that projects outside of the carburetor, is used to rotate the screw, and thus adjust the tip of the valve needle inside the carburetor from the outside of the carburetor. Basically, the engine and carburetor manufacturer, along with the consumer operator, can adjust the fuel flow by adjusting the manual adjust valve.
However, most consumer operators are not familiar with the delicate operation of a manual adjust valve. The instructions say "don't adjust slow speed adjust valve for idle and starting." Yet, in many cases the main adjust screw is reset by a consumer usually trying to improve the temporary poor performance of the engine due to the effects of temperature and altitude. As a result, difficulties arise such as the engine looses power, the engine will not start, or the engine exhaust composition worsens.
Moreover, emission regulations have recently been enacted for utility engines that require that the consumer not be able to operate the adjust valve beyond the limited range set by the manufacturer. Therefore, the regulations require a limit device that allows the consumer to operate the adjust valve within the emission regulation limits. In addition, the regulations require a design for a limit device that is very difficult to remove.
Currently, the limit device for the adjust valves includes a cap with a flange. The cap is installed on the head part of the needle by a tight fit. The slow adjust valve acts as a stopper for the flange of the cap. However, the current cap design can be removed from the head part by pulling in the axial direction exposing the end of the head part, thereby making it possible to rotate the adjust valve beyond the required limits. Even the flange contact stopper is easy to remove. Therefore, it would be desirable to have a reliable limit device that does not allow the consumer to operate the adjust needle beyond the emission regulations.
SUMMARY OF THE PRESENT INVENTION
The tamper resistant limit cap of the present invention serves to limit the adjustment of the fuel valve on the fuel flow passage of the carburetor, which runs from the metering chamber to the air intake, to maintain the emissions from the engine within the regulations. Limiting the adjustment of the fuel valve is accomplished by installing a cap that covers tightly on the head part of the main adjust valve.
According to an exemplary embodiment of the present invention, the cap includes a cylindrical wall. Inside the cap on the cylindrical wall are one or more projections in the axial direction of the adjust valve. The inside diameter created by these projections is smaller than the diameter of the head part. The head part of the main adjust valve, has a holding groove that holds onto one of the projections inside the cap, along with a set of knurls in the axial direction of the adjust valve. Attached to the cap's cylinder wall is an end wall at one end. The end wall has a slot hole in which the slot is wider than the center hole. The slot hole is fitted to the tool groove on the end of the head part. On the outside of the cap is a guide flange and a flange that contacts the slow adjust valve. The guide flange fits an escape groove on the head part of the slow adjust valve.
In operation the carburetor manufacturer adjusts the main fuel valve for the correct effective opening area, and then installs the cap on the head part temporarily. The first projection inside the cap holds the holding groove of the head part to prevent the cap from falling off the adjust valve. In this temporary position the cap and the head part are freely rotatable independent of one another. The engine manufacturer then adjusts the fuel valve by measuring the percentage of CO in the emission or some other procedure that will meet the emission specifications. After the fuel valve is adjusted to meet the emission specifications, the cap is rotated to a position where the needle valve cannot b e rotated in the rich direction because the flange of the cap is in contact with the slow adjust valve head part. Preferably the cap has a guide flange and the head part of the slow fuel adjust valve has an escape groove. Such a configuration allows the engine manufacturer to install a cap to a final position without having to adjust the flange position of the cap.
The cap is then installed by pushing it onto the head part. At this time the first projection inside the cap holds the knurls on the head part, the second projection holds the holding groove on the head part, and the flange of the cap contacts the slow adjust valve head part. It is possible to rotate the main adjust valve, together with the cap, to the lean direction with a small screwdriver only, within a 360 degree angle of rotation. But, the main adjust valve can not be rotated in the rich direction because the slow adjust valve head part stops the flange of the cap.
If the cap has a circular hole at the center of the slot hole and the head part has a narrow tool groove, only a screwdriver that is small enough in diameter to pass through the circular hole and thin enough to fit the narrow tool groove can approach the needle valve. It is possible to rotate the needle valve in the lean direction with a small, thin screwdriver, but it is not possible to rotate in the rich direction because the small thin screwdriver will fail against the large rotating torque required to overcome the stopper. If the cap has a guide flange and the head part slow fuel adjust valve has an escape groove, the engine manufacturer can install a cap to a final position without having to adjust the flange position of the cap.
And object of this invention is to provide an improved tamper resistant limit cap.
Another object of this invention is to provide an improved tamper resistant limit cap that is a reliable limit device that does not allow the consumer to operate the adjust valve beyond the emission regulations.
Further objects and advantages of this present invention will become apparent from a consideration of the drawings and ensuing description.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a preferred embodiment of a tamper resistant limit cap mounted on a carburetor valve assembly.
FIG. 2 is a end view of the tamper resistant limit cap mounted on a carburetor valve assembly.
FIG. 3 is a fragmentary view of the assembly depicted in FIG. 1 showing a tamper resistant limit cap in its shipping or pre-final installation position.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now in detail to the drawings, there is illustrated a novel tamper resistant limit cap. Referring to FIGS. 1, 2, and 3 adjust valves 10 and 18 are shown installed parallel to each other in a main fuel passage 8 and a slow fuel passage 9, respectively. The passages 8 and 9, respectively, run from the metering chamber of the diaphragm, or float type carburetor, to a main nozzle 5 that is open to venturi 3 and 2, and to idle and slow ports 6 and 7 that are open to the side of a throttle valve 4.
The adjust valves 10 and 18 comprise needle valves 11 and 19 within the fuel passages 8 and 9, male screws 12 and 20, for moving the needle valve 11 and 19, screwed into threaded female receptacles in the carburetor body 1, and head parts 13 and 21 projecting outside the carburetor body 1. The head part 13 of the adjust valve 10 in tie main fuel passage 8 has parallel knurls 14 located in the axial direction on the head part's 13 outer round surface. Also, the head part 13 has a circular holding groove 15 and a tool groove 16 on its end surface. The head part 21 of the adjust valve 18 in the slow fuel passage 9 has a circular escape groove 22.
In the preferred embodiment, a cap 25, acting as a limit device, is constructed from plastic. Preferably, the cap 25 includes a cylindrical wall 26, that has a little bigger inside diameter than the outside diameter of the head part 13 of the adjust valve 10. Two projections 28 and 29 are attached to the inside of the cylinder wall 26 and spaced in the axial direction. On the outside of the cylinder wall 26, there is a flange 30 that extends approximately 180 degrees about the circumference of the cylinder wall 26, and a stick shaped guide flange 31. An end wall 27 is attached to the cylinder wall 26. The end wall 27 has a slot hole 32 for approaching the tool groove 16 in the head part 13. The slot hole 32 is wider than the circular hole 33 in the center of the end wall 27.
The projections 28 and 29 are attached on the inside of the cylinder wall 26 symmetrically to each other. The axial distance between the first projection 29 and the second projection 28 is the same as the distance between the holding groove 15, of the head part 13, and the end of the adjust valve 10, as seen in FIG. 3. The flange 30 is installed hear the end wall 27 and the guide flange 31 is installed near the open end of the cap 25, between the end of the flange 30 and the head part 21 of the adjust valve 18 in the slow fuel passage 9 as seen in FIG. 1.
Prior to operation, the carburetor manufacturer adjusts the fuel valve 18 for idle and the fuel valve 10 for part and wide open throttle. Before shipping to the engine manufacturer, the cap 25 is installed on the head part 13 of the adjust valve 10. At this time, the first projection 29 is fit into the holding groove 15, making the cap 25 not easily removable from the head part 13, as seen in FIG. 3.
The carburetor manufacturer ships the above configuration to the engine manufacturer. The engine manufacturer assembles this carburetor on the engine, then adjusts the fuel valve 10, to run at wide open throttle while measuring the CO percentage in the emission. An example of a target percentage of CO is five percent. The engine manufacturer may use some other proven procedure to assure that the engine will meet the emission specifications.
This adjustment of the main fuel adjust valve is done with a small screwdriver that is able to pass through the circular hole 33 to the tool groove 16. The cap 25 is installed on the fuel valve 10, as seen in FIG. 3, such that the cap 25 and the head part 13 can temporarily rotate independently of one another. The adjust valve 10 is able to be rotated with a small amount of torque, so a small screwdriver can adjust the fuel needle even though the screwdriver only fits the center part of the tool groove 16.
After adjusting the engine speed with the adjust valve 10, so that the emissions are within specification, the cap 25 is pushed onto the head part 13 after the flange end 30A of the flange 30 is located to contact the head 21 of the adjust valve 18, as seen in FIG. 2. Preferably the cap 25 has a guide flange 31 and the head part 21 of the slow fuel adjust valve 18 has an escape groove 22. Such a configuration allows the engine manufacturer to install the cap 25 to a final position without having to adjust the flange 30 position of the cap 25.
The cap 25 is then pushed completely on to the head part 13 such that the second projection 28 is fitted to the holding groove 15, which prevents the pulling off of the cap 25, and the first projection 29 fits the knurls 14, which prevents individual rotation of the cap 25 and the head part 13, relative to each other, as seen in FIG. 1. This operation fixes the cap 25 on the adjust valve 10 firmly and places the guide flange 31 into the escape groove 22 of the head part 21 of the slow fuel adjust valve 18. The escape groove 22 allows the guide flange 31 of the cap 25 to pass freely as the cap 25 is rotated in the lean direction.
After the cap 25 is firmly installed, the tool slot 16 of the adjust valve 10 and the slot hole 32 of the cap 25 are usually not aligned with each other. The consumer of the machines or small vehicle cap approach the tool groove 16 with a small screwdriver that can pass through the circular hole 33. Therefore, the adjust valve 10 can be rotated with the same small amount of torque that was required before firmly installing the cap 25. The adjust valve 10 can be rotated only in the lean adjust direction such that the flange 30, at flange end 30A, goes away from the head part 21 in a clockwise direction until the opposite end of the flange 30 contacts the head 21 (see FIG. 2). But, the consumer cannot rotate the adjust valve in the too rich direction with the small screwdriver because the flange end 30A is stopped by the head part 21 and the rotation torque necessary to rotate the cap 25 to destroy the knurls 14 is too big to be exerted with the small screwdriver.
The guide flange 31 allows for easy operation for final installation of the cap 25, because the guide flange 31 always holds the cap 25 where the flange end 30A contacts the head 21 (same as final position).
Also, when the cap 25 is temporarily installed, the adjust valve 10 can be rotated with any relation to the cap 25 with a small amount of torque. The guide flange 31 can be installed on the same circle as flange 30.
In another embodiment of the cap 25 the guide flange 31 is eliminated. If the cap 25 does not have a guide flange 31, and further, the flange 30 does not contact the head 21 when the cap 25 is temporarily installed, a normal screwdriver can approach the tool groove 16 through the slot hole 32 in the end wall 27 of the cap 25 and make adjustments. However, the width of the tool groove 16 comprising a slot having a length and a width is too narrow for a normal screwdriver. When temporarily installing the cap 25, only a small screwdriver can pass through the circular hole 33, of the slot hole 32, in the center of the end wall 27 and adjust the fuel valve 10 in the rich and lean directions. Therefore, only those who have a small screwdriver, which can pass through the circular hole 33 and fit the narrow tool groove 16 can adjust the fuel valve 10 after the temporary installation of the cap 25. Normal commercial screwdrivers, that most have, cannot make the adjustments. A normal big screwdriver can rotate the fuel valve 10 and the cap 25 together, by the slot hole 32 of the cap 25, in only the lean direction.
After the final installation of the cap 25, it is difficult to rotate the adjust valve 10 with a small screwdriver through the circular hole 33 strongly enough to force the knurl 14 past the first projection 29. Another embodiment achieves the same effect of having flange 30 bear against the adjust valve 18, as a stopper, with a cap 25 having a cylinder wall 26, but no end wall 27.
In the above embodiments, only the adjust valve 10 has a limit device. However, in an additional embodiment, the same limit device can also be installed on the other adjust valve 18 in the slow fuel passage 9.
Thus, it should be noted that it is convenient to ship the carburetor with the cap 25 already temporarily installed, so the engine manufacturer can adjust the fuel valve 10 before final installation of the cap 25. After final installation it is only possible to rotate the valve 10 in the lean direction from a predetermined position by the engine manufacturer. It is also difficult to remove the cap 25 as a limit device from the adjust valve 10 because the first projection 29 holds the knurls 14 of the valve 10 firm and the second projection 28 holds the groove 15 firm. Therefore, after final installation the operator can adjust the fuel valve 10 in only the lean direction within the emission regulations.
If the end wall 27 on the cap 25 has a circular hole 33 at the center of the slot hole 32, the usable adjustable tools are limited. This configuration prevents malicious excessive operation and improves reliability. Also, if the cap 25 has a guide flange 31 it makes it easy to install the cap 25 and increases productivity.
Thus, the tamper resistant limit cap of the present invention provides many benefits over the prior art. While the above description contains many specificities, these should not be construed as limitations on the scope of the invention, but rather as an exemplification of the preferred embodiments thereof. Many other variations are possible. Accordingly, the scope of the present invention should be determined not by the embodiments illustrated above, but by the appended claims and their legal equivalents.
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A tamper resistant limit cap for a carburetor having manual adjust valves that are able to adjust the effective area of the main fuel passage and the slow speed fuel passage. The cap covers tightly on the head part of the main fuel adjust valve and includes a flange attached to the outside of the cap that abuts a stop upon rotation of the cap, a guide flange attached to the outside of the cap to locate, upon installation, the final position of the cap, and two projections on the inside of cap to prevent removal of the cap from valve head part or independent rotation of the cap and head part relative to each other.
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BACKGROUND AND SUMMARY OF THE INVENTION
The invention relates to a servo control, especially for power steering for motor vehicles, with a shaft which serves for actuation and is subdivided axially into an input-side primary-shaft part and an output-side secondary-shaft part. One shaft part projects axially into a bush part coupled fixedly in terms of rotation to the other shaft part and forms with the latter a servo-valve arrangement working in dependence on relative rotations between the shaft parts, in the manner of a rotary-slide arrangement. A torsion bar connects the shaft parts in a rotationally elastic manner and is arranged in an axial bore of the shaft parts so as to leave an annular space free in the one shaft part. A prestressed spring is provided which is effective between the bush part and the one shaft part and the prestress of which seeks to keep the bush part and the one shaft part in a middle position relative to one another.
A corresponding power steering is the subject of British Patent Document GB 2,165,502 A. The prestressed spring determines a minimum torque which has to take effect on the shaft in order to obtain an adjustment of the servo-valve arrangement out of the middle position or neutral position. Moreover, this spring, together with the prestress-free torsion bar, determines the amount of further adjustment of the servo-valve arrangement in the event of torques which increase further.
This arrangement ensures that the servo control or power steering works purely mechanically, that is to say without power assistance, within a range of steering forces which is predetermined by the prestress of the prestressed spring. This guarantees, where a power steering of a motor vehicle is concerned, that the driver acquires a good feel for the steering forces actually effective on the steering wheels of the vehicle.
German Patent Document DE 3,925,992 Al discloses a further servo control or power steering, in which two coaxial shaft parts are coupled to one another positively, but with play, in such a way that limited relative rotations between these parts are possible counter to the resistance of a prestressed leg spring arranged between them. These relative rotations bring about a pivoting stroke of a lever which is arranged between the shaft parts and which thereby actuates the control slide of a servo-valve arranged in the one shaft part. The prestressed leg spring projects with two radial legs into axial slots corresponding to one another in axially mutually overlapping endpieces of the two shaft parts. The mounting of the leg spring is comparatively complicated, since a visual check is possible only to a restricted extent and the lever actuating the control slide of the servo-valve also has to be mounted between the two endpieces.
An object of the invention is to achieve an even further constructive simplification in a servo control of the type mentioned in the introduction.
This object is achieved, according to the invention, in that the one shaft part and the bush part have, at their ends facing the other shaft part, corresponding axial slots open towards the other shaft part, and in that there is arranged as a prestressed spring in the annular space between the torsion bar and the one shaft part a leg spring, the legs of which project into respective corresponding axial slots of the bush part and of the one shaft part and, in the circumferential direction of the shaft axis, have a smaller cross-section than the axial slots and, in the middle position, rest on respective corresponding axial edges of the two axial slots.
As a result of the design according to the invention, the mounting of the leg spring and the coupling of the other shaft part take place on the same end face of the bush part. Accordingly, after the arrangement of the bush part on the one shaft part, that is to say after the mounting of the servo-valve arrangement, the leg spring and the further shaft part can be arranged and connected to the bush part respectively. This results in a mounting sequence which can be carried out in a simple way, whilst the arrangement of the leg spring can be carried out completely with a visual check.
Moreover, it is advantageous that, in this design, the legs of the leg spring can also act as a limitation for the maximum relative rotation between the shaft parts.
According to an expedient embodiment of the invention, the leg spring has a flat characteristic, that is to say the prestress of the leg spring is increased only relatively little in the event of additional elastic deformation of the latter. In contrast, the prestress free torsion bar can have a comparatively steep characteristic, that is to say, in order to achieve an additional torsion of the torsion bar, the torques must increase comparatively sharply.
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 shows an axial section through a power steering arrangement constructed according to a preferred embodiment of the invention;
FIG. 2 shows a radial section corresponding to the sectional line II--II in FIG. 1; and
FIG. 3 shows the spring characteristic of the torsion bar and leg spring.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A steering handwheel (not shown) of a motor vehicle and its steering wheels or its steering gears are drive-coupled to one another via a steering shaft which has a primary-shaft part 1 and a coaxial secondary-shaft part 2. The shaft parts 1 and 2 are designed as tubular parts and directly adjoin one another axially. On the end face confronting the secondary-shaft part 2, the primary-shaft part 1 is widened on the inside, so as to produce an inner circumferential groove 3, of which the flank on the right in the drawing is formed by an annular step within the primary-shaft part 1 and of which the flank on the left is formed by the end edge of the secondary-shalt part 2.
Arranged in the interior of the two shaft parts 1 and 2 is a torsion bar 4 which is connected at its ends to the shaft parts 1 and 2 fixedly in terms of rotation by means of crosspins 5. Between these ends, the torsion bar 4 has a cross-section reduced in relation to the cross-section of the interiors of the shaft parts 1 and 2, so that an annular space 6 remains free.
Arranged on the end face of the secondary-shaft part 2 confronting the primary-shaft part 1 is a radial driving pin 7, via which a bush 8 arranged rotatably on the primary-shaft part 1 is coupled fixedly in terms of rotation to the secondary-shaft part 2.
The bush 8 is encased by a stationary housing 9.
A plurality of annular grooves 10 is arranged on the outer circumferential side of the bush 8, so as to form between the bush 8 and the inside of the housing corresponding annular spaces which are closed off by means of lateral sealing rings 11.
The annular spaces formed by the annular grooves 10 are connected via housing-side connections (not shown) to hydraulic lines of a servo-system, the servo-valve arrangement of which is formed in a basically known way by the bush 8 and by a region of the primary-shaft part 1 covered by the latter, control edges 12 being arranged between the bush 8 and primary-shaft part 1, so that, during a relative rotation between the bush 8 and primary-shaft part 1, a more or less large pressure difference can be generated between connections of a servo-motor.
According to FIG. 2, axial slots 13 and 14 located diametrically opposite one another and open towards the end faces of the primary-shaft part 1 and the bush 8 are arranged on the end faces of the primary-shaft part 1 and of the bush 8 which confront the secondary-shaft part 2. In the circumferential direction of the primary-shaft part 1 and the bush 8, the axial slots 13 and 14 have equal widths, so that their axial edges are in alignment with one another in the middle position shown in FIG. 2.
The legs of a leg spring 15 arranged within the inner circumferential groove 3 of the primary-shaft part 1 and annularly surrounding the torsion bar 4 project into the axial slots 13 and 14, that is to say the legs of the leg spring are connected to one another by means of a helical spring region. In the middle position according to FIG. 2, the legs rest with prestress on the lower axial edges of the two axial slots 13 and 14 and correspondingly seek to keep the primary-shaft part 1 and the bush 8 (as well as the secondary-shaft part coupled fixedly in rotation to the bush 8) in the middle position.
The primary-shaft part 1 and the bush 8 can be rotated relative to one another out of this middle position only when a torque exceeding the prestress of the leg spring 15 takes effect.
This relative rotation is possible because the axial slots 13 and 14 have a width, as measured in the circumferential direction of the primary-shaft part 1 and the bush 8, which is clearly larger than the thickness of the legs of the leg spring 15.
FIG. 3 shows the characteristics of the torsion bar 4 and leg spring 15. The angle of rotation is plotted on the abscissa, whilst the torque is plotted on the ordinate. The curve K D (corresponding to the torque based on the torsion bar spring constant times the angle of rotation) shows the conditions when the leg spring 15 is omitted. With a rotation of the primary shaft 1 and the bush 8 or secondary shaft 2 relative to one another, increasing in relation to a middle position, a clearly increasing torque occurs.
The curve K S (corresponding to the torque based on the leg spring coefficient times the angle of rotation) shows the conditions when the torsion bar 4 is omitted. As a result of the prestress of the leg spring 15, a relative rotation between the primary-shaft part 1 and the bush 8 or secondary-shaft part 2 in relation to the middle position is achieved only when a minimum torque is effective. With an increasing angle of rotation, the torque then increases only moderately.
The curve K shows the conditions when the torsion bar 4 and leg spring 15 are jointly effective. It can be seen that the minimum torque which has to be exceeded in order to obtain an angle of rotation relative to the middle position is determined by the leg spring 15. The further increase in the torque is then determined predominantly by the torsion bar 4.
In connection with the power steering, this means that power assistance takes effect only when the said minimum torque occurs between the primary-shaft part 1 and secondary-shaft part 2. In the event of lower torques, no power assistance takes effect, that is to say the steering works purely mechanically.
Although the invention has been described and illustrated in detail, it is to be clearly understood that the same is by way of illustration and example, 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.
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A servo control is disclosed especially for a power steering for motor vehicles. A shaft serves as an actuating member and is subdivided axially into a primary shaft and a secondary shaft. The two shaft parts are coupled elastically to one another via a torsion bar and a prestressed leg spring acting parallel thereto. Accordingly, a relative rotation adjusting a servo-valve arrangement can occur between the two shaft parts only when the shaft is loaded by a torque which exceeds the prestress of the leg spring.
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CROSS-REFERENCES
This application is a divisional of patent application Ser. No. 09/882,092 filed on Jun. 18, 2001 now abandoned, currently pending and which is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to the general field of fly-fishing and is particularly concerned with a fly fishing rod having a detachable reel seat and waist holder therefore. More particularly, the present invention relates to a reel seat holding device for a movable reel and reel seat assembly for fly fishing rods.
BACKGROUND OF THE ART
During most sport fishing activities such as fly casting, spin casting, bait casting and the like, an artificial lure or a live bait having a fishing line attached thereto is projected or cast into fish filled waters in hope that a fish will take the bait. Since most fishes are quite easily scared away by human presence, it is often desirable to cast the bait far away from the fisherman.
Typically, the energy which propels both the lure and the fishing line is stored and subsequently released by the fishing pole which conventionally consists of a thin elongated flexible rod. When the rod releases the potential energy contained therein, this energy is transformed into kinetic energy which is transmitted to the fishing lure and propels the latter over the surface of water away from the fisherman.
During both bait and spin casting activities, the lure or bait being relatively heavy, this causes the fishing rod to flex as the fisherman from the back cast starts the forward cast, thereby storing energy in the rod. At the end of the forward cast, as the rod straightens out, the line is released and allowed to move freely across the water away from the fisherman.
Conversely, in fly casting the artificial lures or flies used are very light weight and not capable of causing the rod to flex. In fact, the lures are so light weight that the resistance due to air friction cannot be overcome unless the fly is attached to a heavier object. Hence, a fly fisherman is really casting the fly line rather than the fly itself. A great deal of efforts has thus been extended on designing fly lines and tailoring casting methods to efficiently propel the line through the air.
Parallel to the search for fly-casting efficiency, other efforts have been made to lighten the fishing rod and reel as much as possible for the fisherman. This search for overall lightness in the fishing gear handled by the fisherman stems from the fact that each cast made to propel the lure the right distance requires constant and always well-controlled muscular efforts.
First, with each cast, the fisherman's arm has to transmit to the rod the energy required to send the line the required distance. That means the fisherman must either make many false throws in sequence to allow the line to go progressively farther or pull back the part of the line that is already in the water in a single sharp movement and then recast in another movement right after it has been pulled back. This effort is required each time the fisherman wants to return the lure to the surface of the water. Therefore a fisherman who casts his line twice a minute during a fishing day lasting eight hours will end up making close to 1,000 casts, all of them different. Furthermore, for each cast, the fisherman must have precise and firm control of the movement of the rod, which has to move through a well-defined axis to get the required propulsion.
Through years of refinement, fly casters have learned to control the loop created in the line by the casting motion. It is well known that this loop is one of the most important parameters for fly casters to control. Thus, fly casters must make subtle movement adjustments to maintain the line loop as small as possible. This is, in part, accomplished by keeping the rod tip in a substantially vertical plane with respect to the ground. These subtle movement adjustments in a somewhat non-ergonomic position may quickly lead to muscle fatigue which, in turn, may deter the overall enjoyment of the fly fishing casting activity. Furthermore, as the infrequently solicited muscles of the hand, wrist and arm become tired, the efficiency of the casting stroke will be lessened.
Accordingly, it would be desirable to provide a fly fishing rod that is lighter in weight than conventional fishing rods so as to lessen the risk of muscle fatigue. The prior art has recognized this need and, hence, has notably proposed various types of fishing equipment made out of lightweight material. Regarding the construction of the rod itself, the use of lighter and lighter materials, for example, graphite and graphite composites, has allowed for significant improvements. The same trend holds for reels, which are being made with ever-lighter metal alloys and with simpler and simpler mechanisms. But progress in this latter area has become less and less a factor in the search for lightness; in the end, it has provided limited improvement since a great portion of the weight resides in the reel and associated reel seat. Nowadays the fishing rods are somehow ⅓ to ⅕ the weight of the total combination of their reel and attachment.
Also, some rod holders have been proposed in order to reduce the fisherman's efforts. But rod holders have heretofore been designed for general-purpose rods almost exclusively. Prior art rod holders have been utterly unamenable to use with a fly rod, instead being configured to accommodate general-purpose rod and reel.
However, the general-purpose rod and reel is proportioned differently from a fly rod. The reel mounted on a general purpose rod is usually located some distance from the end of the rod most proximate to the reel, that is, the reel is farther up the rod, more towards the eyelets of the rod and farther from the end of the rod held in the fisherman's hand.
The fly rod and reel is proportioned quite differently. On a fly rod, the mounting for the reel is located very near the end of the pole where it would be held if it was a general-purpose rod. In fact, the fly rod is actually held by the fisherman in a different way than the general-purpose rod. When using a fly rod, the rod is griped above the reel, the hand of the fisherman being placed between the reel and the rod eyelets. Consequently, the handle end of the fly rod does not extend very far past the mounted fly rod. Essentially, the reel of a fly rod is mounted nearly at the end of the rod, while the general-purpose rod has its reel mounted about one third of the way up the rod towards the eyelets.
The prior art rod holders are constructed so that the end of the rod most proximate to the reel is inserted into the holder. These holders are usually tubular in construction, a configuration most suitable for holding the cylindrical fishing rod. This sort of holder will not work when used with a fly rod. As noted above, the fly rod has little to no handle extending below the reel. Hence, the prior art rod holder simply will not work satisfactorily with a fly rod. Furthermore, the idea of inserting the rod into a holder to take some weight off the fisherman does not work for fly fishing rods. Indeed, once the rod is in its holder, it becomes practically immobile, which is hardly compatible with a fishing style that involves repeated casts.
In order to reduce the weight of the fishing rod the prior art shows attempts at temporarily removing the fishing reel from the fishing rod. For example, U.S. Pat. No. 3,556,365, George Nulan inventor, issued Jan. 19, 1971, discloses a spinning reel transfer mechanism in which a mechanical holder for spinning reel is supported on a frame shaped to fit the contour of the fisherman's body and is attached to a belt for being buckled around the body of the fisherman. From a lower end of the support frame, there is a belt which is disposed for being connected with the belt at the rear of the person wearing it. It does provide means by which a reel is placed on an extension to the mechanical holder leaving the rod free in one hand to facilitate casting.
Although offering the advantage of reducing the overall weight of the fishing rod, the invention disclosed in the hereinabove mentioned patent, suffers from numerous drawbacks. One of the main disadvantages associated with this invention resided in that only the reel is separable from the rod. The intended user thus needs a reel seat which remains attached to the rod and a second reel seat attached to the belt. The intended user must therefore attach the reel to either one of the reel seats. This operation can prove to be both tedious and time consuming.
Accordingly, there exists a need for an improved fly fishing rod having a detachable reel seat and waist holder therefore.
SUMMARY OF THE INVENTION
The invention presented here comes within the perspective of the previous research in the sense that it seeks to enable the fisherman to cast with the lightest possible rod. However, it achieves this objective in a different way. It allows the fisherman to use a rod wherein he can choose, at any time, to detach the reel seat and, more importantly, the reel.
The invention is based on two important observations concerning the function of the reel in fly-fishing. First, practice has shown that the reel plays a secondary role in the casting and retrieval of the lure, since, with each cast, the line that has been cast does not have to be rewound onto the reel. Often, the fisherman does not reel any of it. If he does, he takes in only a small portion of it. Whatever the length of line he does reel in, he only winds up in his hand or lets fall around his feet or in the water this length of line. Doing so allows him to recast freely and rapidly, which he could not do if the line was rewound onto the reel.
Second, the reel, including the part of thereof that stays on the reel after a cast (often 30% to 50% of the line's entire length), is the heaviest part of the rod. The reel can easily be three times heavier than a rod of the highest quality. The technique that allows a person to fish without the reel attached to the rod means a lightening of equipment greater than what has been achieved to date by other inventions.
The fly fishing rod proposed by the present invention has a detachable reel seat which can be readily detached and attached from and to a conventional fly fishing rod through a set of simple ergonomic steps without requiring special tooling or manual dexterity. The attachment and detachment to and from the fly fishing rod can be accomplished quickly even in an harsh environment when manual skills are lessened by cold, humidity or the like.
The idea presented here of a rod with a detachable reel seat is applicable to a new rod specifically designed for that purpose and is equally applicable to all other existing rods. Indeed, the invention makes it possible to design a rod with a reel seat that can be detached from the rod handle instead of having to stay attached, as it is the case with all existing rods on the market. The invention also makes it possible for all existing rods to use a device for holding an additional and movable reel seat used to hold the reel.
In both cases, the reel seat is moved from the rod to a waist holder attached to the fisherman's belt. Reel seats, being somewhat of a more standard nature than the varying reels which are adapted to the user and the environment, can be quickly and ergonomically mounted on a relatively standard waist holder therefore. The proposed waist holder associated with the present invention is specifically adapted to receive a reel and reel seat assembly. The proposed waist holder is specifically designed so as to ergonomically position the reel and reel seat assembly (a right-handed will be using the right model as shown in FIG. 4 and will preferably install it on his right waist). It is also provide with a line positioning means, a guiding eyelet, which further increases ergonometric of the casting procedure.
An intended user of the proposed invention can thus use the fly fishing rod either with the reel and reel seat assembly attached thereto or detached therefrom depending on the particular setting. When desired or needed, the chosen option can be easily modified through simple ergonomic steps. The rod design with a detachable reel seat preserves all the advantages of the traditional rod equipped with its own fixed reel seat and, at the same time, allows the fisherman, whenever he wishes, to take advantages of all the benefits of a rod free from the weight of its reel.
Another advantage of the present invention resides in that the proposed fly fishing rod and associated waist holder is specifically designed so as to be manufacturable using conventional forms of manufacturing thus providing a fly fishing rod and associated waist holder which will be economically feasible, long lasting and relatively trouble free in operation.
According to a general aspect, there is provided a fishing rod which comprises a fishing rod shaft having a primary reel seat and at least one guiding eyelet extending from the fishing rod shaft for guiding a fishing line along the fishing rod shaft; a hollow cylinder having an outer surface, a longitudinal cavity defined therein, and a cylinder mounting foot protruding outwardly from the outer surface, the cylinder mounting foot being juxtaposed to and releasably engaged with the primary reel seat for mounting the hollow cylinder to the fishing rod shaft; and an auxiliary reel seat having a reel mounted thereto through a reel mounting foot, at least a portion of the auxiliary reel seat being releasably and slidably inserted into the cavity of the hollow cylinder with the reel extending outwardly therefrom, the at least one guiding eyelet guiding a fishing line from the reel along the fishing rod shaft by receiving the fishing line therethrough.
According to another general aspect, there is provided a fishing rod comprising a fishing rod shaft with a primary reel seat and at least one guiding eyelet extending from the fishing rod shaft; a hollow cylinder having a cylindrical wall defining a longitudinal cavity, an outer surface and an insertion opening, the hollow cylinder having a cylinder mounting foot extending outwardly from the outer surface of the cylindrical wall, the cylinder mounting foot being releasably engaged with the primary reel seat for mounting the hollow cylinder to the fishing rod shaft; and an auxiliary reel seat releasably and slidably inserted into the longitudinal cavity of the hollow cylinder, the auxiliary reel seat having a reel mounted thereon, the reel extending outwardly through the insertion opening, the at least one guiding eyelet guiding a fishing line from the reel along the fishing rod shaft by receiving the fishing line therethrough.
According to a further general aspect, there is provided a fishing rod comprising: a fishing rod shaft with a reel seat mounted to the fishing rod shaft; a hollow cylinder having a cylindrical wall defining an outer surface, a longitudinal cavity therein and an insertion opening therein, a cylinder mounting foot protruding outwardly from the outer surface, and a coil spring disposed inside said hollow cylinder at a closed end thereof, the cylinder mounting foot being releasably engaged with the reel seat for mounting the hollow cylinder to the fishing rod shaft; and a reel and reel seat assembly having a reel mounted to an auxiliary reel seat through a reel mounting foot, at least a portion of the auxiliary reel seat being releasably and slidably inserted into the cavity of the hollow cylinder with the reel extending outwardly therefrom through the insertion opening, said coil spring being compressed when the at least a portion of the auxiliary reel seat is inserted inside said hollow cylinder.
BRIEF DESCRIPTION OF THE DRAWINGS
Two embodiments of the present invention will now be disclosed, by way of examples, in reference to the following drawings.
FIG. 1 a is a side elevation view with sections taken out illustrating part of a fly fishing rod having a detachable reel seat in accordance with a first embodiment of the present invention with the reel seat being mounted to the fishing rod, FIG. 1 b is a side elevation view of the detachable reel seat being detached from or mounted to the fly fishing rod, and FIG. 1 c is a side elevation view of the detachable reel seat detached from the remainder of the fishing rod;
FIG. 2 a is a perspective view illustrating a sleeve-like adapter having a reel mounted thereto and a cylinder with an opening, which runs from its top down along one side, and adapted for receiving the sleeve-like adapter therein, the sleeve-like adapter being shown before being inserted in the opening of the cylinder and FIG. 2 b is a perspective view of the sleeve-like adapter after the adapter has been inserted in the opening of the cylinder.
FIG. 3 is a perspective view illustrating the sleeve-like adapter and the cylinder shown in FIGS. 2 a and 2 b once installed in place, behind the handgrip and on the original reel seat of the rod, where the reel is normally attached;
FIG. 4 a is a perspective view illustrating a waist holder of the present invention with the cylinder shown in FIGS. 2 a, 2 b and 3 mounted thereto to hold the additional reel seat on a conventional rod and FIG. 4 b is an exploded perspective view, of the waist holder and the cylinder; and
FIG. 5 a is a perspective view illustrating a fishing vest or life jacket with a band, FIG. 5 b is a cross-section view of the fishing vest or life jacket with the band, and FIG. 5 c is a perspective view of the fishing vest or life jacket with the band having the waist holder and the cylinder shown in FIGS. 4 a and 4 b mounted thereto, close to the fisherman's waist.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 , it is shown a fly fishing rod 10 in accordance with a first embodiment of the present invention.
The fishing rod 10 is preferably of the fly fishing type. The fishing rod 10 includes an elongated rod shaft 14 (only a butt section thereof being shown). A set of guiding eyelets 16 (only one of which is shown) are mounted on the rod shaft 14 for guiding a fly line 18 there along.
Typically, although by no means exclusively, the rod shaft 14 includes a tip section releasably attached to the butt section by a male/female ferrule combination as is well known in the art. The proximal end of the butt section part of the rod shaft 14 is attached to a general cylindrical handgrip 20 . A keeper ring 22 is preferably mounted on the rod shaft 14 adjacent the hand grip 20 .
The fishing rod 10 else includes a conventional fly reel 24 for winding the fly line 18 . The fly reel 24 typically includes a spool 26 rotatably mounted on a reel frame by an axle 28 and having a drag 30 attached thereto. A spool handle 32 typically extends laterally from the spool 26 . The fly reel 24 also includes a mounting foot 34 extending radially therefrom. The mounting foot 34 is adapted to be mounted on a reel seat 36 in abutment contact with a cylindrical reel seat base 38 . This base has a butt cap 47 at its proximal end, but is open at its distal end 40 .
The mounting foot 34 is adapted to be maintained in a predetermined relationship relative to the reel seat base 38 by frictional contact with two rings 40 , 44 and a screw locking nut 46 threadably mounted on the threaded proximal end 48 of the reel seat base 38 .
The fishing rod insofar described is somewhat similar to conventional fly fishing rods and modifications to the standard components may be made without departing from the scope of the present invention.
One of the main feature of the present invention resided in that the reel 24 and reel seat 36 combination is attachably connected to hand grip 20 by a reel and reel seat-to-hand grip releasable attachment means 50 .
In a first embodiment of the invention, the reel and reel seat-to-hand grip attachment device 50 includes an attachment rod 52 (being normally a prolongation of the rod shaft 14 ) extending from the handgrip 20 in a direction opposite the rod shaft 14 . The attachment 52 rod is ended with two resilient bushings 53 and 51 and a corresponding attachment bushing channel 55 extending through a connecting segment extending distally from the reel seat base 38 and design so the resilient bushings 53 and 51 are inserted tightly into the bushing channel 55 .
It should be understood that the other reel and reel seat combination to-handle attachment device could be used without departing from the scope of the present invention as long as they allow for efficient releasable connection there between.
FIG. 2 presents a second embodiment of the invention, namely the device used to hold or release an additional reel seat 36 accompanying any conventional fly fishing rod 10 .
The main part of this device is a hollow cylinder 80 that is preferably made of metal or plastic. This cylinder 80 is closed at its proximal end 82 , partially open on one of its sides 84 and its lower part 86 , and fully open at its distal end 88 .
Inside the cylinder 80 , at the closed end 82 , is a coil spring 90 in the form of a cone. At the middle of the topside of the cylinder 80 , a mounting foot 92 is attached in two holes 94 , preferably with rivets or bolts 96 . This mounting foot 92 is used to attach the cylinder 80 to the reel seat 36 of the fly fishing rod 10 . The mounting foot 92 is somewhat similar in its form, and wholly identical in its function, to the mounting foot 34 used to attach a reel 24 to a reel seat 36 .
The purpose of the cylinder 80 is to hold a reel seat 36 , equipped with a reel 24 , in such a way that both are very easily removable. To insert them into the cylinder 80 , it is necessary to place the proximal end 48 of the reel seat 36 into the opening 88 of the cylinder 80 and to slide it to the bottom 82 while pivoting the reel 24 laterally about 90 degrees to the ground (as illustrated in the main drawing in FIG. 2 ), so that it will fit into the cylinder's side opening 84 . When the butt cap 47 of the reel seat 36 sits on and compresses the coil spring 90 at the bottom 82 of the cylinder 80 , it is necessary to return the reel 24 to its normal vertical position. This is done by pivoting it inside the lower opening 86 of the cylinder 80 , all the while taking care to insert the mounting foot 34 of the reel 24 into the narrow groove 98 at the top of the lower opening 86 . The pressure exerted by the compressed spring 90 on the mounting foot 34 holds the reel seats 36 and reel 24 firmly in place inside the cylinder 80 .
The drawing on the lower left side of FIG. 2 illustrates the final position of the reel seat 36 and reel 24 in the cylinder 80 . FIG. 3 shows the cylinder 80 (holding the reel seat 36 and reel 24 ) attached to a conventional handgrip rod 20 and ready to be used.
The fisherman can thus fish with a reel seat 36 and reel 24 which, whenever he chooses, can be detached from the hand grip 10 and held on a support at his waist 12 . To detach them from the cylinder 80 , all that needs to be done is to perform the opposite of the operation described above: push the reel seat 36 towards the bottom 82 of the cylinder 80 to compress the spring 90 and release the mounting foot 34 from the groove 98 into which it has been inserted, then pivot the reel 24 sideways and slide the reel seat 36 and reel 24 out of the cylinder 80 .
FIG. 4 shows the waist holder 12 on the fisherman's belt 66 (on the same side that he holds his fishing rod on). The holder 12 includes a holder base 56 made preferably of plastic or light metal. The holder base 56 defines a base inner surface 58 , a base outer surface 60 , a pair of opposed base lateral surfaces 64 and a pair of opposed base end surfaces 62 , 63 . The base inner surface 58 is preferably given a generally arcuate configuration about its longitudinal axis so as to substantially conform to the configuration of the contour of the waist of the intended fisherman.
Approximately half the distance between the base inner 58 and outer surfaces 60 is a slot 68 , approximately 2 mm wide, open on the inferior surface of the base 63 , running the length of the base 56 and following a curve identical to the curve of the inner surface 58 of the base 56 . The fisherman slides his belt 66 into this slot 68 along the entire length of the base 56 . Even though the belt 66 is held tightly in the slot 68 , the waist holder 12 remains horizontally mobile and can still be removed by the fisherman.
On the outer surface 60 of the base is a groove 70 in the form of a semi-circle running across the entire length of the base 56 . In this groove 70 is set a cylinder 80 similar to the one presented in FIGS. 2 and 3 ; this cylinder 80 is attached to the outer surface 60 of the base 56 of the waist holder 12 by two bolts or rivets 100 , inserted in this outer surface 104 through two holes 102 in the cylinder 80 . After the cylinder 80 has been attached to the base 56 , its front end 88 runs about one centimetre past the edge of the waist holder's base 56 so that the fisherman can insert easily the reel seat 36 into the cylinder 80 . On the inferior part of this front end 88 a laterally open eyelet 106 guides the fishing line 18 from the waist holder 12 to the rod 10 .
This cylinder 80 allows the fisherman to insert the reel seat 36 and the reel 24 from his fishing rod 10 onto the waist holder 12 , and then to detach them, following the procedure described in FIG. 2 . The waist holder 12 is designed to hold either the detachable reel seat 36 seen in FIG. 1 or the movable reel seat 36 shown in FIGS. 2 and 3 . It can thus be adapted to either of the two embodiments of this invention.
The waist holder 12 is configured, sized and positioned so that the fly line 18 is substantially in line with the handle 20 of the rod 10 and the latter is in its frontal casting position substantially horizontal and proximate to the waist of the intended user. Also the sufficient width of the holder base makes it well visible and easy to handle by the angler.
FIG. 5 illustrates a device allowing the waist holder 12 to be worn on the side of the fisherman's life jacket 108 .
A rigid band 110 , preferably made of plastic or metal, about as wide as a belt and only slightly longer than the waist holder 12 itself, can be attached to a life vest 108 . The central (and main) part of the band 110 is slightly curved on its longitudinal axis so that it can be inserted into the slot 68 on the waist holder 12 . At each end 112 , 114 of this curved part, the band becomes flat and extends about three centimetres in an axis parallel to the fishing vest 108 .
These tow ends 112 , 114 of the band 110 are attached to the vest by four bolts 116 which go through these ends 112 , 114 and the vest material 108 . On the inside of the vest 108 , nuts 118 tighten the bolts 116 . These nuts 118 are supported against the inside of the vest 108 on two small plates 120 , each 6-cm by 6-cm, and made of the same rigid materials as the band 110 itself.
Once the rigid band 110 is attached, the fisherman can install his waist holder 12 on it. He then can insert the reel 24 and the reel 36 from the rod 10 into the waist holder 12 .
An identical band device can also be installed in the same way on the cloth-type vest that many fishermen wear.
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The present invention concerns a reel seat holding device for a movable reel and reel seat assembly for fly fishing rods. The holding device comprises a case that is arranged for releasably receiving the reel seat therein, when the reel and reel seat assembly is detached from a fly fishing rod. A device is provided for mounting the case on a fishing rod or an holder. The disclosure of the present invention also relates to a fly fishing rod with a movable reel and reel seat assembly and a waist holder for the holding device.
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FIELD OF THE INVENTION
[0001] The present application relates to a shoring post, in particular to a telescoping shoring post used in systems used for construction.
BACKGROUND TO THE INVENTION
[0002] In typical construction systems, a shoring post is used to help support objects, usually a ceiling or roof. With varying heights of ceilings, it is obviously beneficial to have a shoring post that capable of being quickly adjusted from one height to another, while at the same time ensuring a safe work environment for all workers.
[0003] Truss systems, such as those outlined in U.S. Pat. No. 6,116,567 exist, and involve screw jacks that rotate around the post to adjust the height of the post. While this is fine for small adjustments, if one wishes to extend or retract the post several feet, this could be very time consuming.
[0004] Another type of shoring post, described in Canadian Patent No. 2,249,921, is adjustable and can be used in a system or on their own. These types of shoring posts use a screw, while others of a similar type use a pin-type assembly. While both of these allow for the post to be extended quicker than a screw-jack type, they require the use of small screws and pins, which may not only be difficult to use, but are also easily lost.
[0005] A further prior art post is disclosed in U.S. Pat. No. 5,653,415 to Peri GmBH. The '415 post can be adjusted using pins for quick adjustment to the approximate height, and then a fine adjustment means. The problem with pins is that they can easily be lost and are an extra component that is required when erecting/disassembling the post.
[0006] There remains a need for a telescopic shoring post that can be quickly adjusted from one position to another.
[0007] There also remains a need for a shoring post of simpler design, with significantly fewer pieces involved.
SUMMARY OF THE INVENTION
[0008] The present invention overcomes the deficiencies of the prior art by providing a shoring post, comprising a hollow outer leg, a plurality of slots along the length of the outer leg, an inner leg dimensioned to fit within the outer leg, a tongue plate welded to one end of the inner leg, the tongue plate including a plurality of tongue members, wherein the inner leg may be rotated within the outer leg from a first position where the tongue members are fully within the outer leg, and a second position where the tongue members extend through the slot, locking the inner leg in position relative to the outer leg.
[0009] Additionally, the preferred embodiment of the shoring post includes an adjusting screw assembly, an adjusting handle, and a plurality of support pins, where the screw assembly is used for fine adjustments to the length of the post. There is also a lower outer leg at the opposite end of the screw assembly. Another addition to the preferred embodiment includes a plurality of grooves along the length of the inner leg and the outer leg.
[0010] The present application therefore provides a telescoping post shore comprising: an outer tube; a plurality of slots disposed longitudinally along said outer tube; an inner tube; at least one tongue member affixed to said inner tube and projecting from said inner tube, said at least one tongue member configured to be received by said plurality of slots; wherein said inner tube and at least one tongue member are dimensioned to slide within said outer tube and said inner tube and at least one tongue member can be rotated within said outer tube to engage said at least one tongue member with at least one of said plurality of slots.
[0011] Other aspects and advantages of the device will become apparent from the following Detailed Description and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The present invention will be better understood with reference to the drawings, in which:
[0013] FIG. 1 is a perspective view a shoring post according to the present invention;
[0014] FIG. 2 is a side view of a preferred shoring post;
[0015] FIG. 3 a is a view of section A-A from FIG. 2 , with the tongue in the unlocked position;
[0016] FIG. 3 b is a view of section B-B from FIG. 2 , with the tongue in the locked position;
[0017] FIG. 4 is a side view of the inner tube;
[0018] FIG. 5 a is a view of section C-C from FIG. 4 ;
[0019] FIG. 5 b is a support tongue capable of being fixed to the bottom of the inner tube from FIG. 4 ;
[0020] FIG. 6 is a side view of the outer tube;
[0021] FIG. 7 is a view of section D-D from FIG. 6 ;
[0022] FIG. 8 is a view of section E-E from FIG. 7 ;
[0023] FIG. 9 is a side view of the shoring post with an alternate method of making fine adjustments;
[0024] FIG. 10 is a cross sectional view of an inner an outer tube showing an alternative dimensioning for inner and outer tubes;
[0025] FIG. 11 is a cross sectional view of an inner an outer tube showing a further alternative dimensioning for inner and outer tubes;
[0026] FIG. 12 is a cross sectional view of an inner an outer tube showing yet a further alternative dimensioning for inner and outer tubes; and
[0027] FIG. 13 is a cross sectional view of an inner an outer tube showing an alternative dimensioning for inner and outer tubes without channels.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0028] Reference is now made to the drawings. In the preferred embodiment, each post 10 has an inner tube 12 and an outer tube 14 . The inner tube 12 is adapted to extend telescopically from within the outer tube 14 , as depicted in FIG. 1 . Inner tube 12 can be seen best in FIGS. 4 , 5 a , and 5 b.
[0029] In a preferred embodiment, inner tube 12 has a tongue plate 19 integrally connected to one end. Tongue plate 19 includes a plurality of tongue members 20 located along inner tube 12 . As will be appreciated by one skilled in the art, inner tube 12 can have as few as one tongue member or could have numerous tongue members 20 vertically displaced from one another when inner tube 12 is in an supporting position. Further, tongue members 20 are preferably grouped on the same horizontal plain and across from each other in one embodiment. Alternative embodiments could however include tongue members one each side of inner tube 12 at different levels.
[0030] In a preferred embodiment, tongue members 20 are located at a lower end of inner tube 12 . However, this is not a requirement and tongue members 20 could be at various points along the length of inner tube 12 .
[0031] Tongue members 20 extend orthogonally from inner tube 12 and are dimensioned to extend through slots 22 in outer tube 14 . The tongue members 20 and slots 22 are used to make large adjustments to the post 10 very quickly.
[0032] As can be seen in FIG. 2 , in the preferred embodiment, post 10 includes an upper outer tube 14 and a lower tube 16 . Outer tube 14 includes a screw bore in its lower portion, and lower tube 16 includes a screw bore in its upper end. Between outer tube 14 and lower tube 16 is a adjusting screw assembly 24 . This screw assembly 24 is used to make fine adjustments to the length of the post 10 and includes an adjusting handle 26 and a plurality of support pins 28 . The fine adjustment screw assembly 24 has a double thread so a single rotation will allow twice the distance, compared to a single thread. As will be appreciated, support pins 28 support the screw assembly 24 , and the mechanism thereby can be used to finely adjust post 10 .
[0033] In the preferred embodiment screw assembly 24 is located at approximately the waist height of a worker to facilitate the fine adjustment of post 10 and to ease the removal of post 10 .
[0034] Other methods of fine adjustments may be used in this device, one of which is shown in FIG. 9 , where a release type system 34 is used between the outer tube 14 and the lower tube 16 . Release type systems 34 and other fine adjustment systems are known to those skilled in the art.
[0035] As also seen in FIGS. 1 and 2 , the preferred embodiment also includes a post head 18 at the end of the post 10 , telescoping from the inner tube 12 , used for support. The length that the post head 18 extends from the inner tube 12 and may be adjusted by any of several types of configurations, such as using a screw, or a pin-type configuration. In the embodiments shown in FIG. 2 and in FIG. 9 , a spring pin 38 is used.
[0036] The preferred embodiment of the outer tube 14 is shown in FIGS. 6 to 8 . As can be seen in FIG. 7 , the cross section is approximately rectangular, with an opposite set of outwardly rounded corners 30 , and an opposite set of inwardly rounded corners 32 . The cross-section of the outer leg 14 is dimensioned so that the entire inner leg 12 and tongue members 20 will fit entirely within the outer leg 14 , when the tongue members are located within the outwardly rounded corners 30 ( FIG. 3 a ). This configuration of the outer tube 14 is not essential to the device, however it allows for recesses for the thumb and fingers. In the preferred embodiment shown in FIG. 8 is located an outer hole 44 , dimensioned to receive a support pin 28 .
[0037] As will be appreciated by those skilled in the art, a rectangular cross section is optional and other cross sections are available. Reference is now made to FIGS. 10 to 12 . As seen in FIG. 10 , a square cross section can be used where tongue 20 can interact with a groove 22 (not shown in FIG. 10 ). Other cross sections include a round cross section as seen in FIG. 11 or 12 . Various internal configurations for inner tube 12 are shown in FIGS. 11 and 12 .
[0038] Alternatively, FIG. 13 shows the outer tube 14 having similar dimensions to the outer tube of FIG. 10 . However, in the embodiment of FIG. 13 , no channels 42 need to be present. The embodiment of FIG. 2 shows two channels 42 , but these are not engaged by tongue 20 . In an alternative embodiment, no channels 42 need to be present at all. As will be appreciated, tongue 20 can still engage slots 22 when no channel 42 is present.
[0039] As will further be appreciated by those skilled in the art, the use of slots 22 in channel 42 , as in FIG. 10 , adds the further benefit of having a larger support area for tongue 20 . Specifically, slot 22 includes the wall of channel 42 , thereby providing additional support.
[0040] FIG. 10 further illustrates the use of a tongue 20 that is comprised of a slat. This could be advantageous in circumstances such as when the tongue 20 is not at the bottom of inner post 12 . However, the tongue plate 19 of FIG. 5 b is preferable in most circumstances, since the tongue plate 19 lies under the outer diameter of inner tube 12 , thereby providing support to the complete inner post 12 .
[0041] The slots 22 in the outer tube 14 (best seen in FIG. 1 ) are spaced so that when the inner tube 12 may be rotated from having the tongue members 20 entirely within the outer tube 14 , to having the tongue members 20 extend through the slots 22 in the outer tube, locking the inner tube 12 in place within the outer tube 14 . In the preferred embodiment the tongue members 20 travel along a non-resistant surface, to allow for easier rotation of the inner tube 12 within the outer leg 14 . There is also a small downward indentation (not shown) in the slot 22 , allowing the tongue members 20 to lock into the indentation due to gravity. The indention also locks the tongue precisely into the support position. This prevents the accidental rotation when raised into position or when under load. The indentation in a preferred embodiment is located both above and below the groove in order to allow the post to be used downside-up or downside-down. Further, safety holes 41 accommodate a pin to further prevent the dislodging of tongue 20 and hence inner post 12 .
[0042] In one embodiment, slots 22 are space every 6 inches or 15 cm to allow for the quick rough adjustment of inner tube 12 within outer tube 14 . Other dimensions are also possible.
[0043] Post 10 is therefore configured to the proper length by adjusting inner tube 12 within outer tube 14 using tongue members 20 and slots 22 . Inner tube 12 and outer tube 14 are adjusted to the approximate length required for post 10 . Fine adjustment can then be accomplished using a fine adjustment mechanism such as screw assembly 24 or adjustment mechanism 34 .
[0044] As is best seen in FIG. 7 , tongue members 20 are slid into slots 22 by rotating inner tube 12 through an angle of 45 degrees. Other rotation angles are however possible.
[0045] In the preferred embodiment of the inner tube 12 , as shown in FIGS. 4 , 5 a , and 5 b , the leg is of a general cylindrical shape, which allows for it to be easily rotated within the outer leg 14 . In this embodiment, the tongue plate 19 is welded to the bottom of the inner tube 12 . Other alternatives to welding would be known to those in the art, and any integral connection would be suitable. Also, shown in FIGS. 5 a and 5 b , the preferred embodiment of the tongue plate includes two tongue members 20 , however a different number of tongue members may be used. A connector hole 40 is shown in the embodiment of FIG. 4 , near the opposite end of the tongue plate 19 of inner tube 12 .
[0046] As can be seen in the embodiment shown in FIG. 3 b , support pin 28 fits through the inwardly rounded corners 32 of the outer tube 14 . In this embodiment there are also a pair of spring pins 38 through the support pin 28 , to lock it in place.
[0047] Also shown in the embodiment in FIG. 5 b is a pair of safety holes 41 accommodate pins to further lock the tongue members 20 in place. These safety pins, along with the indentation in the slot 22 are not essential to the device, but are features added to greatly increase the overall safety of the shoring post.
[0048] In the preferred embodiment of the shoring post 10 , there are a plurality of channels 42 located along the length of both the inner leg 12 and the outer leg 14 . A further type of support device in a construction system may be used to engage the channels 42 to add additional support in different directions, or to attach any type of accessories or external bracing using a connector.
[0049] As will be seen from FIGS. 1 , 3 b and 10 , when tongue 20 is engaging slot 22 , channels 42 of inner post 12 align with channels 42 of outer post 14 , thereby allowing accessories or bracing to be added in the same plain to both the inner post 12 and outer post 14 . This is advantageous since the channels 42 can now be used along the entire length of post 10 . Prior art solutions do not have this capability, and in general do not have channels 42 on inner post 12 .
[0050] The present post system therefore provides a means for faster removal or replacement for a post by providing a tongue and groove system for gross adjustment of the inner tube within the outer tube. Tongue members are affixed to inner tube 12 thereby allowing the quick removal and replacement of the post without having to find pins or align holes. The preferred shape of the outer tube 14 is configured for easy handling, allowing the worker's thumbs and fingers to grip the post.
[0051] In a preferred embodiment post 10 is comprised of aluminium. Other materials could be used however.
[0052] These and other advantages of the present system are evident from the above and with reference to the drawings. They are not however meant to limit the invention, the scope of which is defined in the claims below.
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A telescoping post shore having an outer tube; a plurality of slots disposed longitudinally along the outer tube; an inner tube; at least one tongue member affixed to the inner tube and projecting from the inner tube, the at least one tongue member configured to be received by the plurality of slots; wherein the inner tube and at least one tongue member are dimensioned to slide within the outer tube and the inner tube and at least one tongue member can be rotated within the outer tube to engage the at least one tongue member with at least one of the plurality of slots.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation Application of U.S. patent application Ser. No. 12/ 716,722 filed on Mar. 3, 2010, which claims priority to Japanese Patent Application No. 2009-065116 filed on Mar. 17, 2009, the contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a gaming system, and more specifically to a gaming system which is capable of controlling a process of a game (such as a card game and a roulette) played in a player-against-computer manner in a casino or the like gaming facility, detecting cheatings, recording in real time the transaction accompanied with transfer of bets and payouts etc. resulting from exchange of casino chips, and then counting and reflecting, onto a balance sheet in real time, occurrence and transfer of assets as actual economic activities between a player and a casino.
[0004] 2. Description of the Related Art
[0005] Games played in conventional casinos are classified roughly into (1) a human-against-human type (for example, a dealer-against-player type) and (2) a human-against-computer type (for example, a player-against-slot machine type).
[0006] Table games such as poker, baccarat and roulette fall into the above classification of (1). In order to avoid cheating during the process of the game, behaviors of a dealer need to have no influence upon game results.
[0007] Meanwhile, in the conventional casinos, players exchange cash etc. for casino chips at an exchange office, a cashier, or the like place, the casino chips are treated as objects having a value in casinos, and games such as roulette and poker are played by exchange of casino chips.
[0008] When a player wins a game, the player is provided with casino chips as a payout by a casino. On the other hand, when a player loses a game, a casino takes the casino chips bet (namely placed onto a table as a wager) by the player. In this manner, exchanges of valuables by using casino chips take place on a gaming table.
[0009] A casino needs not only to collect income-and-expense information on an automatic gaming machine such as a slot machine with communication but also to count casino chips, to count cash held at a cashier, and the like for checking revenue (income and expense) derived from games and earnings. At a casino or the like facility which is operated 24 hours a day, however, keeping track of revenue (income and expense) derived from games and earnings accurately in real time is difficult. In particular, it is difficult to keep track of revenue (income and expense) derived from games in real time during a dealer continues to play a game of a table game such as roulette, poker or baccarat.
[0010] As a conventional technique for managing casino earnings and the like, it has been proposed to connect a casino gaming machine such as a slot machine to a casino control server, input the earnings derived from the casino gaming machine periodically into the casino control server, and then calculate the earnings, gross profit, etc. by the server (for example, Japanese Unexamined Patent Application Publication No. 2006-338230).
SUMMARY OF THE INVENTION
[0011] A gaming system according to an embodiment of the present invention includes: a reader configured to read chip identification information which identifies a chip used in a casino; a writer configured to write validity information about whether the chip is valid, betting information about whether the chip is being betted, and a determination unit configured to determine whether the chip is valid, wherein the writer is further configured to (a) update the validity information of the chip from invalid to valid when the chip is transferred from the casino to a player, (b) update the validity information of the chip from valid to invalid when the chip is transferred from the player to the casino, (c) update the betting information as being betted when the chip is placed on a betting area, and (d) update the betting information as not being betted when a result of a game is determined.
[0012] The gaming system may further include: a controller configured to control a process of the game based on the chip identification information read by the reader and generate dealer instructions in response to the process of the game; and an instruction unit configured to output the dealer instructions and to pass on the instructions to a dealer of the game.
[0013] The determination unit may be configured to determine abuse of the chip and cheating during the process of the game.
[0014] The instructions generated by the controller may include instructions on how to proceed in the game regardless of detection of cheating during the process of the game.
[0015] The instructions may include instructions to collect the chip from the player who has lost the game or instructions to provide the chip to the player who has won the game.
[0016] A gaming method performed by a gaming system, the method includes: reading, by a chip reader, chip identification information identifying a specific chip among chips used in a casino; writing validity information about whether the chip is valid, betting information about whether the chip is being betted, determining whether the chip is valid, updating the validity information from invalid to valid when the chip is transferred from the casino to a player; updating the validity information from valid to invalid when the chip is transferred from the player to the casino; updating the betting information as being betted when the chip is placed on a betting area, and updating the betting information as not being betted when a result of a game is determined.
[0017] The gaming method may further include: controlling a process of the game based on the chip identification information read by the reader; generating dealer instructions in response to the process of the game; and sending the dealer instructions to a dealer of the game.
[0018] The gaming method may further include: determining abuse of the chip and cheating during the process of the game.
[0019] The instructions generated by the controller may include instructions on how to proceed in the game regardless of detection of cheating during the process of the game.
[0020] The instructions may include instructions to collect the chip from the player who has lost the game or instructions to provide the chip to the player who has won the game.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 is a block diagram showing a configuration example of a gaming system.
[0022] FIG. 2 is a block diagram showing a configuration example of an IC chip reader.
[0023] FIG. 3 is a cross-sectional view of a casino chip.
[0024] FIG. 4 is a functional block diagram showing a configuration example of an IC chip.
[0025] FIG. 5 is a diagram showing an example of arrangement of components included in the gaming system.
[0026] FIG. 6 is a diagram showing an example of a table top when a certain gaming table is viewed from above.
[0027] FIG. 7A is a functional block diagram showing a configuration example of a main manager.
[0028] FIG. 7B is a diagram showing a data configuration example of one of the records stored in a casino chip DB.
[0029] FIG. 8 is a functional block diagram showing a configuration example of a process controller.
[0030] FIG. 9 is a sequence diagram showing how cash and casino chips are transferred.
[0031] FIG. 10 is a diagram showing a data configuration example of journal data generated after completion of S 10 in FIG. 9 .
[0032] FIG. 11 is a diagram showing a data configuration example of journal data generated prior to S 50 in FIG. 9 .
[0033] FIG. 12 is a sequence diagram showing how cash and casino chips are transferred when a dealer wins a game and acquires casino chips that are bet.
[0034] FIG. 13 is a diagram showing a data configuration example of journal data generated after S 145 in FIG. 12 .
[0035] FIG. 14 is a sequence diagram showing the transfer of cash and casino chips when a player exchanges casino chips for cash.
[0036] FIG. 15 is a diagram showing a data configuration example of journal data generated by a journal data generation unit.
[0037] FIG. 16 is a diagram showing a data configuration example of journal data generated by the journal data generation unit.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0038] The embodiment of the present invention will be described below with reference to the accompanying drawings.
[0039] The embodiment of the present invention is proposed as a gaming system in a casino.
1. Configuration Example of Gaming System
[0040] First, a configuration example of a gaming system will be described.
1.1. Overview of Configuration Example
[0041] FIG. 1 is a block diagram showing a configuration example of a gaming system. The gaming system 1 includes: a main manager 10 ; an IC chip reader 20 connected to the main manager 10 so as to communicate therewith and configured to read a casino chip; a monitoring camera 30 configured to take images of casino chips and players; a casino chip 50 with a built-in IC chip 40 (not shown in FIG. 1 ); a process controller 60 connected to the main manager 10 so as to communicate therewith; and an instruction device 70 connected to the process controller 60 so as to carry out a process.
1.2. Main Manager
[0042] The main manager 10 is implemented, for example, by an information processor such as a computer or a work station. The information processor includes a central processing unit (CPU), a main memory (RAM), a read-only memory (ROM), an input-output unit (I/O), and, if necessary, an external storage unit such as a hard disk drive. Functions and the like of the main manager 10 will be described later.
1.3. IC Chip Reader
[0043] The IC chip reader 20 equivalent to a read unit of the present invention reads, through radio communication, information stored in the IC chip 40 in the casino chip 50 that is a storage medium. FIG. 2 is a block diagram showing a configuration example of the IC chip reader 20 .
[0044] The IC chip reader 20 includes a control unit 201 and a transmitting and receiving unit 202 connected to the control unit 201 . The control unit 201 has a function of receiving an instruction from the main manager 10 , driving the transmitting and receiving unit 202 in response to the instruction, and handing over data outputted from the transmitting and receiving unit 202 (data read from the IC chip 40 ) to the main manager 10 . The control unit 201 is, for example, a microcomputer having a CPU, a ROM and a RAM.
[0045] The transmitting and receiving unit 202 has a function of transmitting and receiving data by radio to and from the IC chip 40 through an antenna 15 . To be more specific, the transmitting and receiving unit 202 includes a modulator 203 and a demodulator 204 . The modulator 203 generates a modulated wave by modulating a carrier wave by using a predetermined modulation method based on a base signal corresponding to information such as a predetermined command, request, instruction or the like received from the control unit 201 . The demodulator 204 has a function of demodulating a magnetic field which is load-modulated based on a base signal corresponding to the information stored in the IC chip 40 , retrieving the base signal corresponding to the data, and handing over the retrieved base signal to the control unit 201 . The transmitting and receiving unit 202 is, for example, an RF module having a modulating circuit and a demodulating circuit, or the like.
1.4. Casino Chip and IC Chip
[0046] The casino chip 50 is a game medium exchanged between a dealer, a player and the like instead of cash in a casino. The casino chip 50 is generally formed by molding a resin or the like in a coin shape, a disk shape or the like. FIG. 3 is a cross-sectional view of the casino chip 50 . The casino chip 50 includes a main body 51 formed of a resin and the IC chip 40 embedded in the main body 51 .
[0047] The IC chip 40 stores information which can be read according to a read signal from the IC chip reader 20 . In general, the IC chip 40 holds information in a readable and writable manner, and allows the stored information to be read and overwritten and new information to be stored as needed. In this embodiment, however, the IC chip 40 stores IC chip identification information (e.g., an ID serial number) which uniquely identifies the casino chip 50 having the IC chip 40 embedded therein.
[0048] FIG. 4 is a functional block diagram showing a configuration example of the IC chip 40 . The IC chip 40 includes a memory 41 , a control unit 42 , a transmitting and receiving unit 43 , and an antenna 44 . The memory 41 is a storage storing the IC chip identification information. The control unit 42 interprets a command, request, instruction or the like from the IC chip reader 20 , and executes an operation in response thereto. The transmitting and receiving unit 43 includes a modulator (not shown) and a demodulator (not shown), and performs signal modulation and demodulation for transmitting and receiving data by radio to and from the IC chip reader 20 . The antenna 44 receives a modulated wave from the antenna 15 of the IC chip reader 20 and transmits the received modulated wave to the transmitting and receiving unit 43 , while receiving a modulated signal from the transmitting and receiving unit 43 , and emitting the modulated signal into the air in order for the antenna 15 to receive the modulated signal.
1.5. Monitoring Camera
[0049] The monitoring camera 30 generates image data on a player for recognizing the player (e.g., the face of the player, clothes of a person whose image is taken, movement of his/her hand, and the like), and transmits the image data together with an image of the casino chip 50 to the main manager 10 .
1.6. Process Controller
[0050] The process controller 60 equivalent to a control unit of the present invention has a function of determining a progress of a game based on a transfer situation of the casino chip 50 transmitted from the main manager 10 , and the like, generating instruction information which instructs a dealer what to do based on the determination result, and outputting the instruction information to the instruction device 70 .
[0051] The process controller 60 is implemented, for example, by an information processor such as a computer or a work station. The information processor includes a central processing unit (CPU), a main memory (RAM), a read-only memory (ROM), an input-output unit (I/O), and, if necessary, an external storage unit such as a hard disk drive.
[0052] A configuration of the process controller will be described later.
1.7. Instruction Device
[0053] The instruction device 70 equivalent to an instruction unit of the present invention has a function of outputting the instruction information from the process controller 60 and transmitting instruction contents to the dealer. The instruction contents may be transmitted to the dealer through images, sounds and the like. The instruction device 70 is, for example, a liquid crystal display device, a head set or the like. The instruction contents may be treated as instruction information related to any of the process of a game, such as collecting casino chips 50 from a player who has lost the game, providing casino chips 50 to a player who has won the game, and drawing or standing a card in the case of a card game.
1.8. Component Arrangement Example
[0054] FIG. 5 is a diagram showing an example of arrangement of the components included in the gaming system 1 . In a casino, cashiers are provided for players to exchange cash or the like for the casino chips 50 . At each of the cashiers, the IC chip reader 20 for the cashier is placed. A cashier operator uses the IC chip reader 20 to read the IC chip 40 in exchanging cash or the like for the casino chips 50 .
[0055] Moreover, in the casino, a poker table and a roulette table are placed as gaming tables for playing a game. On the underside or the like of the table top of the poker table or roulette table, the IC chip reader 20 is provided. The IC chip readers 20 thus provided include the one used by the dealer and the one used by each player.
[0056] At each of the poker table and roulette table, the process controller 60 and the instruction device 70 are provided (the process controller 60 and the instruction device 70 are not shown in FIG. 5 ).
[0057] Furthermore, the casino has facilities (such as a store and a restaurant) where the casino chips 50 can be used for payment in the same manner as cash, and a cashier in each of such facilities is also provided with the IC chip reader 20 .
1.9. Arrangement Example of IC Chip Reader at Gaming Table
[0058] A more specific example of the IC chip reader 20 provided on a gaming table will be described. FIG. 6 is a diagram showing an example of a table top when a certain gaming table 600 is viewed from above. At the gaming table 600 , an IC chip reading area 601 for a dealer and IC chip reading areas 602 for players are provided. On the underside of the table corresponding to the IC chip reading areas 601 and 602 , the IC chip readers 20 are provided so that, when the casino chips 50 are placed in the IC chip reading areas 601 and 602 , the IC chip readers 20 can read the IC chip identification information from the IC chips 40 in the casino chips 50 .
1.10. Configuration Example of Main Manager
[0059] A configuration example of the main manager 10 will be described. FIG. 7A is a functional block diagram showing the configuration example of the main manager 10 . Note that respective components correspond to functions implemented by a CPU and programs executed by the CPU. Therefore, the main manager 10 need not actually include hardware corresponding to each of the components.
[0060] The main manager 10 includes: a communication control unit 701 connected to the IC chip readers 20 and the process controllers 60 ; a determination unit 702 connected to the communication control unit 701 ; a casino chip data base (hereinafter referred to as DB) 703 connected to the determination unit 702 ; a journal data generation unit 704 connected to the determination unit 702 ; a journal data DB 705 connected to the journal data generation unit 704 ; an output unit 706 connected to the casino chip DB 703 and the journal data DB 705 ; and a financial statement data generation unit 707 connected to the journal data DB 705 . Note that “connection” here means not only a physically connected state but also a data exchangeable state. Here, the determination unit 702 corresponds to a determination unit of the present invention, the journal data generation unit 704 corresponds to a first generation unit of the present invention, the journal data DB 705 corresponds to an accumulation unit of the present invention, the financial statement data generation unit 707 corresponds to a second generation unit of the present invention, and the output unit 706 corresponds to an output unit of the present invention.
[0061] The communication control unit 701 has a function of communicating with the IC chip readers 20 so as to receive data transmitted from the IC chip readers 20 . Each of the IC chip readers 20 transmits, to the main manager 10 according to a predetermined protocol, the read IC chip identification information, reader identification information (e.g., a reader ID) which identifies the IC chip reader 20 , read date and time information, and the like.
[0062] The communication control unit 701 then transmits the data received from the IC chip reader 20 to a corresponding one of the process controllers 60 .
[0063] The determination unit 702 has a function of updating data stored in the casino chip DB 703 based on the IC chip identification information and reader identification information received through the communication control unit 701 and the data stored in the casino chip DB 703 , and generating journal data for determining contents of journal corresponding to a transaction made between a casino and a player when reading is performed by the IC chip reader 20 .
[0064] Furthermore, the determination unit 702 refers to the contents stored in the casino chip DB 703 and determines whether or not the IC chip 40 read by the IC chip reader 20 is illegitimate. If the IC chip 40 is illegitimate, the determination unit 702 transmits to the corresponding process controller 60 a message notifying the process controller 60 that an illegitimate casino chip 50 is being used.
[0065] The casino chip DB 703 has a function of storing various kinds of information on each of the casino chips 50 in association with the IC chip identification information. The casino chip DB 703 has one record for each casino chip 50 . FIG. 7B is a diagram showing a data configuration example of one of the records stored in the casino chip DB 703 . A record 800 has a chip ID field 801 , a business site identification information field 802 , a nominal displayed amount field 803 , a chip state information field 804 , a chip holder field 805 , a valid/invalid state field 806 , a latest validation date and time field 807 , a validation device information field 808 , a latest invalidation date and time field 809 , and an invalidation device information field 810 .
[0066] The chip ID field 801 stores the IC chip identification information stored in the IC chip 40 . The business site identification information field 802 stores information which identifies a gaming facility, a hotel or the like where a certain casino chip 50 is used. The nominal displayed amount field 803 stores a value of a displayed amount of the casino chip 50 . For example, the value stored in the nominal displayed amount field 803 is “10” when the casino chip 50 is $10, and is “100” when the casino chip 50 is $100. The chip state information field 804 stores information indicating an accounting state of the casino chip 50 (e.g., journal data). The chip holder field 805 stores information indicating a holder of the casino chip 50 , for example, a player identification number and the like. The valid/invalid state field 806 stores information indicating whether the casino chip 50 is valid. The casino chip 50 is validated when the casino chip 50 is read by the IC chip reader 20 at the cashier during handing over of the casino chip 50 in exchange for cash payment at the cashier in the casino. The cashier or dealer checks if the casino chip 50 is valid using the IC chip reader 20 upon receipt of the casino chip 50 from the player. The valid casino chip 50 may be placed onto a table as a wager, exchanged for cash at the cashier or used for payment instead of cash at a facility such as a restaurant. By contrast, an invalid casino chip 50 cannot be used in that manner. This determination is made by the determination unit 702 of the main manager 10 .
[0067] The latest validation date and time field 807 stores the last date and time the casino chip 50 was validated. The validation device information field 808 stores information which identifies the IC chip reader 20 that carried out reading of the IC chip 40 in the casino chip 50 the last time the casino chip 50 was validated. The latest invalidation date and time field 809 stores the last date and time the casino chip 50 was invalidated. The invalidation device information field 810 stores information which identifies the IC chip reader 20 that carried out reading of the IC chip 40 in the casino chip 50 the last time the casino chip 50 was invalidated.
[0068] The journal data generation unit 704 has a function of generating journal data (information including line items of a creditor and a debtor and amounts thereof) corresponding to a transaction state of the casino chip 50 when the IC chip 40 in the casino chip 50 is read by the IC chip reader 20 .
[0069] The journal data DB 705 generates journal book data by accumulatively storing the journal data generated by the journal data generation unit 704 , and generates general ledger data based on the journal book data. The general ledger data represents a balance of the line items included in the journal data.
[0070] The output unit 706 has a function of allowing an operator or the like to view the contents stored in the casino chip DB 703 and the journal data DB 705 . The output unit 706 is, for example, a liquid crystal display device, a printer or the like.
[0071] The financial statement data generation unit 707 performs processing of counting the journal data accumulated in the journal data DB 705 , and the like, and generates, based on this processing, data corresponding to data showing the state of property and the state of profit and loss of the casino, the balance sheet data, a tax amount calculated based on the journal data accumulated in the accumulation unit, and the like. The generated data is handed over to the output unit 706 , and various ledger sheets are outputted, such as a journal book, a general ledger, an auxiliary book, a trial balance, a profit-and-loss statement, a balance sheet, and a tax return form. Note that a user may freely determine, by his/her own choice, which one of the ledger sheets is to be outputted.
1.11. Configuration of Process Controller
[0072] Next, a configuration example of the process controller 60 will be described. FIG. 8 is a functional block diagram showing the configuration example of the process controller 60 . The process controller 60 includes a communication control unit 711 , a progress recognition unit 712 connected to the communication control unit 711 , and an instruction information generation unit 713 connected to the progress recognition unit 712 .
[0073] The communication control unit 711 receives from the main manager 10 the read data on the IC chip 40 received from the IC chip reader 20 . The communication control unit 711 also receives from the main manager 10 a message notifying that an illegitimate casino chip 50 is being used.
[0074] The progress recognition unit 712 has a function of recognizing a progress of a game at a gaming table under the control of the process controller 60 based on, for example, the read data on the IC chip 40 received from the IC chip reader 20 , and determining what kind of instruction is to be given next to the dealer. In addition, the progress recognition unit 712 also has a function of issuing a warning to the dealer through the instruction device 70 based on the message notifying that an illegitimate casino chip 50 is being used, or sending out a warning message (e.g., transmitting an e-mail or sending an automatic sound notification) to a predetermined contact point such as a security at the casino.
[0075] The instruction information generation unit 713 has a function of generating information (such as image data or audio data) for allowing the instruction device 70 to output an instruction to be issued to the dealer, based on the determination made by the progress recognition unit 712 . For example, the instruction information generation unit 713 performs processing of generating a test message such as “Draw another card from the dealer's cards” or audio data such as “Dealer, stand”, and the like.
2. Operation Example of Gaming System
[0076] Next, an operation example of the gaming system 1 will be described.
2.1. Lending of Casino Chip
[0077] First, a player needs to acquire casino chips 50 before playing a game at a casino. Here, the player acquires casino chips 50 in exchange for cash at a cashier in a casino. FIG. 9 is a sequence diagram showing how cash and casino chips 50 are transferred when the player acquires casino chips 50 in exchange for cash at a cashier in the casino, plays a game and then acquires additional casino chips 50 as a payout by winning the game.
[0078] First, the player gives cash to a cashier operator (S 10 ). The cashier operator keeps the received cash in a safe or the like, and allows the IC chip reader 20 for the cashier operator to read the stored casino chips 50 corresponding to the amount of the received cash.
[0079] In the casino chip DB 703 in the main manager 10 , each of the stored casino chips 50 is recorded as being in an invalid state before being read by the IC chip reader 20 for the cashier operator. After the casino chip 50 is read by the IC chip reader for the cashier operator, the main manager 10 , more specifically, the determination unit 702 uses the read IC chip identification information as a key to extract a record corresponding thereto in the casino chip DB 703 in the main manager 10 , and then writes, in the record, more specifically, the valid/invalid state field 806 , data indicating “Valid” meaning that the casino chip 50 having the IC chip 40 is turned into a valid state. In the chip state information field 804 , information indicating that the player has exchanged cash for casino chips 50 (which is called chip transaction state information) is written. At the same time, time information related thereto is written in the latest validation date and time field 807 , and information which can identify the cashier is written in the validation device information field 808 .
[0080] In such a record in the casino chip DB 703 , information useful for reference in case of occurrence of some problem later or in case of taking statistics is written.
[0081] Furthermore, the determination unit 702 in the main manager 10 hands over the information written in the chip state information field 804 to the journal data generation unit 704 . The journal data generation unit 704 generates journal data based on the chip transaction state information. FIG. 10 shows a data configuration example of the journal data generated after completion of S 10 . In the example shown in FIG. 10 , a creditor and a debtor each have a line item and an amount in the journal data. This example uses journal data generated for one casino chip 50 having a display amount of $100. The line item of the debtor is a gaming expenditure (expense), and the gaming expenditure (expense) is described as being increased by $100. The line item of the debtor is cash (assets), and the cash (assets) is described as being increased by $100. The line item of the creditor is a deposit (debt), and the deposit (debt) is described as being increased by $100.
[0082] If the player gives out $1000 cash and receives ten $100 casino chips 50 , ten pieces of the journal data shown in FIG. 10 are generated. The generated journal data is handed over to and stored in the journal data DB 705 .
2.2. When Player Wins a Game
[0083] Referring back to FIG. 9 , a description will be given of an operation example of the gaming system 1 when the player who has received the casino chips 50 plays a game at a gaming table, takes back the bet casino chips by winning the game, and acquires casino chips 50 as a payout from the dealer.
[0084] The player places casino chips 50 as a wager in a bet area on the gaming table (S 30 ). Below the bet area, an IC chip reader 20 is installed. IC chip identification information on the placed casino chips 50 is read by the IC chip reader 20 and then transmitted to the main manager 10 . The determination unit 702 in the main manager 10 extracts a record corresponding to the received IC chip identification information from the casino chip DB 703 , and determines whether the casino chips 50 corresponding to the IC chip identification information are valid. When the casino chips 50 are invalid, the determination unit 702 generates and outputs a message notifying the player, dealer or security that those casino chips 50 cannot be used. At the same time, the determination unit 702 writes information indicating that a bet is being placed into the chip state information field 804 of the corresponding record in the casino chip DB 703 .
[0085] At this point, the determination unit 702 hands over the information written into the chip state information field 804 to the journal data generation unit 704 . The journal data generation unit 704 generates journal data based on the chip transaction state information.
[0086] It is assumed here that an outcome of the game is determined and the player wins the game and is provided with a payout. In this case, the casino chips 50 placed in the bet area are all returned to the player who has made the bet (S 4 ). At the same time, a record corresponding to the casino chip 50 is extracted from the casino chip DB 703 , and information indicating that the casino chip 50 is no longer being bet is written into the chip state information field 804 . This is in order to detect a cheating when a casino chip 50 which is supposed to be in the middle of a game is exchanged for cash at a cashier or the like since the casino chip 50 that is being bet is a deposit that cannot be exchanged for cash until the game is finished and winning or losing is determined.
[0087] Furthermore, the dealer provides the player with the casino chips 50 as a payout (S 50 ). The dealer allows the IC chip reader 20 for the dealer to read the casino chips 50 kept at hand or the like corresponding to the payout. The read IC chip identification information is transmitted to the main manager 10 .
[0088] In the casino chip DB 703 in the main manager 10 , each of the stored casino chips 50 is recorded as being in an invalid state before being read by the IC chip reader 20 for the dealer.
[0089] After the casino chip 50 is read by the IC chip reader 20 for the dealer, the main manager 10 , more specifically, the determination unit 702 uses the read IC chip identification information as a key to extract a record corresponding thereto in the casino chip DB 703 in the main manager 10 , and then writes, in the record, more specifically, the valid/invalid state field 806 , data indicating “Valid” meaning that the casino chip 50 having the IC chip 40 is turned into a valid state. In the chip state information field 804 , information indicating that the player is provided with a payout (which is called chip transaction state information) is written. Furthermore, the determination unit 702 in the main manager 10 hands over the information written into the chip state information field 804 to the journal data generation unit 704 . The journal data generation unit 704 generates journal data based on the chip transaction state information. FIG. 11 shows a data configuration example of journal data generated prior to S 50 . This example uses journal data when the dealer provides the player with a $100 casino chip 50 as a payout. The line item of the debtor is a gaming expenditure (expense), and the gaming expenditure (expense) is described as being increased by $100. The line item of the creditor is an arrearage (debt), and the arrearage (debt) is described as being increased by $100.
[0090] The determination unit 702 rewrites the contents in the chip state information field 804 of the corresponding record into the above contents. The generated journal data is transmitted to and accumulated in the journal data DB 705 .
2.3. When Player Loses a Game
[0091] Next, a description will be given of an operation example of the gaming system 1 when the player loses a game. FIG. 12 is a sequence diagram showing how cash and casino chips 50 are transferred when the player acquires casino chips 50 in exchange for cash at a cashier in the casino and plays a game, and then the dealer acquires casino chips 50 that are bet by winning the game.
[0092] The steps of the player exchanging cash for casino chips 50 at a cashier and placing the casino chips 50 as a wager in a bet area on the gaming table (S 110 to S 135 ) are the same as S 10 to S 35 in FIG. 9 , and thus a description thereof will be omitted.
[0093] After S 35 , the casino chips 50 placed in the bet area is confiscated by the dealer since the player has lost the game (S 140 ). The dealer moves the casino chips 50 placed in the bet area to a reading area of the IC chip reader 20 for the dealer, and then allows the IC chip reader 20 for the dealer to read the confiscated casino chips 50 (S 145 ). The read IC chip identification information is transmitted to the main manager 10 .
[0094] In the casino chip DB 703 in the main manager 10 , each of the confiscated casino chips 50 is recorded as being in a valid state before being read by the IC chip reader 20 for the dealer. After the casino chip 50 is read by the IC chip reader 20 for the dealer, the main manager 10 , more specifically, the determination unit 702 uses the read IC chip identification information as a key to extract a record corresponding thereto in the casino chip DB 703 in the main manager 10 , and then writes, in the record, more specifically, the valid/invalid state field 806 , data indicating “Invalid” meaning that the casino chip 50 having the IC chip 40 is turned into an invalid state. In the chip state information field 804 , information indicating that the casino chip 50 is confiscated from the player (which is called chip transaction state information) is written. Furthermore, the determination unit 702 in the main manager 10 hands over the chip transaction state information to the journal data generation unit 704 . The journal data generation unit 704 generates journal data based on the chip transaction state information. FIG. 13 shows a data configuration example of journal data generated after S 145 .
[0095] This example uses journal data when the player hands over a $100 casino chip 50 that he/she has lost to the dealer. In this example, two kinds of journal data are generated for one casino chip 50 . In one of the journal data, the line item of the debtor is an uncollected balance (assets), and the uncollected balance (assets) is described as being increased by $100. The line item of the creditor is a gaming earning (profit), and the gaming earning (profit) is described as being increased by $100. The other journal data is the one for balancing the deposit from the player. The line item of the debtor is a deposit (debt), and the deposit (debt) is described as being decreased by $100. The line item of the creditor is an uncollected balance (assets), and the uncollected balance (assets) is described as being decreased by $100.
[0096] Furthermore, the determination unit 702 rewrites the contents in the chip state information field 804 of the corresponding record into the above contents.
2.4. Exchange of Casino Chip for Cash
[0097] Next, a description will be given of a case where the player exchanges casino chips 50 for cash at a cashier. FIG. 14 is a sequence diagram showing the transfer of cash and casino chips 50 when the player exchanges casino chips 50 for cash.
[0098] First, the player hands a desired number of casino chips 50 to the cashier operator (S 210 ). The cashier operator allows the IC chip reader 20 for the cashier operator to read the received casino chips 50 (S 220 ).
[0099] In the casino chip DB 703 in the main manager 10 , each of the casino chips 50 needs to be recorded as being in a valid state before being read by the IC chip reader 20 for the cashier operator. The casino chip 50 in an “invalid state” is the one resulting from some kind of cheating.
[0100] After the casino chip 50 is read by the IC chip reader for the cashier operator, the main manager 10 , more specifically, the determination unit 702 uses the read IC chip identification information as a key to extract a record corresponding thereto in the casino chip DB 703 in the main manager 10 , and then determines whether or not the casino chip 50 is in a “valid state”. When there is a casino chip 50 in the invalid state, display of a warning message or the like is performed. In addition, even when the casino chip 50 is in the valid state, the casino chip 50 that is being bet is also the one resulting from some kind of cheating. Similarly, when the IC chip identification information cannot be read and when the content of the business site identification information field 802 in the corresponding record in the casino chip DB 703 is determined to be neither a casino nor a hotel group to which the cashier belongs, display of a warning message or the like is performed.
[0101] As for the casino chip 50 in the valid state, the determination unit 702 writes, in the record, more specifically, the valid/invalid state field 806 , data indicating “Invalid” meaning that the casino chip 50 having the IC chip 40 is turned into an invalid state. In the chip state information field 804 , information indicating that the casino chip 50 is exchanged for cash (which is called chip transaction state information) is written. At the same time, time information related thereto is written in the latest invalidation date and time field 809 , and information which can identify the cashier is written in the invalidation device information field 810 .
[0102] For the casino chip 50 read in S 220 , the determination unit 702 causes the journal data generation unit 704 to generate journal data. The journal data in this case varies depending on whether the casino chip 50 is received from the cashier or from the dealer. The determination of whether the casino chip 50 is received from the cashier or from the dealer is made by the determination unit 702 referring to the record in the casino chip DB 703 , more specifically, the chip state information, the latest validation device information, and the like.
[0103] First, a description will be given of a case where the casino chip 50 is the one received from the cashier. FIG. 15 is a diagram showing a data configuration example of journal data generated by the journal data generation unit 704 when the casino chip 50 to be exchanged is the one received from the cashier. In this example, the line item of the debtor is a deposit (debt), and the deposit (debt) is described as being decreased by $100. The line item of the creditor is cash (assets), and the cash (assets) is described as being decreased by $100.
[0104] Next, a description will be given of a case where the casino chip 50 to be exchanged is the one received from the dealer.
[0105] FIG. 16 is a diagram showing a data configuration example of journal data generated by the journal data generation unit 704 when the casino chip 50 to be exchanged is the one received from the dealer. In this example, the line item of the debtor is an arrearage (debt), and the arrearage (debt) is described as being decreased by $100. The line item of the creditor is cash (assets), and the cash (assets) is described as being decreased by $100.
[0106] Note that, after the reading described above (S 220 ), the cashier provides the player with cash or an object having a value such as a check, which corresponds to the total nominal displayed amount of the casino chips 50 .
[0107] Besides the management operation of the main manager 10 , the process controller 60 controls a process of a game on the gaming table under the control thereof and keeps issuing process instructions to the dealer.
3. Summary
[0108] The journal data described above is generated in real time at the time of occurrence of the transfer of the casino chip (reading by the IC chip reader 20 ), and is accumulated in the journal data DB 705 . Counting this journal data for each line item makes it possible to immediately calculate at any time a total balance of deposits, a total balance of gaming earnings and a total balance of gaming expenditures in the casino at the current point of time. The present invention thus makes it possible to constantly keep track of the income-and-expense condition of the casino.
[0109] Moreover, the present invention makes it possible to detect the use of illegitimate casino chips in real time and to improve the soundness of casino business.
[0110] The latest state when the player places a bet or when an outcome of a game is determined and a payout is provided is reflected on the total balance of deposits, the total balance of gaming earnings and the total balance of gaming expenditures in the casino. The present invention thus makes it possible to keep track of the financial condition and earning condition in real time.
4. Modified Embodiment and Others
[0111] In the above embodiment, the process controller 60 mainly functions to cause the instruction device 70 to send an instruction to the dealer. However, the present invention is still implemented even when the process controller 60 is modified so as to perform a part of the process of a game. For example, in the case of a card game such as poker, a card feeder (not shown) which is controlled by the process controller 60 may be provided on a gaming table and the card feeder may feed a required number of cards to a dealer and a player in accordance with the process of a game. Here, the card feeder takes out (ejects) a specified number of cards from a pile of cards stored in a card stock. Meanwhile, in the case of a roulette game, a roulette game may be executed by causing the process controller 60 to control a roulette machine capable of throwing a ball into a roulette wheel and automatically reading a stop position of the ball.
[0112] According to the present invention, it is possible to control a game under computer control while maintaining the game to be played in a human-against-human manner and also eliminate cheatings which may occur during the process of the game.
[0113] Furthermore, according to the present invention, it is possible to record the transaction between a casino (a gaming facility) and a player in real time and keep track of income and expense of the gaming facility or the player accurately in real time in accordance with the viewpoint of the accrual accounting.
[0114] As a result, it is possible to keep track of earnings derived from a game accurately in real time at an automatic gaming machine such as a slot machine with communication as well as in a game which comprises a dealer and casino chips.
[0115] In the prior art, since casino chips have a value, they need to be managed with equal strictness as in handling cash. By introduction of the system of the present invention, however, strict management of casino chips is made to be not necessary because they have no value (casino chips which are not effective on DB cannot be exchanged for cash), and therefore it is possible to substantially reduce cost in management.
[0116] The gaming system according to the embodiment of the present invention has been described above. However, the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
[0117] Moreover, the effects described in the embodiment of the present invention are only a list of optimum effects achieved by the present invention. Hence, the effects of the present invention are not limited to those described in the embodiment of the present invention.
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A gaming system includes: a reader configured to read chip identification information which identifies a chip used in a casino; a writer configured to write validity information, betting information, and information about whether the chip is received from a cashier or from a dealer into chip information based on the chip identification information; and a determination unit configured to determine the validity, the betting state, and the source based on the chip information, wherein the writer is configured to update the validity information from invalid to valid when the chip is handed from the cashier or the dealer to a player and vice versa, to update the betting information as being betted when the chip is placed on a betting area and vice versa.
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RELATED APPLICATIONS
This patent arises from a continuation of U.S. patent application Ser. No. 13/659,592, filed on Oct. 24, 2012, U.S. patent application Ser. No. 12/244,751, filed on Oct. 2, 2008, now U.S. Pat. No. 8,327,395, and U.S. patent application Ser. No. 12/244,752, filed on Oct. 2, 2008, now U.S. Pat. No. 8,332,883, which are hereby incorporated by reference in their entireties.
This patent claims the benefit of U.S. Patent Application Ser. No. 60/977,035, filed Oct. 2, 2007.
This patent claims the benefit of U.S. Patent Application Ser. No. 60/977,040, filed Oct. 2, 2007.
This patent claims the benefit of U.S. Patent Application Ser. No. 60/977,042, filed Oct. 2, 2007.
This patent claims the benefit of U.S. Patent Application Ser. No. 60/977,045, filed Oct. 2, 2007.
This patent claims the benefit of U.S. Patent Application Ser. No. 60/984,260, filed Oct. 31, 2007.
This patent claims the benefit of U.S. Patent Application Ser. No. 60/984,268, filed Oct. 31, 2007.
This patent claims the benefit of U.S. Patent Application Ser. No. 60/991,591, filed Nov. 30, 2007.
This patent is related to U.S. patent application Ser. No. 11/681,265, filed Mar. 2, 2007; U.S. patent application Ser. No. 11/804,517, filed May 17, 2007; U.S. patent application Ser. No. 11/779,814, filed Jul. 18, 2007; U.S. patent application Ser. No. 11/846,068, filed Aug. 28, 2007; U.S. patent application Ser. No. 11/959,399, filed Dec. 18, 2007; U.S. patent application Ser. No. 12/244,737, filed Oct. 2, 2008; U.S. patent application Ser. No. 12/244,748, filed Oct. 2, 2008; U.S. patent application Ser. No. 12/263,331, filed Oct. 31, 2008; U.S. patent application Ser. No. 12/263,350, filed Oct. 31, 2008; U.S. patent application Ser. No. 12/326,016, filed Dec. 1, 2008; and U.S. patent application Ser. No. 13/252,910, filed Oct. 4, 2011.
TECHNICAL FIELD
This disclosure relates to the field of analysis of physiological responses from viewers of media instances.
BACKGROUND
A key to creating a high performing media instance is to ensure that every event in the media elicits the desired responses from viewers. Here, the media instance can be but is not limited to, a video game, an advertisement clip, a movie, a computer application, a printed media (e.g., a magazine), a website, an online advertisement, a recorded video, a live performance of media, and other types of media.
Physiological data, which includes but is not limited to heart rate, brain waves, electroencephalogram (EEG) signals, blink rate, breathing, motion, muscle movement, galvanic skin response and any other response correlated with changes in emotion of a viewer of a media instance, can give a trace (e.g., a line drawn by a recording instrument) of the viewer's responses while he/she is watching the media instance. The physiological data can be measure by one or more physiological sensors, each of which can be but is not limited to, an electroencephalogram, electrocardiogram, an accelerometer, a blood oxygen sensor, a galvanometer, an electromyograph, skin temperature sensor, breathing sensor, eye tracking, pupil dilation sensing, and any other physiological sensor.
It is well established that physiological data in the human body of a viewer correlates with the viewer's change in emotions. Thus, from the measured “low level” physiological data, “high level” (e.g., easier to understand, intuitive to look at) physiological responses from the viewers of the media instance can be created. An effective media instance that connects with its audience/viewers is able to elicit the desired emotional response. Here, the high level physiological responses include, but are not limited to, liking (valence)—positive/negative responses to events in the media instance, intent to purchase or recall, emotional engagement in the media instance, thinking—amount of thoughts and/or immersion in the experience of the media instance, and adrenaline—anger, distraction, frustration, and other emotional experiences to events in the media instance, and tension and stress.
Advertisers, media producers, educators, scientists, engineers, doctors and other relevant parties have long desired to have greater access to collected reactions to their media products and records of responses through a day from their targets, customers, clients and pupils. These parties desire to understand the responses people have to their particular stimulus in order to tailor their information or media instances to better suit the needs of end users and/or to increase the effectiveness of the media instance created. Making the reactions to the media instances available remotely over the Web to these interested parties has potentially very large commercial and socially positive impacts. Consequently, allowing a user to remotely access and analyze the media instance and the physiological responses from numerous viewers to the media instance is desired.
INCORPORATION BY REFERENCE
Each patent, patent application, and/or publication mentioned in this specification is herein incorporated by reference in its entirety to the same extent as if each individual patent, patent application, and/or publication was specifically and individually indicated to be incorporated by reference. Notwithstanding the prior sentence, U.S. patent application Ser. No. 12/244,737, filed Oct. 2, 2008; U.S. patent application Ser. No. 12/244,748, filed Oct. 2, 2008; U.S. patent application Ser. No. 12/263,331, filed Oct. 31, 2008; U.S. patent application Ser. No. 12/244,752, filed Oct. 2, 2008; U.S. patent application Ser. No. 12/263,350, filed Oct. 31, 2008; U.S. patent application Ser. No. 12/326,016, filed Dec. 1, 2008; and U.S. patent application Ser. No. 13/252,910, filed Oct. 4, 2011 are not incorporated by reference.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration of an exemplary system to support remote access and analysis of media and reactions from viewers.
FIG. 2 is a flow chart illustrating an exemplary process to support remote access and analysis of media and reactions from viewers.
FIG. 3 shows one or more exemplary physiological responses aggregated from the viewers and presented in the response panel of the interactive browser.
FIG. 4 shows exemplary verbatim comments and feedbacks collected from the viewers and presented in the response panel of the interactive browser.
FIG. 5 shows exemplary answers to one or more survey questions collected from the viewers and presented as a pie chart in the response panel of the interactive browser.
FIG. 6 shows exemplary answers to one or more survey questions collected from the viewers and presented as a histogram
FIG. 7 shows an exemplary graph displaying the percentages of viewers who “liked” or “really liked” a set of advertisements.
FIG. 8 is an illustration of an exemplary system to support providing actionable insights based on in-depth analysis of reactions from viewers.
FIG. 9 is a flow chart illustrating an exemplary process to support providing actionable insights based on in-depth analysis of reactions from viewers.
FIG. 10 shows exemplary highlights and arrows representing trends in the physiological responses from the viewers as well as verbal explanation of such markings.
FIG. 11 is an illustration of an exemplary system to support synchronization of media with physiological responses from viewers.
FIG. 12 is a flow chart illustrating an exemplary process to support synchronization of media with physiological responses from viewers.
FIG. 13 is an illustration of an exemplary system to support graphical presentation of verbatim comments from viewers.
FIG. 14 is a flow chart illustrating an exemplary process to support graphical presentation of verbatim comments from viewers.
FIG. 15 shows an exemplary bubble graph presenting summation of positive and negative comments from the viewers to various aspects of the media instance.
FIG. 16 shows an exemplary word cloud presenting key words and concepts from the viewers of the media instance.
DETAILED DESCRIPTION
Examples disclosed herein enable remote and interactive access, navigation, and analysis of reactions from one or more viewers to a specific media instance. Here, the reactions include, but are not limited to, physiological responses, survey results, verbatim feedback, event-based metadata, and derived statistics for indicators of success and failure from the viewers. The reactions from the viewers are aggregated and stored in a database and are delivered to a user via a web-based graphical interface or application, such as a Web browser. Through the web-based graphical interface, the user is able to remotely access and navigate the specific media instance, together with one or more of: the aggregated physiological responses that have been synchronized with the media instance, the survey results, and the verbatim feedbacks related to the specific media instance. Instead of being presented with static data (such as a snapshot) of the viewers' reactions to the media instance, the user is now able to interactively divide, dissect, parse, and analysis the reactions in any way he/she prefer. The examples disclosed herein provide automation that enables those who are not experts in the field of physiological analysis to understand and use physiological data by enabling these non-experts to organize the data and organize and improve presentation or visualization of the data according to their specific needs. In this manner, the examples disclosed herein provide an automated process that enables non-experts to understand complex data, and to organize the complex data in such a way as to present conclusions as appropriate to the media instance.
In the following description, numerous specific details are introduced to provide a thorough understanding of, and enabling description for, example systems and methods. One skilled in the relevant art, however, will recognize that these examples can be practiced without one or more of the specific details, or with other components, systems, etc. In other instances, well-known structures or operations are not shown, or are not described in detail, to avoid obscuring aspects of the disclosed examples.
Having multiple reactions from the viewers (e.g., physiological responses, survey results, verbatim feedback, events tagged with metadata, etc.) available in one place and at a user's fingertips, along with the automated methods for aggregating the data provided herein, allows the user to view the reactions to hundreds of media instances in one sitting by navigating through them. For each of the media instances, the integration of multiple reactions provides the user with more information than the sum of each of the reactions to the media instance. For a non-limiting example, if one survey says that an ad is bad, that is just information; but if independent surveys, verbatim feedbacks and physiological data across multiple viewers say the same, the reactions to the media instance become more trustworthy. By combining this before a user sees it, the correct result is presented to the user.
FIG. 1 is an illustration of an example system to support automated remote access and analysis of media and reactions from viewers. Although this diagram depicts components as functionally separate, such depiction is merely for illustrative purposes. It will be apparent to those skilled in the art that the components portrayed in this figure can be arbitrarily combined or divided into separate software, firmware and/or hardware components. Furthermore, it will also be apparent to those skilled in the art that such components, regardless of how they are combined or divided, can execute on the same computing device or multiple computing devices, and wherein the multiple computing devices can be connected by one or more networks.
Referring to FIG. 1 , an authentication module 102 is operable to authenticate identity of a user 101 requesting access to a media instance 103 together with one or more reactions 104 from a plurality of viewers of the media instance remotely over a network 107 . Here, the media instance and its pertinent data can be stored in a media database 105 , and the one or more reactions from the viewers can be stored in a reaction database 106 , respectively. The network 107 can be, but is not limited to, one or more of the internet, intranet, wide area network (WAN), local area network (LAN), wireless network, Bluetooth, and mobile communication networks. Once the user is authenticated, a presentation module 108 is operable to retrieve and present the requested information (e.g., the media instance together with one or more reactions from the plurality of viewers) to the user via an interactive browser 109 . The interactive browser 109 comprises at least two panels including a media panel 110 , which is operable to present, play, and pause the media instance, and a response panel 111 , which is operable to display the one or more reactions corresponding to the media instance, and provide the user with a plurality of features to interactively divide, dissect, parse, and analyze the reactions.
FIG. 2 is a flow chart illustrating an exemplary process to support remote access and analysis of media and reactions from viewers. Although this figure depicts functional steps in a particular order for purposes of illustration, the process is not limited to any particular order or arrangement of steps. One skilled in the art will appreciate that the various steps portrayed in this figure could be omitted, rearranged, combined and/or adapted in various ways.
Referring to FIG. 2 , a media instance and one or more reactions to the instance from a plurality of viewers are stored and managed in one or more databases at step 201 . Data or information of the reactions to the media instance is obtained or gathered from each user via a sensor headset, one example of which is described in U.S. patent application Ser. No. 12/206,676, filed Sep. 8, 2008, U.S. patent application Ser. No. 11/804,517, filed May 17, 2007, and U.S. patent application Ser. No. 11/681,265, filed Mar. 2, 2007. At step 202 , the identity of a user requesting access to the media instance and the one or more reactions remotely is authenticated. At step 203 , the requested media instance and the one or more reactions are retrieved and delivered to the user remotely over a network (e.g., the Web). At step 204 , the user may interactively aggregate, divide, dissect, parse, and analyze the one or more reactions to draw conclusions about the media instance.
In some examples, alternative forms of access to the one or more reactions from the viewers other than over the network may be adopted. For non-limiting examples, the reactions can be made available to the user on a local server on a computer or on a recordable media such as a DVD disc with all the information on the media.
In some examples, with reference to FIG. 1 , an optional analysis module 112 is operable to perform in-depth analysis on the viewers' reactions to a media instance as well as the media instance itself (e.g., dissecting the media instance into multiple scenes/events/sections). Such analysis provides the user with information on how the media instance created by the user is perceived by the viewers. In addition, the analysis module is also operable to categorize viewers' reactions into the plurality of categories.
In some examples, user database 113 stores information of users who are allowed to access the media instances and the reactions from the viewers, and the specific media instances and the reactions each user is allowed to access. The access module 106 may add or remove a user for access, and limit or expand the list of media instances and/or reactions the user can access and/or the analysis features the user can use by checking the user's login name and password. Such authorization/limitation on a user's access can be determined based upon who the user is, e.g., different amounts of information for different types of users. For a non-limiting example, Company ABC can have access to certain ads and survey results of viewers' reactions to the ads, which Company XYZ cannot or have only limited access to.
In some examples, one or more physiological responses aggregated from the viewers can be presented in the response panel 111 as lines or traces 301 in a two-dimensional graph or plot as shown in FIG. 3 . Horizontal axis 302 of the graph represents time, and vertical axis 303 of the graph represents the amplitude (intensity) of the one or more physiological responses. Here, the one or more physiological responses are aggregated over the viewers via one or more of: max, min, average, deviation, or a higher ordered approximation of the intensity of the physiological responses from the viewers. The responses are synchronized with the media instance at each and every moment over the entire duration of the media instance, allowing the user to identify the second-by second changes in viewers' emotions and their causes. A cutting line 304 marks the physiological responses from the viewers corresponding to the current scene (event, section, or moment in time) of the media instance. The cutting line moves in coordination with the media instance being played.
In some examples, change (trend) in amplitude of the aggregated responses is also a good measure of the quality of the media instance. If the media instance is able to change viewers emotions up and down in a strong manner (for a non-limiting example, mathematical deviation of the response is large), such strong change in amplitude corresponds to a good media instance that puts the viewers into different emotional states. In contrast, a poor performing media instance does not put the viewers into different emotional states. The amplitudes and the trend of the amplitudes of the responses are good measures of the quality of the media instance. Such information can be used by media designers to identify if the media instance is eliciting the desired response and which key events/scenes/sections of the media instance need to be changed in order to match the desired response. A good media instance should contain multiple moments/scenes/events that are intense and produce positive amplitude of response across viewers. A media instance that failed to create such responses may not achieve what the creators of the media instance have intended.
In some examples, other than providing a second by second view for the user to see how specific events in the media instance affect the viewers' emotions, the aggregated responses collected and calculated can also be used for the compilation of aggregate statistics, which are useful in ranking the overall affect of the media instance. Such statistics include but are not limited to Average Liking and Heart Rate Deviation.
In some examples, the viewers of the media instance are free to write comments (e.g., what they like, what they dislike, etc.) on the media instance, and the verbatim (free flowing text) comments or feedbacks 401 from the viewers can be recorded and presented in a response panel 111 as shown in FIG. 4 . Such comments can be prompted, collected, and recorded from the viewers while they are watching the specific media instance and the most informative ones are put together and presented to the user. The user may then analyze, and digest keywords in the comments to obtain a more complete picture of the viewers' reactions. In addition, the user can search for specific keywords he/she is interested in about the media instance, and view only those comments containing the specified keywords.
In some examples, the viewers' comments about the media instance can be characterized as positive or negative in a plurality of categories/topics/aspects related to the product, wherein such categories include but are not limited to, product, event, logo, song, spokesperson, jokes, narrative, key events, storyline. These categories may not be predetermined, but instead be extracted from the analysis of their comments.
In some examples, answers to one or more survey questions 501 aggregated from the viewers can be rendered graphically, for example, by being presented in the response panel 111 in a graphical format 502 as shown in FIG. 5 Alternatively, FIG. 6 is an exemplary histogram displaying the response distribution of viewers asked to rate an advertisement on a scale of 1-5. Here, the graphical format can be but is not limited to, a bar graph, a pie chart (e.g., as shown in FIG. 5 ), a histogram (e.g., as shown in FIG. 6 ), or any other suitable graph type.
In some examples, the survey questions can be posed or presented to the viewers while they are watching the specific media instance and their answers to the questions are collected, recorded, summed up by pre-defined categories via a surveying module 114 . Once the survey results are made available to the user (creator of the media instance), the user may pick any of the questions, and be automatically presented with survey results corresponding to the question visually to the user. The user may then view and analyze how viewers respond to specific questions to obtain a more complete picture of the viewers' reactions.
In some examples, many different facets of the one or more reactions from the viewers described above can be blended into a few simple metrics that the user can use to see how it is currently positioned against the rest of their industry. For the user, knowing where it ranks in its industry in comparison to its competition is often the first step in getting to where it wants to be. For a non-limiting example, in addition to the individual survey results of a specific media instance, the surveying module may also provide the user with a comparison of survey results and statistics to multiple media instances. This automation allows the user not only to see the feedback that the viewers provided with respect to the specific media instance, but also to evaluate how the specific media instance compares to other media instances designed by the same user or its competitors. FIG. 7 shows an exemplary graph displaying the percentages of viewers who “liked” or “really liked” a set of advertisements, which helps to determine if a new ad is in the top quartile with respect to other ads.
Some examples disclosed herein provide a user not only with tools for accessing and obtaining a maximum amount of information out of reactions from a plurality of viewers to a specific media instance, but also with actionable insights on what changes the user can make to improve the media instance based on in-depth analysis of the viewers' reactions. Such analysis requires expert knowledge on the viewers' physiological behavior and large amounts of analysis time, which the user may not possess. Here, the reactions include but are not limited to, physiological responses, survey results, and verbatim feedbacks from the viewers, to name a few. The reactions from the viewers are aggregated and stored in a database and presented to the user via a graphical interface, as described above. In some examples, predefined methods for extracting information from the reactions and presenting that information are provided so that the user is not required to be an expert in physiological data analysis to reach and understand conclusions supported by the information. Making in-depth analysis of reactions to media instances and actionable insights available to a user enables a user who is not an expert in analyzing physiological data to obtain critical information that can have significant commercial and socially positive impacts.
FIG. 8 is an illustration of an exemplary system to support providing actionable insights based on in-depth analysis of reactions from viewers. Although this diagram depicts components as functionally separate, such depiction is merely for illustrative purposes. It will be apparent to those skilled in the art that the components portrayed in this figure can be arbitrarily combined or divided into separate software, firmware and/or hardware components. Furthermore, it will also be apparent to those skilled in the art that such components, regardless of how they are combined or divided, can execute on the same computing device or multiple computing devices, and wherein the multiple computing devices can be connected by one or more networks.
Referring to FIG. 8 , a collection module 803 is operable to collect, record, store and manage one or more reactions 802 from a plurality of viewers of a media instance 801 . The viewers from whom reactions 802 are collected can be in the same physical location or different physical locations. Additionally, the viewers can be viewing the media instance and the reactions collected at the same time, or at different times (e.g., viewer 1 is viewing the media instance at 9 AM while viewer 2 is viewing the media instance at 3 PM). Data or information of the reactions to the media instance is obtained or gathered from each user via a sensor headset. In some examples, the sensor headset integrates sensors into a housing which can be placed on a human head for measurement of physiological data. The device includes at least one sensor and can include a reference electrode connected to the housing. A processor coupled to the sensor and the reference electrode receives signals that represent electrical activity in tissue of a user. The processor generates an output signal including data of a difference between an energy level in each of a first and second frequency band of the signals. The difference between energy levels is proportional to release level present time emotional state of the user. The headset includes a wireless transmitter that transmits the output signal to a remote device. The headset therefore processes the physiological data to create the output signal that correspond to a person's mental and emotional state (reactions or reaction data). An example of a sensor headset is described in U.S. patent application Ser. Nos. 12/206,676, filed Sep. 8, 2008, 11/804,517, filed May 17, 2007, and 11/681,265, filed Mar. 2, 2007.
The media instance and its pertinent data can be stored in a media database 804 , and the one or more reactions from the viewers can be stored in a reaction database 805 , respectively. An analysis module 806 performs in-depth analysis on the viewers' reactions and provides actionable insights on the viewers' reactions to a user 807 so that the user can draw its own conclusion on how the media instance can/should be improved. A presentation module 808 is operable to retrieve and present the media instance 801 together with the one or more reactions 802 from the viewers of the media instance via an interactive browser 809 . Here, the interactive browser includes at least two panels—a media panel 810 , operable to present, play, and pause the media instance, and a reaction panel 811 , operable to display the one or more reactions corresponding to the media instance as well as the key insights provided by the analysis module 806 .
FIG. 9 is a flow chart illustrating an exemplary automatic process to support providing actionable insights based on in-depth analysis of reactions from viewers. Although this figure depicts functional steps in a particular order for purposes of illustration, the process is not limited to any particular order or arrangement of steps. One skilled in the art will appreciate that the various steps portrayed in this figure could be omitted, rearranged, combined and/or adapted in various ways.
Referring to FIG. 9 , one or more reactions to a media instance from a plurality of viewers are collected, stored and managed in one or more databases at step 901 . At step 902 , in-depth analysis is performed on the viewers' reactions using expert knowledge, and actionable insights are generated based on the viewers' reactions and provided to a user at step 903 so that the user can draw its own conclusion on the media instance can/should be improved. At step 904 , the one or more reactions can be presented to the user together with the actionable insights to enable the user to draw its own conclusions about the media instance. The configuration used to present the reactions and actionable insights can be saved and tagged with corresponding information, allowing it to be recalled and used for similar analysis in the future.
In some examples, the analysis module is operable to provide insights or present data based in-depth analysis on the viewers' reactions to the media instance on at least one question. An example question is whether the media instance performs most effectively across all demographic groups or especially on a specific demographic group, e.g., older women? Another example question is whether certain elements of the media instance, such as loud noises, were very effective at engaging viewers in a positive, challenging way? Yet another example question is whether thought provoking elements in the media instance were much more engaging to viewers than product shots? Also, an example question includes whether certain characters, such as lead female characters, appearing in the media instance were effective for male viewers and/or across target audiences in the female demographic? Still another example question includes whether physiological responses to the media instance from the viewers were consistent with viewers identifying or associating positively with the characters in the media instance? A further question is whether the media instance was universal—performed well at connecting across gender, age, and income boundaries, or highly polarizing?
The analysis module therefore automates the analysis through use of one or more questions, as described above. The questions provide a context for analyzing and presenting the data or information received from viewers in response to the media instance. The analysis module is configured, using the received data, to answer some number of questions, where answers to the questions provide or correspond to the collected data. When a user desires results from the data for a particular media instance, the user selects a question to which they desire an answer for the media instance. In response to the question selection, the results of the analysis are presented in the form of an answer to the question, where the answer is derived or generated using the data collected and corresponding to the media instance. The results of the analysis can be presented using textual and/or graphical outputs or presentations. The results of the analysis can also be generated and presented using previous knowledge of how to represent the data to answer the question, the previous knowledge coming from similar data analyzed in the past. Furthermore, presentation of data of the media instance can be modified by the user through user or generation of other questions.
The analysis module performs the operations described above in conjunction with the presentation module, where the presentation module includes numerous different renderings for data. In operation, a rendering is specified or selected for a portion of data of a media instance, and the rendering is then tagged with one or more questions that apply to the data. This architecture allows users to modify how data is represented using a set of tools. The system remembers or stores information of how data was represented and the question or question type that was being answered. This information of prior system configurations allows the system, at a subsequent time, to self-configure to answer the same or similar questions for the same media instance or for different media instances. Users thus continually improve the ability of the system to answer questions and improve the quality of data provided in the answers.
In some examples, the presentation module is operable to enable the user to pick a certain section 1001 of the reactions to the media instance 1002 , such as the physiological responses 1003 from the viewers shown in the reaction panel 1011 via, for a non-limiting example, “shading”, as shown in FIG. 10 . The analysis module 1006 may then perform the analysis requested on the shaded section of media instance and/or physiological responses automatically to illustrate the responses in a way that a lay person can take advantage of expert knowledge in parsing the viewers' reaction. The analyzed results can then be presented to the user in real time and can be shared with other people.
In some examples, the analysis module is operable to analyze the shaded section of the media instance and/or responses by being preprogrammed either by an analyst or the user themselves. Usually, a user is most often interested in a certain number of attributes of the viewers' responses. The analysis module provides the user with insights, conclusions, and findings that they can review from the bottom up. Although the analysis result provides inside and in-depth analysis of the data as well as various possible interpretations of the shaded section of the media instance, which often leaves a conclusion evident, such analysis, however, is no substitute for reaching conclusion by the user. Instead the user is left to draw his/her own conclusion about the section based on the analysis provided.
In some examples, a user may pick a section and choose one of the questions/tasks/requests 1004 that he/she is interested in from a prepared list. The prepared list of questions may include but is not limited to any number of questions. Some example questions follow along with a response evoked in the analysis module.
An example question is “Where were there intense responses to the media instance?” In response the analysis module may calculate the intensity of the responses automatically by looking for high coherence areas of responses.
Another example question is “Does the media instance end on a happy note?” or “Does the audience think the event (e.g., joke) is funny?” In response the analysis module may check if the physiological data shows that viewer acceptance or approval is higher in the end than at the beginning of the media instance.
Yet another example question is “Where do people engage in the spot?” In response to this question the analysis module may check if there is a coherent change in viewers' emotions.
Still another example question is “What is the response to the brand moment?” In response the analysis module may check if thought goes up, but acceptance or approval goes down during the shaded section of the media.
An additional example question is “Which audience does the product introduction work on best?” In response the analysis module analyzes the responses from various segments of the viewers, which include but are not limited to, males, females, gamers, republicans, engagement relative to an industry, etc.
In some examples, the presentation module ( FIG. 8, 807 ) is operable to present the analysis results in response to the questions raised together with the viewers' reactions to the user graphically on the interactive browser. For non-limiting examples, line highlights 1005 and arrows 1006 representing trends in the physiological responses from the viewers can be utilized as shown in FIG. 10 , where highlights mark one or more specific physiological responses (e.g., thought in FIG. 10 ) to be analyzed and the up/down arrows indicate rise/fall in the corresponding responses. In addition, other graphic markings can also be used, which can be but are not limited to, text boxes, viewing data from multiple groups at once (comparing men to women) and any graphic tools that are commonly used to mark anything important. For another non-limiting example, a star, dot and/or other graphic element may be used to mark the point where there is the first coherent change and a circle may be used to mark the one with the strongest response.
In some examples, verbal explanation 1007 of the analysis results in response to the questions raised can be provided to the user together with graphical markings shown in FIG. 10 . Such verbal explanation describes the graphical markings (e.g., why an arrow rises, details about the arrow, etc.). For the non-limiting example of an advertisement video clip shown in FIG. 10 , verbal explanation 1007 states that “Thought follows a very regular sinusoidal pattern throughout this advertisement. This is often a result of tension-resolution cycles that are used to engage viewers by putting them in situations where they are forced to think intensely about what they are seeing and then rewarding them with the resolution of the situation.” For another non-limiting example of a joke about a man hit by a thrown rock, the verbal explanation may resemble something like: “The falling of the man after being hit by a rock creates the initial coherent, positive response in liking. This shows that the actual rock throw is not funny, but the arc that the person's body takes is. After the body hits the ground, the response reverts to neutral and there are no further changes in emotions during this section.”
In some examples, with reference to FIG. 8 , an optional authentication module 813 is operable to authenticate identity of the user requesting access to the media instance and the verbatim reactions remotely over a network 812 . Here, the network can be but is not limited to, internet, intranet, wide area network (WAN), local area network (LAN), wireless network, Bluetooth, and mobile communication network.
In some examples, optional user database 814 stores information of users who are allowed to access the media instances and the verbatim reactions from the viewers, and the specific media instances and the reactions each user is allowed to access. The access module 810 may add or remove a user for access, and limit or expand the list of media instances and/or reactions the user can access and/or the analysis features the user can use by checking the user's login name and password. Such authorization/limitation on a user's access can be determined to based upon who the user is, e.g., different amounts of information for different types of users. For a non-limiting example, Company ABC can have access to certain ads and feedbacks from viewers' reactions to the ads, to which Company XYZ cannot have access or can have only limited access.
In some examples, a specific media instance is synchronized with physiological responses to the media instance from a plurality of viewers continuously over the entire time duration of the media instance. Once the media instance and the physiological responses are synchronized, an interactive browser enables a user to navigate through the media instance (or the physiological responses) in one panel while presenting the corresponding physiological responses (or the section of the media instance) at the same point in time in another panel.
The interactive browser allows the user to select a section/scene from the media instance, correlate, present, and compare the viewers' physiological responses to the particular section. Alternatively, the user may monitor the viewers' physiological responses continuously as the media instance is being displayed. Being able to see the continuous (instead of static snapshot of) changes in physiological responses and the media instance side by side and compare aggregated physiological responses from the viewers to a specific event of the media instance in an interactive way enables the user to obtain better understanding of the true reaction from the viewers to whatever stimuli being presented to them.
FIG. 11 is an illustration of an exemplary system to support synchronization of media with physiological responses from viewers of the media. Although this diagram depicts components as functionally separate, such depiction is merely for illustrative purposes. It will be apparent to those skilled in the art that the components portrayed in this figure can be arbitrarily combined or divided into separate software, firmware and/or hardware components. Furthermore, it will also be apparent to those skilled in the art that such components, regardless of how they are combined or divided, can execute on the same computing device or multiple computing devices, and wherein the multiple computing devices can be connected by one or more networks.
Referring to FIG. 11 , a synchronization module 1103 is operable to synchronize and correlate a media instance 1101 with one or more physiological responses 1102 aggregated from one or more viewers of the media instance continuously at each and every moment over the entire duration of the media instance. Here, the media instance and its pertinent data can be stored in a media database 1104 , and the one or more physiological responses aggregated from the viewers can be stored in a reaction database 1105 , respectively. An interactive browser 1106 comprises at least two panels including a media panel 1107 , which is operable to present, play, and pause the media instance, and a reaction panel 1108 , which is operable to display and compare the one or more physiological responses (e.g., Adrenaline, Liking, and Thought) corresponding to the media instance as lines (traces) in a two-dimensional line graph. A horizontal axis of the graph represents time, and a vertical axis represents the amplitude (intensity) of the one or more physiological responses. A cutting line 1109 marks the physiological responses from the viewers to the current scene (event, section, or moment in time) of the media instance, wherein the cutting line can be chosen by the user and move in coordination with the media instance being played. The interactive browser enables the user to select an event/section/scene/moment from the media instance presented in the media panel 1107 and correlate, present, and compare the viewers' physiological responses to the particular section in the reaction panel 1108 . Conversely, interactive browser also enables the user to select the cutting line 1109 of physiological responses from the viewers in the reaction panel 1108 at any specific moment, and the corresponding media section or scene can be identified and presented in the media panel 1107 .
In some examples, the synchronization module 1103 synchronizes and correlates a media instance 1101 with one or more physiological responses 1102 aggregated from a plurality of viewers of the media instance by synchronizing each event of the media. The physiological response data of a person includes but is not limited to heart rate, brain waves, electroencephalogram (EEG) signals, blink rate, breathing, motion, muscle movement, galvanic skin response, skin temperature, and any other physiological response of the person. The physiological response data corresponding to each event or point in time is then retrieved from the media database 1104 . The data is offset to account for cognitive delays in the human brain corresponding to the signal collected (e.g., the cognitive delay of the brain associated with human vision is different than the cognitive delay associated with auditory information) and processing delays of the system, and then synchronized with the media instance 1101 . Optionally, an additional offset may be applied to the physiological response data 1102 of each individual to account for time zone differences between the viewer and reaction database 1105 .
FIG. 12 is a flow chart illustrating an exemplary process to support synchronization of media with physiological responses from viewers of the media. Although this figure depicts functional steps in a particular order for purposes of illustration, the process is not limited to any particular order or arrangement of steps. One skilled in the art will appreciate that the various steps portrayed in this figure could be omitted, rearranged, combined and/or adapted in various ways.
Referring to FIG. 12 , a media instance is synchronized with one or more physiological responses aggregated from a plurality of viewers of the media instance continuously at each and every moment over the entire duration of the media instance at step 1201 . At step 1202 , the synchronized media instance and the one or more physiological responses from the viewers are presented side-by-side. An event/section/scene/moment from the media instance can be selected at step 1203 , and the viewers' physiological responses to the particular section can be correlated, presented, and compared at step 1204 . Alternatively, the viewers' physiological responses can be monitored continuously as the media instance is being displayed at step 1205 .
In some examples, with reference to FIG. 11 , an aggregation module 1110 is operable to retrieve from the reaction database 1105 and aggregate the physiological responses to the media instance across the plurality of viewers and present each of the aggregated responses as a function over the duration of the media instance. The aggregated responses to the media instance can be calculated via one or more of: max, min, average, deviation, or a higher ordered approximation of the intensity of the physiological responses from the viewers.
In some examples, change (trend) in amplitude of the aggregated responses is a good measure of the quality of the media instance. If the media instance is able to change viewers emotions up and down in a strong manner (for a non-limiting example, mathematical deviation of the response is large), such strong change in amplitude corresponds to a good media instance that puts the viewers into different emotional states. In contrast, a poor performing media instance does not put the viewers into different emotional states. Such information can be used by media designers to identify if the media instance is eliciting the desired response and which key events/scenes/sections of the media instance need to be changed in order to match the desired response. A good media instance should contain multiple moments/scenes/events that are intense and produce positive amplitude of response across viewers. A media instance failed to create such responses may not achieve what the creators of the media instance have intended.
In some examples, the media instance can be divided up into instances of key moments/events/scenes/segments/sections in the profile, wherein such key events can be identified and/tagged according to the type of the media instance. In the case of video games, such key events include but are not limited to, elements of a video game such as levels, cut scenes, major fights, battles, conversations, etc. In the case of Web sites, such key events include but are not limited to, progression of Web pages, key parts of a Web page, advertisements shown, content, textual content, video, animations, etc. In the case of an interactive media/movie/ads, such key events can be but are not limited to, chapters, scenes, scene types, character actions, events (for non-limiting examples, car chases, explosions, kisses, deaths, jokes) and key characters in the movie.
In some examples, an event module 1111 can be used to quickly identify a numbers of moments/events/scenes/segments/sections in the media instance retrieved from the media database 1104 and then automatically calculate the length of each event. The event module may enable each user, or a trained administrator, to identify and tag the important events in the media instance so that, once the “location” (current event) in the media instance (relative to other pertinent events in the media instance) is selected by the user, the selected event may be better correlated with the aggregated responses from the viewers.
In some examples, the events in the media instance can be identified, automatically if possible, through one or more applications that parse user actions in an environment (e.g., virtual environment, real environment, online environment, etc.) either before the viewer's interaction with the media instance in the case of non-interactive media such as a movie, or afterwards by reviewing the viewer's interaction with the media instance through recorded video, a log of actions or other means. In video games, web sites and other electronic interactive media instance, the program that administers the media can create this log and thus automate the process.
An example enables graphical presentation and analysis of verbatim comments and feedbacks from a plurality of viewers to a specific media instance. These verbatim comments are first collected from the viewers and stored in a database before being analyzed and categorized into various categories. Once categorized, the comments can then be presented to a user in various graphical formats, allowing the user to obtain an intuitive visual impression of the positive/negative reactions to and/or the most impressive characteristics of the specific media instance as perceived by the viewers.
An example enables graphical presentation and analysis of verbatim comments and feedbacks from a plurality of viewers to a specific media instance. These verbatim comments are first collected from the viewers and stored in a database before being analyzed and categorized into various categories. Once categorized, the comments can then be presented to a user in various graphical formats, allowing the user to obtain an intuitive visual impression of the positive/negative reactions to and/or the most impressive characteristics of the specific media instance, as perceived by the viewers. Instead of parsing through and dissecting the comments and feedbacks word by word, the user is now able to visually evaluate how well the media instance is being received by the viewers at a glance.
FIG. 13 is an illustration of an exemplary system to support graphical presentation of verbatim comments from viewers. Although this diagram depicts components as functionally separate, such depiction is merely for illustrative purposes. It will be apparent to those skilled in the art that the components portrayed in this figure can be arbitrarily combined or divided into separate software, firmware and/or hardware components. Furthermore, it will also be apparent to those skilled in the art that such components, regardless of how they are combined or divided, can execute on the same computing device or multiple computing devices, and wherein the multiple computing devices can be connected by one or more networks.
Referring to FIG. 13 , a collection module 1303 is operable to collect, record, store and manage verbatim reactions 1302 (comments and feedbacks) from a plurality of viewers of a media instance 1301 . Here, the media instance and its pertinent data can be stored in a media database 1304 , and the verbatim reactions from the viewers can be stored in a reaction database 1305 , respectively. An analysis module 1306 is operable to analyze the verbatim comments from the viewers and categorize them into the plurality of categories. A presentation module 1307 is operable to retrieve and categorize the verbatim reactions to the media instance into various categories, and then present these verbatim reactions to a user 1308 based on their categories in graphical forms via an interactive browser 1309 . The interactive browser includes at least two panels—a media panel 1310 , which is operable to present, play, and pause the media instance, and a comments panel 1311 , which is operable to display not only the one or more reactions corresponding to the media instance, but also one or more graphical categorization and presentation of the verbatim reactions to provide the user with both a verbal and/or a visual perception and interpretation of the feedbacks from the viewers.
FIG. 14 is a flow chart illustrating an exemplary process to support graphical presentation of verbatim comments from viewers. Although this figure depicts functional steps in a particular order for purposes of illustration, the process is not limited to any particular order or arrangement of steps. One skilled in the art will appreciate that the various steps portrayed in this figure could be omitted, rearranged, combined and/or adapted in various ways.
Referring to FIG. 14 , verbatim reactions to a media instance from a plurality of viewers are collected, stored and managed at step 1401 . At step 1402 , the collected verbatim reactions are analyzed and categorized into various categories. The categorized comments are then retrieved and presented to a user in graphical forms based on the categories at step 1403 , enabling the user to visually interpret the reactions from the viewers at step 1404 .
In some examples, the viewers of the media instance are free to write what they like and don't like about the media instance, and the verbatim (free flowing text) comments or feedbacks 501 from the viewers can be recorded and presented in the comments panel 111 verbatim as shown in FIG. 4 described above. In some examples, the analysis module is operable to further characterize the comments in each of the plurality of categories as positive or negative based on the words used in each of the comments. Once characterized, the number of positive or negative comments in each of the categories can be summed up. For a non-limiting example, comments from viewers on a certain type of events, like combat, can be characterized and summed up as being 40% positive, while 60% negative. Such an approach avoids single verbatim response from bias the responses from a group of viewers, making it easy for the user to understand how viewers would react to every aspect of the media instance.
In some examples, the analysis module is operable to characterize the viewers' comments about the media instance as positive or negative in a plurality of categories/topics/aspects related to the product, wherein such categories include but are not limited to, product, event, logo, song, spokesperson, jokes, narrative, key events, storyline. These categories may not be predetermined, but instead be extracted from the analysis of their comments.
In some examples, the presentation module is operable to present summation of the viewers' positive and negative comments to various aspects/topics/events of the media instance to the user (creator of the media instance) in a bubble graph, as shown in FIG. 15 . The vertical axis 1501 and horizontal axis 1502 of the bubble graph represent the percentage of positive or negative comments from the viewers about the media instance, respectively. Each bubble 1503 in the graph represents one of the topics the viewers have commented upon, marked by the name of the event and the percentages of the viewers' negative and positive feedbacks on the event. The size of the bubble represents the number of viewers commenting on this specific aspect of the media instance, and the location of the bubble on the graph indicates whether the comments from the viewers are predominantly positive or negative.
In some examples, the verbatim comments from the viewers can be analyzed, and key words and concepts (adjectives) can be extracted and presented in a word cloud, as shown in FIG. 16 , rendering meaningful information from the verbatim comments more accessible. Every word in the word cloud is represented by a circle, square, any other commonly used geometric shape or simply by the word itself as shown in FIG. 16 . Each representation is associated with a corresponding weight represented using font sizes or other visual clues. For the non-limiting example in FIG. 16 , the size of each word in the word cloud represents the number of times or percentages of the viewers use the word in their responses. This is useful as a means of displaying “popularity” of an adjective that has been democratically ‘voted’ on to describe the media instance and where precise results are not desired. Here, the three most popular adjectives used to describe the media instance are “fun”, “cool”, and “boring”.
In some examples, the viewers may simply be asked to answer a specific question, for example, “What are three adjectives that best describe your response to this media.” The adjectives in the viewers' responses to the question can then be collected, categorized, and summed up, and presented in a Word cloud. Alternatively, the adjectives the viewers used to describe their responses to the media instance may be extracted from collected survey data.
In some examples, with reference to FIG. 13 , an optional authentication module 1313 is operable to authenticate identity of the user requesting access to the media instance and the verbatim reactions remotely over a network 1313 . Here, the network can be but is not limited to, internet, intranet, wide area network (WAN), local area network (LAN), wireless network, Bluetooth, and mobile communication network.
In some examples, optional user database 1314 stores information of users who are allowed to access the media instances and the verbatim reactions from the viewers, and the specific media instances and the reactions each user is allowed to access. The access module 1310 may add or remove a user for access, and limit or expand the list of media instances and/or reactions the user can access and/or the analysis features the user can use by checking the user's login name and password. Such authorization/limitation on a user's access can be determined to based upon who the user is, e.g., different amounts of information for different types of users. For a non-limiting example, Company ABC can have access to certain ads and feedback from viewers' reactions to the ads, while Company XYZ cannot have access or can only have limited access to the same ads and/or feedback.
Some of the examples described herein include a method comprising: receiving a media instance, the media instance including a plurality of media events; receiving reaction data from a plurality of viewers while the plurality of viewers are viewing the media instance; generating aggregated reaction data by aggregating the reaction data from the plurality of viewers; generating synchronized data by synchronizing the plurality of media events of the media instance with corresponding aggregated reaction data; and providing controlled access to the synchronized data from a remote device.
The method of a disclosed example comprises providing, via the controlled access, remote interactive manipulation of the reaction data synchronized to corresponding events of the media instance.
The manipulation of a disclosed example includes at least one of dividing, dissecting, aggregating, parsing, organizing, and analyzing the reaction data.
The method of a disclosed example comprises providing controlled access to at least one of the reaction data and aggregated reaction data.
The method of a disclosed example comprises enabling via the controlled access interactive analysis of at least one of the media instance and the synchronized data.
The method of a disclosed example comprises enabling via the controlled access interactive analysis of at least one of the reaction data, the aggregated reaction data, and parsed reaction data.
The reaction data of a disclosed example includes at least one of physiological responses, survey results, feedback generated by the viewers, metadata, and derived statistics.
The reaction data of a disclosed example includes physiological responses.
The reaction data of a disclosed example includes survey results.
The reaction data of a disclosed example includes feedback generated by the viewers.
The reaction data of a disclosed example includes metadata, wherein the metadata is event-based metadata.
The reaction data of a disclosed example includes derived statistics, wherein the derived statistics are derived statistics for indicators of success and failure of the media instance
Receiving the reaction data of a disclosed example comprises receiving the reaction data from a plurality of sensor devices via wireless couplings, wherein each viewer wears a sensor device of the plurality of sensor devices.
The method of a disclosed example comprises presenting a user interface (UI), wherein the controlled access is made via the UI.
The method of a disclosed example comprises presenting the synchronized data using a rendering of a plurality or renderings.
The plurality of renderings of a disclosed example includes text, charts, graphs, histograms, images, and video.
The aggregating of a disclosed example comprises aggregating the reaction data according to at least one of maximums, minimums, averages, deviations, derivatives, amplitudes, and trends of at least one parameter of the reaction data.
The method of a disclosed example comprises selecting, via the controlled access, a portion of the media instance for which at least one of the synchronized data, the reaction data, the aggregated reaction data, and parsed reaction data is viewed. The portion of a disclosed example includes a point in time. The portion of a disclosed example includes a period of time.
The method of a disclosed example comprises automatically analyzing the reaction data.
The method of a disclosed example comprises providing remote access to results of the analyzing, and presenting the results, the presenting including presenting actionable insights corresponding to a portion of the media instance via at least one of a plurality of renderings, wherein the actionable insights correspond to emotional reactions of the plurality of viewers.
The analyzing of a disclosed example includes applying expert knowledge of physiological behavior to the reaction data.
The method of a disclosed example comprises generating a first set of questions that represent the results.
The analyzing of a disclosed example includes analyzing the reaction data in the context of the first set of questions.
The method of a disclosed example comprises selecting at least one rendering of the plurality of renderings.
The method of a disclosed example comprises tagging the selected rendering with at least one question of the first set of questions.
A user of a disclosed example can modify the presenting of the results via the selecting of at least one rendering of the plurality of renderings.
The presenting of a disclosed example includes presenting the results via presentation of the first set of questions.
The method of a disclosed example comprises, in response to the user selecting a question of the first set of questions, presenting an answer to the selected question that includes the actionable insight.
The method of a disclosed example comprises receiving comments from the plurality of viewers in response to the viewing. The comments of a disclosed example are textual comments. The synchronized data of a disclosed example includes the comments.
The method of a disclosed example comprises presenting survey questions to the plurality of viewers, the survey questions relating to the media instance. The method of a disclosed example comprises receiving answers to the survey questions from the plurality of viewers. The answers to the survey questions of a disclosed example are textual comments. The synchronized data of a disclosed example includes the answers to the survey questions.
The plurality of viewers of a disclosed example is at a location.
The plurality of viewers of a disclosed example is at a plurality of locations.
A first set of the plurality of viewers of a disclosed example is at a first location and a second set of the plurality of viewers is at a second location different from the first location.
A first set of the plurality of viewers of a disclosed example is viewing the media instance at a first time and a second set of the plurality of viewers is viewing the media instance at a second time different from the first time.
The reaction data of a disclosed example corresponds to electrical activity in brain tissue of the user.
The reaction data of a disclosed example corresponds to electrical activity in muscle tissue of the user.
The reaction data of a disclosed example corresponds to electrical activity in heart tissue of the user.
Examples described herein include a method comprising: receiving a media instance; receiving reaction data from a plurality of viewers, the reaction data generated in response to viewing of the media instance and including physiological response data; aggregating the reaction data from the plurality of viewers; and providing remote access to at least one of the reaction data and aggregated reaction data, wherein the remote access enables interactive analysis of at least one of the media instance, the reaction data, aggregated reaction data, and parsed reaction data.
Examples described herein include a method comprising: receiving a media instance; receiving reaction data from a plurality of viewers, the reaction data generated in response to viewing of the media instance and including physiological response data; aggregating the reaction data from the plurality of viewers; and enabling remote interactive analysis of the media instance and at least one of the reaction data, aggregated reaction data, and parsed reaction data.
Examples described herein include a method comprising: receiving a media instance; receiving reaction data from a plurality of viewers, the reaction data generated in response to viewing of the media instance and including physiological response data; and enabling remote interactive manipulation of the reaction data synchronized to corresponding events of the media instance, the manipulation including at least one of dividing, dissecting, aggregating, parsing, and analyzing the reaction data.
Examples described herein include a system comprising: a processor coupled to a database, the database including a media instance and reaction data, the media instance comprising a plurality of media events, the reaction data received from a plurality of viewers viewing the media instance; a first module coupled to the processor, the first module generating aggregated reaction data by aggregating the reaction data from the plurality of viewers, the first module generating synchronized data by synchronizing the plurality of media events of the media instance with corresponding aggregated reaction data; and a second module coupled to the processor, the second module comprising a plurality of renderings and a user interface (UI) that provide controlled access to the synchronized data from a remote device.
The controlled access of a disclosed example is through the UI and includes remote interactive manipulation of the reaction data synchronized to corresponding events of the media instance.
The manipulation of a disclosed example includes at least one of dividing, dissecting, aggregating, parsing, organizing, and analyzing the reaction data.
The controlled access of a disclosed example includes access to at least one of the reaction data and aggregated reaction data.
The controlled access of a disclosed example includes interactive analysis of at least one of the media instance and the synchronized data.
The controlled access of a disclosed example includes interactive analysis of at least one of the reaction data, the aggregated reaction data, and parsed reaction data.
The plurality of renderings of a disclosed example includes text, charts, graphs, histograms, images, and video.
The UI of a disclosed example presents the synchronized data using at least one rendering of the plurality or renderings.
The UI of a disclosed example allows selection of a portion of the media instance for which at least one of the synchronized data, the reaction data, the aggregated reaction data, and parsed reaction data is viewed. The portion of a disclosed example includes a point in time. The portion of a disclosed example includes a period of time.
The first module of a disclosed example analyzes the reaction data.
The UI of a disclosed example provides remote access to results of the analysis.
The UI of a disclosed example presents the results using at least one rendering of the plurality of renderings, the results including actionable insights corresponding to a portion of the media instance.
The actionable insights of a disclosed example correspond to emotional reactions of the plurality of viewers.
The analyzing of a disclosed example comprises applying expert knowledge of physiological behavior to the reaction data.
The system of a disclosed example comprises generating a first set of questions that represent the results.
The analyzing of a disclosed example includes analyzing the reaction data in the context of the first set of questions.
The system of a disclosed example comprises selecting at least one rendering of the plurality of renderings.
The system of a disclosed example comprises tagging the selected rendering with at least one question of the first set of questions.
A user of a disclosed example can modify presentation of the results via the UI by selecting at least one rendering of the plurality of renderings.
The presenting of a disclosed example includes presenting the results via presentation of the first set of questions on the UI.
The system of a disclosed example comprises, in response to the user selecting a question of the first set of questions, presenting via the UI an answer to the selected question that includes the actionable insight.
The reaction data of a disclosed example includes at least one of physiological responses, survey results, feedback generated by the viewers, metadata, and derived statistics.
The reaction data of a disclosed example includes physiological responses.
The reaction data of a disclosed example includes survey results.
The reaction data of a disclosed example includes feedback generated by the viewers.
The reaction data of a disclosed example includes metadata. The metadata of a disclosed example is event-based metadata.
The reaction data of a disclosed example includes derived statistics. The derived statistics of a disclosed example are derived statistics for indicators of success and failure of the media instance.
The system of a disclosed example comprises a plurality of sensor devices, wherein each viewer wears a sensor device of the plurality of sensor devices, wherein each sensor device receives the reaction data from a corresponding view and transmits the reaction data to at least one of the first module and the database.
The aggregating of a disclosed example comprises aggregating the reaction data according to at least one of maximums, minimums, averages, deviations, derivatives, amplitudes, and trends of at least one parameter of the reaction data.
The system of a disclosed example comprises a third module coupled to the second module, the third module receiving comments from the plurality of viewers in response to the viewing. The comments of a disclosed example are textual comments. The synchronized data of a disclosed example includes the comments.
The system of a disclosed example comprises a third module coupled to the second module, the third module presenting survey questions to the plurality of viewers via the UI, the survey questions relating to the media instance.
The third module of a disclosed example receives answers to the survey questions from the plurality of viewers via the UI. The answers to the survey questions of a disclosed example are textual comments. The synchronized data of a disclosed example includes the answers to the survey questions.
The plurality of viewers of a disclosed example is at a location.
The plurality of viewers of a disclosed example is at a plurality of locations.
A first set of the plurality of viewers of a disclosed example is at a first location and a second set of the plurality of viewers are at a second location different from the first location.
A first set of the plurality of viewers of a disclosed example is viewing the media instance at a first time and a second set of the plurality of viewers are viewing the media instance at a second time different from the first time.
The reaction data of a disclosed example corresponds to electrical activity in brain tissue of the user.
The reaction data of a disclosed example corresponds to electrical activity in muscle tissue of the user.
The reaction data of a disclosed example corresponds to electrical activity in heart tissue of the user.
Examples described herein include a system comprising: a processor coupled to a database, the database including a media instance and reaction data of a plurality of viewers, the reaction data generated in response to viewing of the media instance and including physiological response data; a first module that aggregates the reaction data from the plurality of viewers; and a second module that provides remote access to at least one of the reaction data and aggregated reaction data, wherein the remote access enables interactive analysis of at least one of the media instance, the reaction data, aggregated reaction data, and parsed reaction data.
Examples described herein include a system comprising: a processor coupled to a database, the database receiving a media instance and reaction data from a plurality of viewers, the reaction data generated in response to viewing of the media instance and including physiological response data; a first module aggregating the reaction data from the plurality of viewers; and a second module enabling remote interactive analysis and presentation of the media instance and at least one of the reaction data, aggregated reaction data, and parsed reaction data.
Examples described herein include a system comprising: a processor coupled to a database, the database receiving a media instance and reaction data from a plurality of viewers, the reaction data generated in response to viewing of the media instance and including physiological response data; and an interface coupled to the processor, the interface enabling remote interactive manipulation of the reaction data synchronized to corresponding events of the media instance, the manipulation including at least one of dividing, dissecting, aggregating, parsing, and analyzing the reaction data.
Examples described herein include a method comprising: receiving a media instance, the media instance including a plurality of media events; receiving reaction data from a plurality of viewers while the plurality of viewers are viewing the media instance; automatically analyzing the reaction data; and providing remote access to results of the analyzing, and presenting the results, the presenting including presenting actionable insights corresponding to a portion of the media instance via at least one of a plurality of renderings, wherein the actionable insights correspond to emotional reactions of the plurality of viewers.
The analyzing of a disclosed example includes applying expert knowledge of physiological behavior to the reaction data.
The method of a disclosed example comprises generating a first set of questions that represent the results.
The analyzing of a disclosed example includes analyzing the reaction data in the context of the first set of questions.
The method of a disclosed example comprises selecting at least one rendering of the plurality of renderings.
The method of a disclosed example comprises tagging the selected rendering with at least one question of the first set of questions.
A user of a disclosed example can modify the presenting of the results via the selecting of at least one rendering of the plurality of renderings.
The presenting of a disclosed example includes presenting the results via presentation of the first set of questions.
The method of a disclosed example comprises, in response to the user selecting a question of the first set of questions, presenting an answer to the selected question that includes the actionable insight.
The method of a disclosed example comprises selecting a second set of questions that represent the results, wherein the second set of questions were generated prior to the first set of questions to represent previous results from analysis of preceding reaction data of a preceding media instance, wherein the preceding reaction data is similar to the reaction data.
The analyzing of a disclosed example includes analyzing the reaction data in the context of the second set of questions.
The method of a disclosed example comprises selecting at least one rendering of the plurality of renderings.
The method of a disclosed example comprises tagging the selected rendering with at least one question of the second set of questions.
A user of a disclosed example can modify the presenting of the results via the selecting of at least one rendering of the plurality of renderings.
The presenting of a disclosed example includes presenting the results via presentation of the second set of questions.
The method of a disclosed example comprises, in response to the user selecting a question of the second set of questions, presenting an answer to the selected question that includes the actionable insight.
The method of a disclosed example comprises selecting a set of the reaction data to which the analyzing is applied, the selecting including selecting a portion of the media instance to which the set of the reaction data corresponds. The portion of a disclosed example includes a point in time. The portion of a disclosed example includes a period of time.
The method of a disclosed example comprises generating aggregated reaction data by aggregating the reaction data from the plurality of viewers.
The aggregating of a disclosed example comprises aggregating the reaction data according to at least one of maximums, minimums, averages, deviations, derivatives, amplitudes, and trends of at least one parameter of the reaction data.
The method of a disclosed example comprises generating synchronized data by synchronizing the plurality of media events of the media instance with the reaction data.
The method of a disclosed example comprises enabling remote interactive manipulation of the media instance.
The method of a disclosed example comprises enabling remote interactive manipulation of the reaction data.
The method of a disclosed example comprises enabling remote interactive manipulation of the plurality of renderings.
The method of a disclosed example comprises enabling remote interactive manipulation of the actionable insights.
The plurality of renderings of a disclosed example includes text, charts, graphs, histograms, images, and video.
The reaction data of a disclosed example includes at least one of physiological responses, survey results, feedback generated by the viewers, metadata, and derived statistics
The reaction data of a disclosed example includes physiological responses
The reaction data of a disclosed example includes survey results.
The reaction data of a disclosed example includes feedback generated by the viewers.
The reaction data of a disclosed example includes metadata, wherein the metadata is event-based metadata.
The reaction data of a disclosed example includes derived statistics, wherein the derived statistics are derived statistics for indicators of success and failure of the media instance.
Receiving the reaction data of a disclosed example comprises receiving the reaction data from a plurality of sensor devices via wireless couplings, wherein each viewer wears a sensor device of the plurality of sensor devices.
The reaction data of a disclosed example corresponds to electrical activity in brain tissue of the user.
The reaction data of a disclosed example corresponds to electrical activity in muscle tissue of the user.
The reaction data of a disclosed example corresponds to electrical activity in heart tissue of the user.
A first set of the plurality of viewers of a disclosed example is at a first location and a second set of the plurality of viewers is at a second location different from the first location
A first set of the plurality of viewers of a disclosed example is viewing the media instance at a first time and a second set of the plurality of viewers is viewing the media instance at a second time different from the first time.
Examples described herein include a method comprising: receiving a media instance; receiving reaction data from a plurality of viewers while the plurality of viewers are viewing the media instance; automatically analyzing the reaction data; and presenting the results by presenting actionable insights corresponding to a portion of the media instance via at least one of a plurality of renderings, wherein the actionable insights correspond to emotional reactions of the plurality of viewers.
Examples described herein include a method comprising: receiving a media instance; receiving reaction data from a plurality of viewers viewing the media instance; analyzing the reaction data; and presenting results of the analyzing by presenting a set of questions corresponding to a portion of the media instance, the set of questions corresponding to at least one of a plurality of renderings, wherein answers to questions of the set of questions present actionable insights of the reaction data, the actionable insights corresponding to emotional reactions of the plurality of viewers.
Examples described herein include a system comprising: a processor coupled to a database, the database including a media instance and reaction data, the media instance including a plurality of media events, the reaction data received from a plurality of viewers while the plurality of viewers are viewing the media instance; a first module coupled to the processor, the first module analyzing the reaction data; and a second module coupled to the processor, the second module comprising a plurality of renderings and a user interface (UI) that provide remote access to results of the analyzing and the results, the results including actionable insights corresponding to a portion of the media instance, wherein the actionable insights correspond to emotional reactions of the plurality of viewers.
The analyzing of a disclosed example includes applying expert knowledge of physiological behavior to the reaction data.
The first module of a disclosed example generates a first set of questions that represent the results.
The analyzing of a disclosed example includes analyzing the reaction data in the context of the first set of questions.
At least one of the second module and the UI of a disclosed example enables selection of at least one rendering of the plurality of renderings.
At least one of the second module and the UI of a disclosed example enables tagging of a selected rendering with at least one question of the first set of questions.
A user of a disclosed example can modify presentation of the results via the UI by selecting at least one rendering of the plurality of renderings.
At least one of the second module and the UI of a disclosed example presents the results via presentation of the first set of questions.
In response to receipt of a selected question of the first set of questions, the second module of a disclosed example presents an answer to the selected question that includes the actionable insight.
The first module of a disclosed example selects a second set of questions that represent the results, wherein the second set of questions were generated prior to the first set of questions to represent previous results from analysis of preceding reaction data of a preceding media instance, wherein the preceding reaction data is similar to the reaction data.
The analyzing of a disclosed example includes analyzing the reaction data in the context of the second set of questions.
The UI of a disclosed example enables selection of at least one rendering of the plurality of renderings.
The method of a disclosed example comprises tagging the selected rendering with at least one question of the second set of questions.
A user of a disclosed example can modify presentation of the results via the UI by the selecting of at least one rendering of the plurality of renderings.
At least one of the second module and the UI of a disclosed example presents the results via presentation of the second set of questions.
In response to the user selecting a question of the second set of questions, at least one of the second module and the UI of a disclosed example presents an answer to the selected question that includes the actionable insight.
The UI of a disclosed example enables selection of a set of the reaction data to which the analyzing is applied, the selecting including selecting a portion of the media instance to which the set of the reaction data corresponds. The portion of a disclosed example includes a point in time. The portion of a disclosed example includes a period of time.
The first module of a disclosed example generates aggregated reaction data by aggregating the reaction data from the plurality of viewers.
The aggregating of a disclosed example comprises aggregating the reaction data according to at least one of maximums, minimums, averages, deviations, derivatives, amplitudes, and trends of at least one parameter of the reaction data.
The method of a disclosed example comprises generating synchronized data by synchronizing the plurality of media events of the media instance with the reaction data.
The method of a disclosed example comprises enabling remote interactive manipulation of the media instance via the UI.
The method of a disclosed example comprises enabling remote interactive manipulation of the reaction data via the UI.
The method of a disclosed example comprises enabling remote interactive manipulation of the plurality of renderings via the UI.
The method of a disclosed example comprises enabling remote interactive manipulation of the actionable insights via the UI.
The plurality of renderings of a disclosed example includes text, charts, graphs, histograms, images, and video.
The reaction data of a disclosed example includes at least one of physiological responses, survey results, feedback generated by the viewers, metadata, and derived statistics.
The reaction data of a disclosed example includes physiological responses.
The reaction data of a disclosed example includes survey results.
The reaction data of a disclosed example includes feedback generated by the viewers.
The reaction data of a disclosed example includes metadata, wherein the metadata is event-based metadata.
The reaction data of a disclosed example includes derived statistics, wherein the derived statistics are derived statistics for indicators of success and failure of the media instance.
The method of a disclosed example comprises a plurality of sensor devices, wherein each viewer wears a sensor device of the plurality of sensor devices, wherein each sensor device receives the reaction data from a corresponding view and transmits the reaction data to at least one of the first module and the database.
The reaction data of a disclosed example corresponds to electrical activity in brain tissue of the user.
The reaction data of a disclosed example corresponds to electrical activity in muscle tissue of the user.
The reaction data of a disclosed example corresponds to electrical activity in heart tissue of the user.
A first set of the plurality of viewers of a disclosed example is at a first location and a second set of the plurality of viewers of a disclosed example is at a second location different from the first location.
A first set of the plurality of viewers of a disclosed example is viewing the media instance at a first time and a second set of the plurality of viewers is viewing the media instance at a second time different from the first time.
Examples described herein include a system comprising: a processor coupled to a database, the database receiving a media instance and reaction data from a plurality of viewers while the plurality of viewers are viewing the media instance; a first module coupled to the processor, the first module automatically analyzing the reaction data; and a second module coupled to the processor, the second module presenting the results by presenting actionable insights corresponding to a portion of the media instance via at least one of a plurality of renderings, wherein the actionable insights correspond to emotional reactions of the plurality of viewers.
Examples described herein include a system comprising: a processor coupled to a database, the database receiving a media instance and reaction data from a plurality of viewers viewing the media instance; a first module coupled to the processor, the first module analyzing the reaction data; and a second module coupled to the processor, the second module presenting results of the analyzing by presenting a set of questions corresponding to a portion of the media instance, the set of questions corresponding to at least one of a plurality of renderings, wherein answers to questions of the set of questions present actionable insights of the reaction data, the actionable insights corresponding to emotional reactions of the plurality of viewers.
Examples described herein may be implemented using a conventional general purpose or a specialized digital computer or microprocessor(s) programmed according to the teachings of the present disclosure, as will be apparent to those skilled in the computer art Appropriate software coding can readily be prepared by skilled programmers based on the teachings of the present disclosure, as will be apparent to those skilled in the software art. The teachings of this disclosure may also be implemented by the preparation of integrated circuits or by interconnecting an appropriate network of conventional component circuits, as will be readily apparent to those skilled in the art.
A disclosed example includes a computer program product which is a machine readable medium (media) having instructions stored thereon/in which can be used to program one or more computing devices to perform any of the features presented herein. The machine readable medium can include, but is not limited to, one or more types of disks including floppy disks, optical discs, DVD, CD-ROMs, micro drive, and magneto-optical disks, ROMs, RAMs, EPROMs, EEPROMs, DRAMs, VRAMs, flash memory devices, magnetic or optical cards, nanosystems (including molecular memory ICs), or any type of media or device suitable for storing instructions and/or data. Stored on any one of the computer readable medium (media), the teachings of the present disclosure include software for controlling both the hardware of the general purpose/specialized computer or microprocessor, and for enabling the computer or microprocessor to interact with a human viewer or other mechanism utilizing the results of the teachings of this disclosure. Such software may include, but is not limited to, device drivers, operating systems, execution environments/containers, and applications.
The examples described herein include and/or run under and/or in association with a processing system. The processing system includes any collection of processor-based devices or computing devices operating together, or components of processing systems or devices, as is known in the art. For example, the processing system can include one or more of a portable computer, portable communication device operating in a communication network, and/or a network server. The portable computer can be any of a number and/or combination of devices selected from among personal computers, cellular telephones, personal digital assistants, portable computing devices, and portable communication devices, but is not so limited. The processing system can include components within a larger computer system.
The processing system of a disclosed example includes at least one processor and at least one memory device or subsystem. The processing system can also include or be coupled to at least one database. The term “processor” as generally used herein refers to any logic processing unit, such as one or more central processing units (CPUs), digital signal processors (DSPs), application-specific integrated circuits (ASIC), etc. The processor and memory can be monolithically integrated onto a single chip, distributed among a number of chips or components of the systems described herein, and/or provided by some combination of algorithms. The methods described herein can be implemented in one or more of software algorithm(s), programs, firmware, hardware, components, circuitry, in any combination.
The components described herein can be located together or in separate locations. Communication paths couple the components and include any medium for communicating or transferring files among the components. The communication paths include wireless connections, wired connections, and hybrid wireless/wired connections. The communication paths also include couplings or connections to networks including local area networks (LANs), metropolitan area networks (MANs), wide area networks (WANs), proprietary networks, interoffice or backend networks, and the Internet. Furthermore, the communication paths include removable fixed mediums like floppy disks, hard disk drives, and CD-ROM disks, as well as flash RAM, Universal Serial Bus (USB) connections, RS-232 connections, telephone lines, buses, and electronic mail messages.
Aspects of the systems and methods described herein may be implemented as functionality programmed into any of a variety of circuitry, including programmable logic devices (PLDs), such as field programmable gate arrays (FPGAs), programmable array logic (PAL) devices, electrically programmable logic and memory devices and standard cell-based devices, as well as application specific integrated circuits (ASICs). Some other possibilities for implementing aspects of the systems and methods include: microcontrollers with memory (such as electronically erasable programmable read only memory (EEPROM)), embedded microprocessors, firmware, software, etc. Furthermore, aspects of the systems and methods may be embodied in microprocessors having software-based circuit emulation, discrete logic (sequential and combinatorial), custom devices, fuzzy (neural) logic, quantum devices, and hybrids of any of the above device types. Of course the underlying device technologies may be provided in a variety of component types, e.g., metal-oxide semiconductor field-effect transistor (MOSFET) technologies like complementary metal-oxide semiconductor (CMOS), bipolar technologies like emitter-coupled logic (ECL), polymer technologies (e.g., silicon-conjugated polymer and metal-conjugated polymer-metal structures), mixed analog and digital, etc.
It should be noted that any system, method, and/or other components disclosed herein may be described using computer aided design tools and expressed (or represented), as data and/or instructions embodied in various computer-readable media, in terms of their behavioral, register transfer, logic component, transistor, layout geometries, and/or other characteristics. Computer-readable media in which such formatted data and/or instructions may be embodied include, but are not limited to, non-volatile storage media in various forms (e.g., optical, magnetic or semiconductor storage media) and carrier waves that may be used to transfer such formatted data and/or instructions through wireless, optical, or wired signaling media or any combination thereof. Examples of transfers of such formatted data and/or instructions by carrier waves include, but are not limited to, transfers (uploads, downloads, e-mail, etc.) over the Internet and/or other computer networks via one or more data transfer protocols (e.g., HTTP, HTTPs, FTP, SMTP, WAP, etc.). When received within a computer system via one or more computer-readable media, such data and/or instruction-based expressions of the above described components may be processed by a processing entity (e.g., one or more processors) within the computer system in conjunction with execution of one or more other computer programs.
Unless the context clearly requires otherwise, throughout the description and the claims, the words “comprise,” “comprising,” and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in a sense of “including, but not limited to.” Words using the singular or plural number also include the plural or singular number respectively. Additionally, the words “herein,” “hereunder,” “above,” “below,” and words of similar import, when used in this application, refer to this application as a whole and not to any particular portions of this application. When the word “or” is used in reference to a list of two or more items, that word covers all of the following interpretations of the word: any of the items in the list, all of the items in the list and any combination of the items in the list.
The above description of example systems and methods is not intended to be exhaustive or to limit the systems and methods to the precise forms disclosed. While specific examples of, and examples for, the systems and methods are described herein for illustrative purposes, various equivalent modifications are possible within the scope of the systems and methods, as those skilled in the relevant art will recognize. The teachings of the systems and methods provided herein can be applied to other systems and methods, not only for the systems and methods described above.
The elements and acts of the various examples described above can be combined to provide other examples. These and other changes can be made to the systems and methods in light of the above detailed description.
In general, in the following claims, the terms used should not be construed to limit the claims to the specific examples disclosed in the specification and the claims, but should be construed to include all systems and methods under the claims. Accordingly, the examples are not limited by the disclosure, but instead the scope of the examples is to be determined entirely by the claims.
While certain aspects of the examples are presented below in certain claim forms, the inventors contemplate the various aspects of the examples in any number of claim forms. Accordingly, the inventors reserve the right to add additional claims after filing the application to pursue such additional claim forms for other aspects disclosed in the various examples.
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Example systems, methods and machine readable media are disclosed. An example system includes a synchronizer to determine a total amount to offset first-neuro-response data gathered from a subject exposed to media to align the first neuro-response data with second neuro-response data simultaneously gathered from the subject. The first neuro-response data is associated with a first sensory component of the media and the second neuro-response data is associated with a second sensory component of the media. The total amount to offset is based on a first cognitive delay associated with the first neuro-response data and a second cognitive delay associated with the second neuro-response data. The synchronizer is to time shift at least one of the first neuro-response data or the second neuro-response based on the total amount to form aligned data. The example system includes an analyzer to determine an effectiveness of the media based on the aligned data.
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This application is a continuation-in-part of U.S. patent application Ser. No. 08/758,489 filed Nov. 29, 1996, now U.S. Pat. No. 5,800,679.
FIELD OF THE INVENTION
The present invention relates to a method for cleaning a web, such as a textile web and a paper or board web, in which a blowing is directed at the web to separate dust and other contaminants from the web, and a suction effect is applied to the web for removing the dust and contaminants that are separated out of connection with the web.
BACKGROUND OF THE INVENTION
In material web forming and handling devices such as paper machines, a boundary layer of air is formed at both sides of the paper web, which usually moves at quite a high speed, as well as at both sides of a textile web or drying wire which is used to carry the paper web. Each boundary layer of air carries along with it dust that has been separated from the fibre mesh of the web and from the fillers in the web. The dust spreads into the environment surrounding the textile machine, paper machine or other device and is partly also carried to the web reel. Moreover, after the manufacture of the paper, dust and contaminants, such as debris and fibers, adhere to the face of the web.
In a paper machine, one important and significant source of dust is the slitting process, in which an abundance of dust is separated from the web when the web is slit into component webs or reels in the longitudinal direction. Problems related to the production and presence of dust also occur in the manufacture of tissue paper, in particular in connection with creping by means of a doctor, wherein the paper web is separated by means of a doctor blade from a face of a steam-heated yankee cylinder, in which connection a particularly large quantity of dust is detached from the web, which dust is drawn along by the paper web and spreads into the surrounding environment. Dust and contaminants cause problems in the further processing of the paper, for example in printing operations, because it is of vital importance from the point of view of the quality of printing that the printing rolls remain clean. Also, dust spreads both in the paper mill and in further processing of the web into the environment, and dust may result in risks for occupational health because it may contain various particles of fillers.
With respect to the prior art, reference is made to the U.S. Pat. No. 3,239,863, which describes a web cleaning device including a chamber space in which two air nozzles have been formed directed at the web. The space between the nozzles is closed so that it forms an exhaust chamber for the air coming out of the nozzles and for the dust separated from the web. In this prior art arrangement, one of the more noticeable problems is how to produce a sufficiently high air blow rate to separate the dust adhering to the web as well as the requirement to construct the device so that it is placed quite far at a distance from the web, in which case it is mainly suitable for general removal of dust, but not for detaching dust or contaminants from the web.
One prior art construction for the problems described above is described in the current assignee's Finnish Patent No. 95,611 (Finnish Patent Application No. 942269) which describes dust removing method and apparatus in which it has been considered novel that the web is subjected to a high-pressure blowing so as to separate the dust from the web and in the running direction of the web, before and after the high-pressure blowing, dust and other particles that has been separated from the web are absorbed.
OBJECTS AND SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide new and improved methods for cleaning a paper or board web and a textile web such as an air-permeable wire.
It is another object of the present invention to further develop the construction of Finnish Patent No. 95,611 so that a more efficient and simpler solution is obtained, whose cost of manufacture is also lower and which is also suitable for cleaning a web from both sides across the entire width of the web.
It is a further object of the invention to provide a construction in which there are no problems of runnability, for example, arising from the vacuum necessary for sucking the dust, and by whose means it is possible to prevent access of dust as leakage flow back onto the web and into the environment.
It is another object of the invention to provide a new and improved method and device for removing dust and other undesirable contaminants from a material web as the web is running in a paper machine or other equivalent material web forming or handling device.
In view of achieving the objects stated above and others, in the method in accordance with the invention, a vortex flow is produced before a dust separating blowing is directed at the web in the running direction thereof so as to prevent carriage of the dust into the environment and to compensate for the suction effect. The vortex flow may be produced by coordinating the joint effect of the blowing direction of the dust separating blowing, the shape of a face of a dust removing device facing the web, and an air flow traveling along with the web. If an additional blowing is directed in association with a face of a dust removing device facing the web, the vortex flow may be generated by coordinating the joint effect of the blowing direction of the dust separating blowing, the shape of the face of the dust removing device facing the web, an air flow traveling along with the web and the blowing direction of the additional blowing.
For the purposes herein, the term "web" encompasses a paper or board web formed in a paper or board machine, as well as a textile web, such as an air-permeable drying wire which is used in a paper or board machine to carry the paper or board web.
In another embodiment of the method for cleaning a web in accordance with the invention, a first dust separating blowing is directed at a first side of the web to separate dust and other undesirable particles therefrom, suction is applied to the first side of the web to remove the dust and particles separated from the web proximate to and before the first dust separating blowing, and a vortex flow is generated on the first side of the web at a location before the first dust separating blowing is directed at the first side of the web in a running direction of the web. In this manner, the carrying of the dust and particles along with the web into a surrounding environment is reduced and the effect of the suction on the runnability of the web is compensated for. The vortex flow may be generated by coordinating the joint effect of the blowing direction of the first dust separating blowing, the shape of a face of a frame of a dust removing device facing the web, and an air flow traveling along with the web. An additional blowing may be directed along a face of the frame of the dust removing device facing the web, in which case, the joint effect of the blowing direction of the first dust separating blowing, the shape of the face of the frame facing the web, an air flow traveling along with the web and the blowing direction of the additional blowing are coordinated to generate the vortex flow.
In some embodiments, a second dust separating blowing is directed at a second side of the web opposite the first side of the web to separate dust and other particles from the web, suction is applied to the second side of the web to remove the dust separated from the web, and a vortex flow is generated on the second side of the web at a location after the second dust separating blowing is directed at the second side of the web in a running direction of the web. In one particularly advantageous embodiment, the first dust separating blowing is directed at the first side of the web at a location in opposed relationship to a location at which suction is applied to the second side of the web and the second dust separating blowing is directed at the second side of the web at a location in opposed relationship to a location at which suction is applied to the first side of the web. The dust separation blowings may be heated to thereby heat and dry the web.
In yet another embodiment of the method, the generation of a vortex flow is not required. Rather, a dust separating blowing is directed at each side of the web and suction is applied at a location in opposed relationship to each location at which a dust separating blowing is directed at the web. In other words, a first dust separating blowing is directed at the first side of the web and suction is applied to the second side of the web at a location in opposed relationship to the location at which the first dust separating blowing is directed at the web. Also, a second dust separating blowing is directed at the second side of the web and suction is applied to the first side of the web at a location in opposed relationship to a location at which the second dust separating blowing is directed at the web. Such an embodiment is most effective for an air-permeable textile web such as a drying wire. Also, it is advantageous if the force of the first and second dust separating blowings are regulated such that dust is separated from both the first and second sides of the web by the effect of each of the first and second dust separating blowings. Nevertheless, a vortex flow may be generated on the first side of the web at a location before the first dust separating blowing is directed at the first side of the web and after the suction is applied to the first side of the web.
The device in accordance with the invention comprises an arrangement for producing a vortex flow before a blow device for generating a dust separation blowing in the running direction of the web so as to prevent carriage of the dust into the environment, i.e., along with the web through the terminal end of the device, and to compensate for the suction effect, i.e., the detrimental effect of the suction on the runnability of the web.
In the arrangement in accordance with the invention, the face of the blow device that is placed facing the web is shaped so that part of the cleaning jet is turned back towards the nozzle slot, in which case, by means of the vortex formed, it is possible to control the vacuum in the space and thereby to avoid problems of runnability caused by an excessively high vacuum. Also in the arrangement in accordance with the invention, the suction chamber is shaped and dimensioned so that the high-speed cleaning jet has enough time and space to be turned into the exhaust air duct, whereby access of dust as a leakage flow back onto the web and into the environment are precluded. The arrangement in accordance with the invention is suitable for cleaning the web from both sides and moreover, if necessary, in particular when a web wider than normal is being run through the machine. With a view toward cleaning the web edges by means of the dust removing device, the ends of the device can be provided with side blow nozzles. In the arrangement in accordance with the invention, the exhaust air duct is preferably shaped so that an intensive vortex is formed in the duct, whereby the duct remains clean and moreover, the bottom of the pressure chamber is shaped so that, with an adequate flushing velocity, adhering of dust to the faces in the device is substantially prevented.
In the arrangement in accordance with the invention, the blow nozzle slot is designed so that the slot is adjustable, in which case the intensity of the dust separation blowing can be regulated readily.
The dust removing device in accordance with the invention can also be arranged to be inclinable in the running direction of the web in compliance with the angle of arrival of the web into connection with the blow device and with the paper grade (grade of the web) that is run, so as to obtain an optimal cleaning result.
The device in accordance with the invention extends preferably across the entire width of the machine and, if necessary, for example when placed at spreader rolls after a slitter, it can be bent to the desired form, for example to the form of deflected rolls, and the bending can be controlled, for example, by means of measurement of distance from the web face.
In the following, the invention will be described in more detail with reference to the figures in the accompanying drawing. The invention is, however, by no means strictly confined to the details of the illustrated embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
The following drawings are illustrative of embodiments of the invention and are not meant to limit the scope of the invention as encompassed by the claims.
FIG. 1 is a schematic vertical sectional view in the machine direction of a device in accordance with the invention and which can be used in a method in accordance with the invention.
FIG. 2 is a schematic illustration of a device in accordance with the invention in the direction of width of the web and which can be used in a method in accordance with the invention.
FIG. 3 is a schematic illustration of an arrangement of the device in accordance with the invention at both sides of the web and which can be used in a method in accordance with the invention.
FIG. 4 is a schematic illustration of a further exemplifying embodiment of the face of the suction chamber in a device in accordance with the invention and which can be used in a method in accordance with the invention.
FIG. 5 shows a second further exemplifying embodiment of the face of the suction chamber in a device in accordance with the invention and which can be used in a method in accordance with the invention.
FIG. 6 is a schematic illustration of another arrangement of the device in accordance with the invention at both sides of the web and which can be used in a method in accordance with the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the accompanying drawings wherein the same reference numerals refer to the same or similar elements, in the exemplifying embodiment shown in FIG. 1, air or another equivalent flow medium is passed into a dust removing device designated generally at 10 along an intake air duct 11. From the intake air duct 11, the air is passed into a blow-air chamber 13 defined in a frame 10A, and from the air-blow chamber 13, the air is passed through a nozzle opening 20 as a high-pressure air jet P directed toward a web W running past the device 10. Reference character "W" thus designates any web, paper, board or textile, which needs to be cleaned (which cleaning encompasses the removal of dust and other particles). The running direction of the web W is denoted by reference arrow S, and the air flow traveling along with the web is denoted by reference arrow P 1 . The frame 10A of the dust removing device 10 also includes an exhaust air chamber denoted by reference numeral 14, and a vortex chamber 16 is shaped within the exhaust air chamber 14 and produces an intensive vortex therein to keep the exhaust air chamber 14 clean. From the exhaust air chamber 14, the air is passed into an exhaust air duct 15 fluidly coupled thereto.
With respect to the positioning of the duct removing device 10, the dust removing device 10 is placed near the web W so that a space 25 is formed between the surface of the dust removing device 10 facing the web W and the web W. In this space 25, a vortex air flow P 2 is formed by the joint effect of the dust separation blowing P at a bottom face 17 of the device and the air flow P 1 carried along with the web W, and by means of the vortex P 2 , the access of dust as a leakage flow back along with the web W, and thus into the surrounding environment, is prevented. The vortex P 2 is formed by means of the dust separation blowing P, by means of the air flow P 1 traveling along with the web W, by means of the shape of the face 17 of the suction chamber 14 of the dust removing device 10 placed facing the web W, and by means of the dimensioning of the vortex space 25, for example, by regulating the distance of the device 10 from the web W. The generation of the vortex P 2 is dispensable in certain embodiments, such as when a dust separating blowing and suction are provided on an opposite side of the web as discussed below.
Dust is separated from the web when a sharp air jet, a dust separation blow P, is blown out of the nozzle opening 20, which jet penetrates through the boundary layer and separates the particles of dust from the web face. The separated dust is removed into the suction chamber 14 by a suction effect generated proximate to and before the nozzle opening 20, and the air that contains dust particles is then passed to a cleaning stage, for example, in a wet separator.
The blow pressure of the dust separation blowing may be regulated to be from about 2 kPa to about 50 kPa, preferably from about 15 kPa to about 35 kPa, for example, when the dust removing device in accordance with the invention is used for removing dust from printing papers/boards. The blow velocity to be used in the dust separation blowing P may be regulated or controlled to be from about 50 meters per second to about 400 meters per second, preferably from about 50 meters per second to about 300 meters per second. Of course, the values to be used for the blow pressure and velocity may be outside of these ranges and depend on the strength of the web that is being run, i.e., on the intensity of blowing that the web can endure and on the intensity of blowing that is necessary to separate the dust from the web face. It has been recognized that when softer paper grades are being run, lower values are used. The vacuum in the suction chamber 14 should be from about 0.5 kPa to about 6 kPa, preferably from about 1 kPa to about 3 kPa, but, of course, the values of vacuum to be used in the suction chamber also depend on the paper grade that is being run and may be outside of these ranges in certain situations. The distance of the blow device from the web face should be from about 1 mm to about 40 mm, preferably from about 2 mm to about 10 mm.
In certain embodiments, the nozzle opening 20 is adjustable so that the intensity and the direction of 11 the dust separation blowing P can be regulated by adjusting the nozzle opening 20. If necessary, the dust removing device 10 can also be inclined by appropriate pivot means, the movement being represented schematically by the arrow R, in compliance with or as a function of the angle of arrival of the web W, and if it is paper or board web, with the grade of the web W that is being run, so that an optimal cleaning result is obtained.
As shown in FIG. 2, the dust removing device 10 extends substantially across the entire width of the web W, and, if necessary, it can be bent to the desired deflected shape, for example, of the spreader rolls after a slitter, i.e., in correspondence with the curvature of the web. The bending can be controlled, for example, by means of measurements of distance E' from the web W face and the positioning of regulation members 40 which are controlled based on the measurement results and based on control signals from a control unit 50 so that the dust removing device 10 is bent to the desired shape. For cleaning of the edges of the web W, it is possible to provide the ends of the dust removing device 10 with side blow nozzles, out of which the blowing PS is blown. This arrangement is particularly advantageous when a web W wider than normal is run.
In the exemplifying embodiment shown in FIG. 1, the vortex P 2 has been produced so that the face 17 of the dust removing device 10 that is placed facing the web and that starts from the suction chamber 14 has, in the direction of arrival of the web W, first been formed as convex towards the web W, after which there follows a linear portion, which ends in the nozzle opening 20. The vortex P 2 can be intensified by also shaping a guide face 18 of the dust removing device 10 that defines an inlet opening 21 of the air flow P 1 arriving along with the web W, for example, curved, as shown in FIG. 1. The guide face 18 can also be shaped in some other way, compare, for example, FIGS. 4 and 5. In the illustrated embodiments, on the whole, the air flows passing in the dust removing device 10 are denoted by arrows.
FIG. 3 is a schematic illustration of an exemplifying embodiment in which dust removing devices 10 as described above are placed at both sides of the web W. This arrangement is constructed preferably so that the nozzle openings 20 of the dust removing devices 10 are placed facing one another, in which case the vortex spaces 25, in which the vortex flow P 2 is produced by the effect of the lower face 17 of the device 10, of the dust separation blowing P, and of the air flow P 2 , are placed substantially one opposite to the other.
FIG. 4 shows an exemplifying embodiment of the shape of the lower face 17 of the air chamber 13 in the dust removing device 10 so as to produce a vortex P 2 in the space 25. In this exemplifying embodiment, the lower face 17 has been shaped concave in relation to the web W face from the suction chamber 14 to the nozzle opening 20. The guide face 18 that defines the inlet opening 21 for the air flow P 1 is bent so that it is substantially L-shaped in relation to the running direction of the web W.
FIG. 5 shows a second exemplifying embodiment for producing a vortex air flow P 2 in the space 25, and in this exemplifying embodiment the vortex flow P 2 is produced, besides by means of the dust separation blowing P, the air flow P 1 traveling along with the web W, and the shape of the lower face 17, also by means of a blowing P 3 through a nozzle opening 27 formed in the lower face 17. Blowing P 3 is directed in a direction parallel to the lower face 17 and generally in the running direction S of the web and thus has a directional component substantially contrary to the direction of the dust separation blowing P. In this exemplifying embodiment, the lower face 17 is substantially linear, and the guide face 18 is curved but bent towards the direction of arrival S of the web W.
The scope of the invention, of course, also includes embodiments in which the embodiments are connected with guide faces 18 and/or lower faces 17 of different types and shapes.
FIG. 6 is a schematic illustration of an exemplifying embodiment in which dust removing devices 10 as described above are placed at both sides of the web W. Differing from the embodiment in FIG. 3, the lower dust removing device, designated 10A, has been turned 180° about a vertical axis so that the suction chamber 14 above the web W is situated in opposed relationship to a location at which the dust separating blowing PA is operative against the web. Similarly, the suction chamber 14 below the web W is situated in opposed relationship to a location at which the dust separating blowing P is operative against the web. In this manner, there is a partial vacuum at one side of the web and a blowing at the same point on the opposite side of the web, i.e., a positive pressure is arranged to affect the web W at the point where suction is prevailing thereby enhancing the removal of dust and other undesirable particles from the web W. This arrangement is particularly advantageous when a textile web such as a drying wire is being cleaned, i.e., dust and other particles are being removed therefrom. The blowings P,PA clean the web W on both sides because a portion of the blowings pass through the web W while the suction prevailing at the opposed side of the web W enables the separated materials to be effectively collected. The blowings P,PA may also be heated so that the web W is heated and dried.
In this embodiment, a vortex may not be generated on either side of the web. Rather, there is sufficient dust separation and removal resulting from the two dust separating blowings P,PA and the application on suction on an opposite side of the web in opposed relationship to each dust separating blowing P,PA.
The examples provided above are not meant to be exclusive. Many other variations of the present invention would be obvious to those skilled in the art, and are contemplated to be within the scope of the appended claims. For example, a vortex flow can be produced in a number of different ways besides the exemplifying embodiments illustrated in the figures.
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A method for cleaning a web by removing dust and other particles therefrom in which a blowing is directed at a web to cause the separation of dust from the web and a suction effect is applied to the web to remove the dust separated from the web. A vortex flow may be produced before the dust separating blowing in the running direction of the web to prevent carriage of the dust into the environment and to compensate for the suction effect on the runnability of the web.
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BACKGROUND OF THE INVENTION
[0001] It is highly desirable for tires to exhibit good traction characteristics on both dry and wet surfaces. However, it has traditionally been very difficult to improve the traction characteristics of a tire without compromising its rolling resistance and tread wear. Low rolling resistance is important because good fuel economy is virtually always an important consideration. Good tread wear is also an important consideration because it is generally the most important factor that determines the life of the tire.
[0002] The traction, tread wear, and rolling resistance of a tire is dependent to a large extent on the dynamic viscoelastic properties of the elastomers utilized in making the tire tread. In order to reduce the rolling resistance of a tire, rubbers having a high rebound have traditionally been utilized in making the tire's tread. On the other hand, in order to increase the wet skid resistance of a tire, rubbers that undergo a large energy loss have generally been utilized in the tire's tread. In order to balance these two viscoelastically inconsistent properties, mixtures of various types of synthetic and natural rubber are normally utilized in tire treads. For instance various mixtures of styrene-butadiene rubber and polybutadiene rubber are commonly used as a rubber material for automobile tire treads. However, such blends are not totally satisfactory for all purposes.
[0003] The inclusion of styrene-butadiene rubber (SBR) in tire tread formulations can significantly improve the traction characteristics of tires made therewith. However, styrene is a relatively expensive monomer and the inclusion of SBR is tire tread formulations leads to increased costs.
[0004] Carbon black is generally included in rubber compositions which are employed in making tires and most other rubber articles. It is desirable to attain the best possible dispersion of the carbon black throughout the rubber to attain optimized properties. It is also highly desirable to improve the interaction between the carbon black and the rubber. By improving the affinity of the rubber compound to the carbon black, physical properties can be improved. Silica can also be included in tire tread formulations to improve rolling resistance.
[0005] U.S. Pat. No. 4,843,120 discloses that tires having improved performance characteristics can be prepared by utilizing rubbery polymers having multiple glass transition temperatures as the tread rubber. These rubbery polymers having multiple glass transition temperatures exhibit a first glass transition temperature which is within the range of about −110° C. to −20° C. and exhibit a second glass transition temperature which is within the range of about −50° C. to 0° C. According to U.S. Pat. No. 4,843,120, these polymers are made by polymerizing at least one conjugated diolefin monomer in a first reaction zone at a temperature and under conditions sufficient to produce a first polymeric segment having a glass transition temperature which is between −110° C. and −20° C. and subsequently continuing said polymerization in a second reaction zone at a temperature and under conditions sufficient to produce a second polymeric segment having a glass transition temperature which is between −20° C. and 20° C. Such polymerizations are normally catalyzed with an organolithium catalyst and are normally carried out in an inert organic solvent.
[0006] U.S. Pat. No. 5,137,998 discloses a process for preparing a rubbery terpolymer of styrene, isoprene, and butadiene having multiple glass transition temperatures and having an excellent combination of properties for use in making tire treads which comprises: terpolymerizing styrene, isoprene and 1,3-butadiene in an organic solvent at a temperature of no more than about 40° C. in the presence of (a) at least one member selected from the group consisting of tripiperidino phosphine oxide and alkali metal alkoxides and (b) an organolithium compound.
[0007] U.S. Pat. No. 5,047,483 discloses a pneumatic tire having an outer circumferential tread where said tread is a sulfur cured rubber composition comprised of, based on 100 parts by weight rubber (phr), (A) about 10 to about 90 parts by weight of a styrene, isoprene, butadiene terpolymer rubber (SIBR), and (B) about 70 to about 30 weight percent of at least one of cis 1,4-polyisoprene rubber and cis 1,4-polybutadiene rubber wherein said SIBR rubber is comprised of (1) about 10 to about 35 weight percent bound styrene, (2) about 30 to about 50 weight percent bound isoprene and (3) about 30 to about 40 weight percent bound butadiene and is characterized by having a single glass transition temperature (Tg) which is in the range of about −10° C. to about −40° C. and, further the said bound butadiene structure contains about 30 to about 40 percent 1,2-vinyl units, the said bound isoprene structure contains about 10 to about 30 percent 3,4-units, and the sum of the percent 1,2-vinyl units of the bound butadiene and the percent 3,4-units of the bound isoprene is in the range of about 40 to about 70 percent.
[0008] U.S. Pat. No. 5,272,220 discloses a styrene-isoprene-butadiene rubber which is particularly valuable for use in making truck tire treads which exhibit improved rolling resistance and tread wear characteristics, said rubber being comprised of repeat units which are derived from about 5 weight percent to about 20 weight percent styrene, from about 7 weight percent to about 35 weight percent isoprene, and from about 55 weight percent to about 88 weight percent 1,3-butadiene, wherein the repeat units derived from styrene, isoprene and 1,3-butadiene are in essentially random order, wherein from about 25% to about 40% of the repeat units derived from the 1,3-butadiene are of the cis-microstructure, wherein from about 40% to about 60% of the repeat units derived from the 1,3-butadiene are of the trans-microstructure, wherein from about 5% to about 25% of the repeat units derived from the 1,3-butadiene are of the vinyl-microstructure, wherein from about 75% to about 90% of the repeat units derived from the isoprene are of the 1,4-microstructure, wherein from about 10% to about 25% of the repeat units derived from the isoprene are of the 3,4-microstructure, wherein the rubber has a glass transition temperature which is within the range of about −90° C. to about −70° C., wherein the rubber has a number average molecular weight which is within the range of about 150,000 to about 400,000, wherein the rubber has a weight average molecular weight of about 300,000 to about 800,000, and wherein the rubber has an inhomogeneity which is within the range of about 0.5 to about 1.5.
[0009] U.S. Pat. No. 5,239,009 reveals a process for preparing a rubbery polymer which comprises: (a) polymerizing a conjugated diene monomer with a lithium initiator in the substantial absence of polar modifiers at a temperature which is within the range of about 5° C. to about 100° C. to produce a living polydiene segment having a number average molecular weight which is within the range of about 25,000 to about 350,000; and (b) utilizing the living polydiene segment to initiate the terpolymerization of 1,3-butadiene, isoprene, and styrene, wherein the terpolymerization is conducted in the presence of at least one polar modifier at a temperature which is within the range of about 5° C. to about 70° C. to produce a final segment which is comprised of repeat units which are derived from 1,3-butadiene, isoprene, and styrene, wherein the final segment has a number average molecular weight which is within the range of about 25,000 to about 350,000. The rubbery polymer made by this process is reported to be useful for improving the wet skid resistance and traction characteristics of tires without sacrificing tread wear or rolling resistance.
[0010] U.S. Pat. No. 5,061,765 discloses isoprene-butadiene copolymers having high vinyl contents which can reportedly be employed in building tires which have improved traction, rolling resistance, and abrasion resistance. These high vinyl isoprene-butadiene rubbers are synthesized by copolymerizing 1,3-butadiene monomer and isoprene monomer in an organic solvent at a temperature which is within the range of about −10° C. to about 100° C. in the presence of a catalyst system which is comprised of (a) an organoiron compound, (b) an organoaluminum compound, (c) a chelating aromatic amine, and (d) a protonic compound; wherein the molar ratio of the chelating amine to the organoiron compound is within the range of about 0.1:1 to about 1:1, wherein the molar ratio of the organoaluminum compound to the organoiron compound is within the range of about 5:1 to about 200:1, and herein the molar ratio of the protonic compound to the organoaluminum compound is within the range of about 0.001:1 to about 0.2: 1.
[0011] U.S. Pat. No. 5,405,927 discloses an isoprene-butadiene rubber which is particularly valuable for use in making truck tire treads, said rubber being comprised of repeat units which are derived from about 20 weight percent to about 50 weight percent isoprene and from about 50 weight percent to about 80 weight percent 1,3-butadiene, wherein the repeat units derived from isoprene and 1,3-butadiene are in essentially random order, wherein from about 3% to about 10% of the repeat units in said rubber are 1,2-polybutadiene units, wherein from about 50% to about 70% of the repeat units in said rubber are 1,4-polybutadiene units, wherein from about 1% to about 4% of the repeat units in said rubber are 3,4-polyisoprene units, wherein from about 25% to about 40% of the repeat units in the polymer are 1,4-polyisoprene units, wherein the rubber has a glass transition temperature which is within the range of about −90° C. to about −75° C., and wherein the rubber has a Mooney viscosity which is within the range of about 55 to about 140.
[0012] U.S. Pat. No. 5,654,384 discloses a process for preparing high vinyl polybutadiene rubber which comprises polymerizing 1,3-butadiene monomer with a lithium initiator at a temperature which is within the range of about 5° C. to about 100° C. in the presence of a sodium alkoxide and a polar modifier, wherein the molar ratio of the sodium alkoxide to the polar modifier is within the range of about 0.1:1 to about 10:1; and wherein the molar ratio of the sodium alkoxide to the lithium initiator is within the range of about 0.05:1 to about 10:1. By utilizing a combination of sodium alkoxide and a conventional polar modifier, such as an amine or an ether, the rate of polymerization initiated with organolithium compounds can be greatly increased with the glass transition temperature of the polymer produced also being substantially increased. The rubbers synthesized using such catalyst systems also exhibit excellent traction properties when compounded into tire tread formulations. This is attributable to the unique macrostructure (random branching) of the rubbers made with such catalyst systems.
[0013] U.S. Pat. No. 5,620,939, U.S. Pat. No. 5,627,237, and U. S. Pat. No. 5,677,402 also disclose the use of sodium salts of saturated aliphatic alcohols as modifiers for lithium initiated solution polymerizations. Sodium t-amylate is a preferred sodium alkoxide by virtue of its exceptional solubility in non-polar aliphatic hydrocarbon solvents, such as hexane, which are employed as the medium for such solution polymerizations. However, using sodium t-amylate as the polymerization modifier in commercial operations where recycle is required can lead to certain problems. These problems arise due to the fact that sodium t-amylate reacts with water to form t-amyl alcohol during steam stripping in the polymer finishing step. Since t-amyl alcohol forms an azeotrope with hexane, it co-distills with hexane and thus contaminates the feed stream.
[0014] Tire rubbers which are prepared by anionic polymerization are frequently coupled with a suitable coupling agent, such as a tin halide, to improve desired properties. Tin-coupled polymers are known to improve treadwear and to reduce rolling resistance when used in tire tread rubbers. Such tin-coupled rubbery polymers are typically made by coupling the rubbery polymer with a tin coupling agent at or near the end of the polymerization used in synthesizing the rubbery polymer. In the coupling process, live polymer chain ends react with the tin coupling agent thereby coupling the polymer. For instance, up to four live chain ends can react with tin tetrahalides, such as tin tetrachloride, thereby coupling the polymer chains together.
[0015] The coupling efficiency of the tin coupling agent is dependant on many factors, such as the quantity of live chain ends available for coupling and the quantity and type of polar modifier, if any, employed in the polymerization. For instance, tin coupling agents are generally not as effective in the presence of polar modifiers. However, polar modifiers such as tetramethylethylenediamine, are frequently used to increase the glass transition temperature of the rubber for improved properties, such as improved traction characteristics in tire tread compounds. Coupling reactions that are carried out in the presence of polar modifiers typically have a coupling efficiency of about 50-60% in batch processes. Lower coupling efficiencies are typically attained in continuous processes.
[0016] U.S. patent application Ser. No. 09/461,653 discloses that coupling efficiency can be significantly improved by conducting the coupling reactions in the presence of a lithium salt of a saturated aliphatic alcohol, such as lithium t-amylate. In the alternative coupling efficiency can also be improved by conducting the coupling reaction in the presence of a lithium halide, or a lithium phenoxide. U.S. patent application Ser. No. 09/461,653 specifically discloses a process for coupling a living rubbery polymer that comprises reacting the living rubbery polymer with coupling agent selected from the group consisting of tin halides and silicon halides in the presence of a lithium salt of a saturated aliphatic alcohol. The lithium salt of the saturated aliphatic alcohol can be added immediately prior to the coupling reaction or it can be present throughout the polymerization and coupling process.
[0017] Each tin tetrahalide molecule or silicon tetrahalide molecule is capable of reacting with up to four live polymer chain ends. However, since perfect stoichiometry is difficult to attain, some of the tin halide molecules often react with less than four live polymer chain ends. The classical problem is that if more than a stoichiometric amount of the tin halide coupling agent is employed, then there will be an insufficient quantity of live polymer chain ends to totally react with the tin halide molecules on a four-to-one basis. On the other hand, if less than a stoichiometric amount of the tin halide coupling agent is added, then there will be an excess of live polymer chain ends and some of the live chain ends will not be coupled. It is accordingly important for the stoichiometry to be exact and for all to the living polymer chain-ends to react with the coupling agent.
[0018] Conventional tin coupling results in the formation of a coupled polymer that is essentially symmetrical. In other words, all of the polymer arms on the coupled polymer are of essentially the same chain length. All of the polymer arms in such conventional tin-coupled polymers are accordingly of essentially the same molecular weight. This results in such conventional tin-coupled polymers having a low polydispersity. For instance, conventional tin-coupled polymers normally having a ratio of weight average molecular weight to number average molecular weight which is within the range of about 1.01 to about 1.1
[0019] U.S. Pat. No. 5,486,574 discloses dissimilar arm asymmetric radical or star block copolymers for adhesives and sealants. U.S. Pat. No. 5,096,973 discloses ABC block copolymers based on butadiene, isoprene and styrene and further discloses the possibility of branching these block copolymers with tetrahalides of silicon, germanium, tin or lead.
SUMMARY OF THE INVENTION
[0020] The tin coupling efficiency (degree of coupling) attained with living polymers is normally reduced when polar modifiers, such as tetramethylethylenediamine (TMEDA) are present. However, polar modifiers are needed to increase the glass transition temperature of rubbery polymers to obtain desired properties, such as improved traction characteristics in tire tread compounds. Although a coupling efficiency within the range of 50 to 60 percent can be achieved in batch processes used in the synthesis of tin coupled styrene-butadiene rubbers, much lower levels of coupling are realized in continuous processes.
[0021] It has been unexpectedly found that the coupling efficiency of rubbery polymers made with polar modifiers can be significantly improved by initiating the anionic polymerization with certain alkylsilyloxy protected functional lithium initiators. These alkylsilyloxy protected functional lithium initiators can be of the structural formula:
[0022] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms. In the alternative these alkylsilyloxy protected functional lithium initiators can be of the structural formula:
[0023] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein Y represents phosphorous or nitrogen, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms.
[0024] It is normally preferred for the alkylsilyloxy protected functional lithium initiator to be of the structural formula:
[0025] wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms. In fact, coupling efficiencies of at least 70 percent are realized by utilizing the process of the present invention. In most, cases, coupling efficiencies of at least 80 percent are realized by utilizing the process of the present invention.
[0026] The present invention more specifically discloses a process for synthesizing and coupling a rubbery polymer that comprises (1) polymerizing at least one conjugated diolefin monomer in the presence of a polar modifier to produce a living rubbery polymer, wherein said polymerization is an anionic polymerization that is initiated with an alkylsilyloxy protected functional lithium initiator having a the structural formula selected from the group consisting of (a):
[0027] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group;
[0028] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein Y represents phosphorous or nitrogen, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group; and (c):
[0029] wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group; and (2) reacting the living rubbery polymer with a coupling agent selected from the group consisting of tin halides and silicon halides.
[0030] The present invention further discloses a process for synthesizing and coupling a rubbery polymer that comprises (1) polymerizing at least one conjugated diolefin monomer in the presence of a polar modifier to produce a living rubbery polymer, wherein said polymerization is an anionic polymerization that is initiated with an alkylsilyloxy protected functional lithium initiator having a the structural formula selected from the group consisting of (a):
[0031] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms, and (b):
[0032] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein Y represents phosphorous or nitrogen, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms; and (2) reacting the living rubbery polymer with a coupling agent selected from the group consisting of tin halides and silicon halides.
[0033] The present invention also reveals a. process for synthesizing and coupling a rubbery polymer that comprises (1) polymerizing at least one conjugated diolefin monomer in the presence of a polar modifier to produce a living rubbery polymer, wherein said polymerization is an anionic polymerization that is initiated with an alkylsilyloxy protected functional lithium initiator of the structural formula:
[0034] wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms, and (2) reacting the living rubbery polymer with a coupling agent selected from the group consisting of tin halides and silicon halides.
[0035] The subject invention also reveals an initiator which is particularly useful for initiating the anionic polymerization of conjugated diolefin monomers into rubbery polymers said initiator having a structural formula selected from the group consisting of (a):
[0036] wherein X represents a group IVa element selected from the group consisting of carbon, germanium, and tin, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group; (b):
[0037] wherein X represents a group IVa element selected from the group consisting of carbon, germanium, and tin, wherein Y represents phosphorous or nitrogen, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group; and (c):
[0038] wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group; and (2) reacting the living rubbery polymer with a coupling agent selected from the group consisting of tin halides and silicon halides.
[0039] The present invention also reveals a process for synthesizing a rubbery polymer that comprises polymerizing at least one conjugated diolefin monomer in the presence of a polar modifier to produce a living rubbery polymer, wherein said polymerization is an anionic polymerization that is initiated with an alkylsilyloxy protected functional lithium initiator having a the structural formula selected from the group consisting of (a):
[0040] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group; (b):
[0041] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein Y represents phosphorous or nitrogen, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group; and (c):
[0042] wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group.
DETAILED DESCRIPTION OF THE INVENTION
[0043] Virtually any type of rubbery polymer prepared by anionic polymerization can be synthesized and coupled in accordance with this invention. The rubbery polymers that can be coupled will typically be synthesized by a solution polymerization technique that utilizes as the initiator an alkylsilyloxy protected functional lithium initiator of the structural formula: (a):
[0044] wherein X represents a group IVa element selected from the group consisting of carbon, germanium, and tin, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group; or (b):
[0045] wherein X represents a group IVa element selected from the group consisting of carbon, germanium, and tin, wherein Y represents phosphorous or nitrogen, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group; or (c):
[0046] wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms, and wherein A represents an alkylene group. The alkylene group can be straight chained or branched. For instance, A can represent a straight chained alkylene group of the structural formula —(CH 2 ) n or it can represent a branched alkylene group, such as:
[0047] wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms. R will typically represent an alkyl group containing from 1 to about 4 carbon atoms. It is preferred for R to represent methyl groups.
[0048] The alkylsilyloxy protected functional lithium initiator will typically be of the structural formula:
[0049] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms, or an alkylsilyloxy protected functional lithium compound of the structural formula:
[0050] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein Y represents phosphorous or nitrogen, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms. These rubbery polymers will accordingly normally contain a “living” lithium chain end.
[0051] It is normally preferred for the alkylsilyloxy protected functional lithium initiator to be of the structural formula:
[0052] wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms. In fact, coupling efficiencies of at least 70 percent are realized by utilizing the process of the present invention. In most, cases, coupling efficiencies of at least 80 percent are realized by utilizing the process of the present invention.
[0053] The polymerizations employed in synthesizing the living rubbery polymers will normally be carried out in a hydrocarbon solvent. Such hydrocarbon solvents are comprised of one or more aromatic, paraffinic or cycloparaffinic compounds. These solvents will normally contain from about 4 to about 10 carbon atoms per molecule and will be liquid under the conditions of the polymerization. Some representative examples of suitable organic solvents include pentane, isooctane, cyclohexane, methylcyclohexane, isohexane, n-heptane, n-octane, n-hexane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isobutylbenzene, petroleum ether, kerosene, petroleum spirits, petroleum naphtha, and the like, alone or in admixture.
[0054] In the solution polymerization, there will normally be from 5 to 30 weight percent monomers in the polymerization medium. Such polymerization media are, of course, comprised of the organic solvent and monomers. In most cases, it will be preferred for the polymerization medium to contain from 10 to 25 weight percent monomers. It is generally more preferred for the polymerization medium to contain 15 to 20 weight percent monomers.
[0055] The rubbery polymers that are coupled in accordance with this invention can be made by the homopolymerization of a conjugated diolefin monomer or by the random copolymerization of a conjugated diolefin monomer with a vinyl aromatic monomer. It is, of course, also possible to make living rubbery polymers that can be coupled by polymerizing a mixture of conjugated diolefin monomers with one or more ethylenically unsaturated monomers, such as vinyl aromatic monomers. The conjugated diolefin monomers which can be utilized in the synthesis of rubbery polymers which can be coupled in accordance with this invention generally contain from 4 to 12 carbon atoms. Those containing from 4 to 8 carbon atoms are generally preferred for commercial purposes. For similar reasons, 1,3-butadiene and isoprene are the most commonly utilized conjugated diolefin monomers. Some additional conjugated diolefin monomers that can be utilized include 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, and the like, alone or in admixture.
[0056] Some representative examples of ethylenically unsaturated monomers that can potentially be synthesized into rubbery polymers which can be coupled in accordance with this invention include alkyl acrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and the like; vinylidene monomers having one or more terminal CH 2 ═CH— groups; vinyl aromatics such as styrene, α-methylstyrene, bromostyrene, chlorostyrene, fluorostyrene and the like; α-olefins such as ethylene, propylene, 1-butene and the like; vinyl halides, such as vinylbromide, chloroethane (vinylchloride), vinylfluoride, vinyliodide, 1,2-dibromoethene, 1,1-dichloroethene (vinylidene chloride), 1,2-dichloroethene and the like; vinyl esters, such as vinyl acetate; α,β-olefinically unsaturated nitriles, such as acrylonitrile and methacrylonitrile; α,β-olefinically unsaturated amides, such as acrylamide, N-methyl acrylamide, N,N-dimethylacrylamide, methacrylamide and the like.
[0057] Rubbery polymers which are copolymers of one or more diene monomers with one or more other ethylenically unsaturated monomers will normally contain from about 50 weight percent to about 99 weight percent conjugated diolefin monomers and from about 1 weight percent to about 50 weight percent of the other ethylenically unsaturated monomers in addition to the conjugated diolefin monomers. For example, copolymers of conjugated diolefin monomers with vinylaromatic monomers, such as styrene-butadiene rubbers which contain from 50 to 95 weight percent conjugated diolefin monomers and from 5 to 50 weight percent vinylaromatic monomers, are useful in many applications.
[0058] Vinyl aromatic monomers are probably the most important group of ethylenically unsaturated monomers which are commonly incorporated into polydienes. Such vinyl aromatic monomers are, of course, selected so as to be copolymerizable with the conjugated diolefin monomers being utilized. Generally, any vinyl aromatic monomer which is known to polymerize with organolithium initiators can be used. Such vinyl aromatic monomers typically contain from 8 to 20 carbon atoms. Usually, the vinyl aromatic monomer will contain from 8 to 14 carbon atoms. The most widely used vinyl aromatic monomer is styrene. Some examples of vinyl aromatic monomers that can be utilized include styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, α-methylstyrene, 4-phenyistyrene, 3-methylstyrene and the like.
[0059] Some representative examples of rubbery polymers which can be coupled in accordance with this invention include polybutadiene, polyisoprene, styrene-butadiene rubber (SBR), α-methylstyrene-butadiene rubber, α-methylstyrene-isoprene rubber, styrene-isoprene-butadiene rubber (SIBR), styrene-isoprene rubber (SIR), isoprene-butadilene rubber (IBR), α-methylstyrene-isoprene-butadiene rubber and α-methylstyrene-styrene-isoprene-butadiene rubber. In cases where the rubbery polymer is comprised of repeat units that are derived from two or more monomers, the repeat units which are derived from the different monomers will normally be distributed in an essentially random manner.
[0060] The polymerizations employed in making the rubbery polymer are typically initiated by adding an organolithium initiator to an organic polymerization medium that contains the monomers. Such polymerizations are typically carried out utilizing continuous polymerization techniques. In such continuous polymerizations, monomers and initiator are continuously added to the organic polymerization medium with the rubbery polymer synthesized being continuously withdrawn. Such continuous polymerizations are typically conducted in a multiple reactor system.
[0061] The organolithium initiators that are employed in synthesizing living rubbery polymers which can be coupled in accordance with this invention are typically alkylsilyloxy protected functional lithium compounds of the structural formula:
[0062] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms, or an alkylsilyloxy protected functional lithium compound of the structural formula:
[0063] wherein X represents a group IVa element selected from the group consisting of carbon, silicon, germanium, and tin, wherein Y represents phosphorous or nitrogen, wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms. It is typically preferred for X to represents silicon, tin, or germanium. It is normally most preferred for X to represent silicon.
[0064] It is typically most preferred for the alkylsilyloxy protected functional lithium compound to be of the structural formula:
[0065] wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms. It is normally preferred for n to represent an integer from 1 to about 6. It is more preferred from n to represent an integer from 2 to 4. It is typically most preferred from n to represent 3. In most cases, R will represent alkyl groups containing from 1 to about 4 carbon atoms. R will preferable represent methyl groups, ethyl groups, normal-propyl groups, or isopropyl groups. It is typically most preferred for R to represent methyl groups. A highly preferred initiator is 3-(t-butyldimethylsilyloxy)-1-propyllithium which is commercially available from FMC Corporation.
[0066] The amount of organolithium initiator utilized will vary with the monomers being polymerized and with the molecular weight that is desired for the polymer being synthesized. However, as a general rule, from 0.01 to 1 phm (parts per 100 parts by weight of monomer) of an organolithium initiator will be utilized. In most cases, from 0.01 to 0.1 phm of an organolithium initiator will be utilized with it being preferred to utilize 0.025 to 0.07 phm of the organolithium initiator.
[0067] The polymerization temperature utilized can vary over a broad range of from about −20° C. to about 180° C. In most cases, a polymerization temperature within the range of about 30° C. to about 125° C. will be utilized. It is typically preferred for the polymerization temperature to be within the range of about 45° C. to about 100° C. It is typically most preferred for the polymerization temperature to be within the range of about 60° C. to about 85° C. The pressure used will normally be sufficient to maintain a substantially liquid phase under the conditions of the polymerization reaction.
[0068] The polymerization is conducted for a length of time sufficient to permit substantially complete polymerization of monomers. In other words, the polymerization is normally carried out until high conversions are attained. The polymerization is then terminated by the addition of a tin halide and/or silicon halide. The tin halide and/or the silicon halide are continuous added in cases where asymmetrical coupling is desired. This continuous addition of tin coupling agent and/or the silicon coupling agent is normally done in a reaction zone separate from the zone where the bulk of the polymerization is occurring. In other words, the coupling will typically be added only after a high degree of conversion has already been attained. For instance, the coupling agent will normally be added only after a monomer conversion of greater than about 90 percent has been realized. It will typically be preferred for the monomer conversion to reach at least about 95 percent before the coupling agent is added. As a general rule, it is most preferred for the monomer conversion to exceed about 98 percent before the coupling agent is added. The coupling agents will normally be added in a separate reaction vessel after the desired degree of conversion has been attained. The coupling agents can be added in a hydrocarbon solution, e.g., in cyclohexane, to the polymerization admixture with suitable mixing for distribution and reaction.
[0069] In cases where the rubbery polymer will be used in compounds that are loaded primarily with carbon black, the coupling agent will typically be a tin halide. The tin halide will normally be a tin tetrahalide, such as tin tetrachloride, tin tetrabromide, tin tetrafluoride or tin tetraiodide. However, tin trihalides can also optionally be used. Polymers coupled with tin trihalides having a maximum of three arms. This is, of course, in contrast to polymers coupled with tin tetrahalides which have a maximum of four arms. To induce a higher level of branching, tin tetrahalides are normally preferred. As a general rule, tin tetrachloride is most preferred.
[0070] In cases where the rubbery polymer will be used in compounds that are loaded with high levels of silica, the coupling agent will typically be a silicon halide. The silicon coupling agents that can be used will normally be silicon tetrahalides, such as silicon tetrachloride, silicon tetrabromide, silicon tetrafluoride or silicon tetraiodide. However, silicon trihalides can also optionally be used. Polymers coupled with silicon trihalides having a maximum of three arms. This is, of course, in contrast to polymers coupled with silicon tetrahalides which have a maximum of four arms. To induce a higher level of branching, silicon tetrahalides are normally preferred. As a general rule, silicon tetrachloride is most preferred of the silicon coupling agents.
[0071] A combination of a tin halide and a silicon halide can optionally be used to couple the rubbery polymer. By using such a combination of tin and silicon coupling agents improved properties for tire rubbers, such as lower hysteresis, can be attained. It is particularly desirable to utilize a compination of tin and silicon coupling agents in tire tread compounds that contain both silica and carbon black. In such cases, the molar ratio of the tin halide to the silicon halide employed in coupling the rubbery polymer will normally be within the range of 20:80 to 95:5. The molar ratio of the tin halide to the silicon halide employed in coupling the rubbery polymer will more typically be within the range of 40:60 to 90:10. The molar ratio of the tin halide to the silicon halide employed in coupling the rubbery polymer will preferably be within the range of 60:40 to 85:15. The molar ratio of the tin halide to the silicon halide employed in coupling the rubbery polymer will most preferably be within the range of 65:35 to 80:20.
[0072] Broadly, and exemplary, a range of about 0.01 to 4.5 milliequivalents of tin coupling agent (tin halide and silicon halide) is employed per 100 grams of the rubbery polymer. It is normally preferred to utilize about 0.01 to about 1.5 milliequivalents of the coupling agent per 100 grams of polymer to obtain the desired Mooney viscosity. The larger quantities tend to result in production of polymers containing terminally reactive groups or insufficient coupling. One equivalent of tin coupling agent per equivalent of lithium is considered an optimum amount for maximum branching. For instance, if a mixture tin tetrahalide and silicon tetrahalide is used as the coupling agent, one mole of the coupling agent would be utilized per four moles of live lithium ends. In cases where a mixture of tin trihalide and silicon trihalide is used as the coupling agent, one mole of the coupling agent will optimally be utilized for every three moles of live lithium ends. The coupling agent can be added in a hydrocarbon solution, e.g., in cyclohexane, to the polymerization admixture in the reactor with suitable mixing for distribution and reaction.
[0073] After the coupling has been completed, a tertiary chelating alkyl 1,2-ethylene diamine or a metal salt of a cyclic alcohol can optionally be added to the polymer cement to stabilize the coupled rubbery polymer. The tertiary chelating amines that can be used are normally chelating alkyl diamines of the structural formula:
[0074] wherein n represents an integer from 1 to about 6, wherein A represents an alkylene group containing from 1 to about 6 carbon atoms and wherein R′, R″, R′″ and R″″ can be the same or different and represent alkyl groups containing from 1 to about 6 carbon atoms. The alkylene group A is of the formula —(—CH 2 —) m wherein m is an integer from 1 to about 6. The alkylene group will typically contain from 1 to 4 carbon atoms (m will be 1 to 4) and will preferably contain 2 carbon atoms. In most cases, n will be an integer from 1 to about 3 with it being preferred for n to be 1. It is preferred for R′, R″, R′″ and R″″ to represent alkyl groups which contain from 1 to 3 carbon atoms. In most cases, R′, R′″, R′″ and R″″ will represent methyl groups.
[0075] In most cases, from about 0.01 phr (parts by weight per 100 parts by weight of dry rubber) to about 2 phr of the chelating alkyl 1,2-ethylene diamine or metal salt of the cyclic alcohol will be added to the polymer cement to stabilize the rubbery polymer. Typically, from about 0.05 phr to about 1 phr of the chelating alkyl 1,2-ethylene diamine or metal salt of the cyclic alcohol will be added. More typically, from about 0.1 phr to about 0.6 phr of the chelating alkyl 1,2-ethylene diamine or the metal salt of the cyclic alcohol will be added to the polymer cement to stabilize the rubbery polymer.
[0076] After the polymerization, coupling, and optionally the stabilization step, has been completed, the coupled rubbery polymer can be recovered from the organic solvent. The coupled rubbery polymer can be recovered from the organic solvent and residue by means such as decantation, filtration, centrification and the like. It is often desirable to precipitate the coupled rubbery polymer from the organic solvent by the addition of lower alcohols containing from about 1 to about 4 carbon atoms to the polymer solution. Suitable lower alcohols for precipitation of the rubber from the polymer cement include methanol, ethanol, isopropyl alcohol, normal-propyl alcohol and t-butyl alcohol. The utilization of lower alcohols to precipitate the asymmetrically tin-coupled rubbery polymer from the polymer cement also “kills” any remaining living polymer by inactivating lithium end groups. After the coupled rubbery polymer is recovered from the solution, steam-stripping can be employed to reduce the level of volatile organic compounds in the coupled rubbery polymer.
[0077] The coupled rubbery polymers that can be made by using the technique of this invention are comprised of a tin and/or silicon atoms having at least three polydiene arms covalently bonded. In the case of asymmetrically coupled rubbery polymers made by the technique of this invention at least one of the polydiene arms bonded to the tin atoms and/or the silicon atoms has a number average molecular weight of less than about 40,000, at least one of the polydiene arms bonded to the tin atoms and/or the silicon atoms has a number average molecular weight of at least about 80,000. The ratio of the weight average molecular weight to the number average molecular weight of the asymmetrically coupled rubbery polymer will also normally be within the range of about 2 to about 2.5.
[0078] The asymmetrically coupled rubbery polymers that can be made by the process of this invention contain stars of the structural formula:
[0079] wherein M represents silicon or tin, wherein R 1 , R 2 , R 3 and R 4 can be the same or different and are selected from the group consisting of alkyl groups and polydiene arms (polydiene rubber chains), with the proviso that at least three members selected from the group consisting of R 1 , R 2 , R 3 and R 4 are polydiene arms, with the proviso that at least one member selected from the group consisting of R 1 , R 2 , R 3 and R 4 is a low molecular weight polydiene arm having a number average molecular weight of less than about 40,000, with the proviso that at least one member selected from the group consisting of R 1 , R 2 , R 3 and R 4 is a high molecular weight polydiene arm having a number average molecular weight of greater than about 80,000, and with the proviso that the ratio of the weight average molecular weight to the number average molecular weight of the asymmetrical tin-coupled rubbery polymer is within the range of about 2 to about 2.5. It should be noted that R 1 , R 2 , R 3 and R 4 can be alkyl groups because it is possible for the tin halide coupling agent to react directly with alkyl lithium compounds which are used as the polymerization initiator. The ratio of silicon containing stars to tin containing stars will be within the range of about 20:80 to about 80:20 in cases where the rubber is coupled with both a silicon and a tin coupling agent.
[0080] In most cases, four polydiene arms will be covalently bonded to the tin atom or the silicon atom in the asymmetrical tin-coupled rubbery polymer. In such cases, R 1 , R 2 , R 3 and R 4 will all be polydiene arms. The asymmetrical tin-coupled rubbery polymer will often contain a polydiene arm of intermediate molecular weight as well as the low molecular weight arm and the high molecular weight arm. Such intermediate molecular weight arms will have a molecular weight that is within the range of about 45,000 to about 75,000. It is normally preferred for the low molecular polydiene arm to have a molecular weight of less than about 30,000 with it being most preferred for the low molecular weight arm to have a molecular weight of less than about 25,000. It is normally preferred for the high molecular polydiene arm to have a molecular weight of greater than about 90,000 with it being most preferred for the high molecular weight arm to have a molecular weight of greater than about 100,000. The arms of the coupled polymer will typically be either homopolymers or random copolymers. In other words, the arms of the coupled polymers will normally not be block copolymers.
[0081] This invention is illustrated by the following examples which are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, all parts and percentages are given by weight.
EXAMPLE 1
[0082] In this experiment, a tin coupled styrene-butadiene rubber was prepared at 70° C. In the procedure used, 2300 g of a silica/alumina/molecular sieve dried premix containing 19.5 weight percent styrene/1,3-butadiene mixture in hexanes was charged into a one-gallon (3.8 liters) reactor. The ratio of styrene to 1,3-butadiene was 15:85. After the amount of impurity in the premix was determined, 2.4 ml of 1 M solution of TMEDA (N,N,N′,N′-tetramethylethylene-diamine in hexanes), and 4.3 ml. of 0.7 M solution of 3-(t-butyldimethylsilyloxy)-1-propyllithium (in cyclohexane) were added to the reactor. The target Mn (number averaged molecular weight) was 150,000. The polymerization was allowed to proceed at 70° C. for 1.5 hours. The GC analysis of the residual monomers contained in the polymerization mixture indicated that most of the monomers were converted to polymer. After a small aliquot of polymer cement was removed from the reactor (for analysis), 1.2 ml. of a 0.6 M solution of tin tetrachloride (in hexanes) was added to the reactor and the coupling reaction was carried out the same temperature for an hour. At this time, 1.0 phr (parts per 100 parts of rubber by weight) of BHI (2,6-di-tert-butyl-4-methylphenol) and 3.0 ml of 1 M solution of TMEDA were added to the reactor to shortstop the polymerization and to stabilized the polymer. After evaporating the hexanes, the resulting polymer was dried in a vacuum oven at 50° C. The coupled styrene-butadiene rubber (SBR) produced was determined to have a glass transition temperature (Tg) at −45° C. It was also determined to have a microstructure, which contained 49 percent 1,2-polybutadiene units, 37 percent 1,4-polybutadiene units and 14 percent random polystyrene units. The Mooney viscosity (ML-4) at 100° C. for this coupled polymer was also determined to be 114. The ML-4 for the base polymer (before coupling) was 25. Based on GPC measurement, the coupling efficiency was 83%.
COMPARATIVE EXAMPLE 2
[0083] The procedure described in Example 1 was utilized in this example except that 2.92 ml of 1 M solution of n-butyllithium (in hexanes) was used as the polymerization initiator. The Tg and microstructure of the resulting coupled SBR are shown in Table 1. The Mooney viscosities of the base and coupled polymers are also shown in Table 1. The coupling efficiency was 55%, based on GPC measurement.
TABLE 1 Exam- Tg ML-4 Microstructure (%) Coupling ple (° C.) Base Coupled 1,2-PBd 1,4-PBd Styrene Efficiency 1 −44 25 114 49 37 14 83% 2 −45 25 85 49 37 14 55
EXAMPLE 3
[0084] The tin coupled SBR prepared in this experiment was synthesized in a three-reactor (1 gallon, 2 gallon, 2 gallon) continuous system at 80° C. A premix containing styrene and 1,3-butadiene in hexanes was charged into the first polymerization reactor continuously at a rate of 98 grams per minute. The premix monomer solution containing a ratio of styrene to 1,3-butadiene of 18:82 and had a total monomer concentration of 16%. Polymerization was initiated by adding 3-(t-butyl-dimethylsilyloxy)-1-propyl lithium (0.6 mmole/100 grams of monomer) and TMEDA (1 mmole/100 grams monomer) to the first reactor continuously. The resulting polymerization medium containing the live ends was continuously pushed to the second rector (for completing the polymerization) and then the third reactor where the coupling agent, tin tetrachloride, (0.15 mmole/100 grams monomer) was added continuously. The residence time for all reactors was set at one hour to achieve complete monomer conversion in the second reactor and complete coupling at the third reactor. The polymerization medium was continuously pushed over to a holding tank containing stabilizer and antioxidant. The resulting polymer cement was then steam stripped and the recovered SBR was dried in a vented oven at 50° C. The polymer was determined to have a glass transition temperature at −43° C. and have a Mooney ML-4 viscosity of 80. The Mooney viscosity of base (uncoupled precursor) was 32. It was also determined to have a microstructure, which contained 18% random polystyrene units, 41% 1,2-polybutadiene units, and 41% 1,4-polybutdiene units.
EXAMPLE 4
[0085] The produce described in Example 3 was utilized in this example except that n-butyllithium was used as the initiator. The Tg and microstructure of the resulting coupled SBR are shown in Table 2. The Mooney viscosities of the base and coupled polymers are also shown in Table 2.
TABLE 2 Tg ML-4 Microstructure (%) Example (° C.) Base Coupled 1,2-PBd 1,4-PBd Styrene 3 −43 32 80 41 41 18 4 −42 42 68 42 41 17
EXAMPLE 5
[0086] In this example, a 50/50 isoprene-butadiene rubber (IBR) containing a silyloxyl functional group was prepared. In the procedure used, 2300 g of a silica/alumina/molecular sieve dried premix containing 19.0 weight percent isoprene/1,3-butadiene mixture in hexanes was charged into a one-gallon (3.8 liters) reactor. The ratio of styrene to 1,3-butadiene was 50:50. After the amount of impurity in the premix was determined, 1.7 ml of 1 M solution of TMEDA (N,N,N′,N′-tetramethylethylene-diamine in hexanes), and 2.5 ml. of 0.7 M solution of 3-(t-butyldimethylsilyloxy)-1-propyllithium (in cyclohexane) were added to the reactor. The target Mn (number averaged molecular weight) was 250,000. The polymerization was allowed to proceed at 70° C. for 2.5 hours. The GC analysis of the residual monomers contained in the polymerization mixture indicated that most of the monomers were converted to polymer. At this time, the polymerization mixture was shortstopped with 2.0 ml. of 1 M ethanol solution (in hexanes). The resulting polymer was stabilized with 1.0 phr (parts per 100 parts of rubber by weight) of BHIT (2,6-di-tert-butyl-4-methylphenol). After evaporating the hexanes, the resulting polymer was dried in a vacuum oven at 50° C. The IBR produced was determined to have a glass transition temperature (Tg) at −45° C. It was also determined to have a microstructure, which contained 24 percent 1,2-polybutadiene units, 26 percent 1,4-polybutadiene units, 22 percent 1,4-polyisoprene units, 27 percent 3,4-polyisoprene units and 1% 1,2-polyisoprene unit. The Mooney viscosity (ML-4) at 100° C. for this polymer was also determined to be 65.
EXAMPLE 6
[0087] In this example, a telechelic 50/50 isoprene-butadiene rubber containing a silyloxyl functional group at the beginning of the polymer chain and an alkoxysilyl functional group at the end of polymer chain was prepared. The procedure described in Example 5 was used in this example except that 3-chloropropyltriethoxysilane was added to the polymerization mixture at the completion of polymerization (2.5 hours) to form an ethoxysilyl end functionalized IBR. The telichelic IBR produced was determined to have a glass transition temperature (Tg) at −44° C. It was also determined to have a microstructure which contained 25 percent 1,2-polybutadiene units, 25 percent 1,4-polybutadiene units, 22 percent 1,4-polyisoprene units, 27 percent 3,4-polyisoprene units and 1% 1,2-polyisoprene unit. The Mooney viscosity (ML-4) at 100° C. for this polymer was also determined to be 69.
EXAMPLE 7
[0088] In this example, a telechelic 50/50 isoprene-butadiene rubber containing a silyloxy functional group at the beginning of the polymer chain and a alkoxysilyl sulfane functional group at the end of polymer chain was prepared. The procedure described in Example 5 was used in this example except that bis(3-triethoxylsilylpropyl)disulfane was used in place of 3-chloropropyltriethoxy-silane to functionalize the polymer chain ends. The resulting telichelic IBR produced was determined to have a glass transition temperature (Tg) a −45° C. It was also determined to have a microstructure which contained 24 percent 1,2-polybutadiene units, 26 percent 1,4-polybutadiene units, 22 percent 1,4-polyisoprene units, 22 percent 3,4-polyisoprene units and 2% 1,2-polyisoprene unit. The Mooney viscosity (ML-4) at 100° C. for this polymer was also determined to be 72.
EXAMPLE 8
[0089] In this example, a 30/70 styrene-butadiene rubber (SBR) containing a silyloxy functional group was prepared. The procedure described in Example 5 was utilized in this example except that a mixture of styrene and 1,3-butadiene in hexanes was used as the monomers. The ratio of styrene to 1,3-butadiene was 30:70. The silyloxy functionalized SBR produced was determined to have a glass transition temperature (Tg) at −29° C. It was also determined to have a microstructure which contained 41 percent 1,2-polybutadiene units, 31 percent 1,4-polybutadiene units and 28 percent random polystyrene units. The Mooney viscosity (ML-4) at 100° C. for this polymer was also determined to be 70.
EXAMPLE 9
[0090] In this example, a telechelic 30/70 styrene-butadiene rubber containing a silyloxy functional group at the beginning of the polymer chain and an alkoxysilyl finctional group at the end of polymer chain was prepared. The procedure described in Example 6 was utilized in this example except that a mixture of styrene and 1,3-butadiene in hexanes was used as the monomers. The ratio of styrene to 1,3-butadiene was 30:70. The telichelic SBR produced was determined to have a glass transition temperature (Tg) at −30° C. It was also determined to have a microstructure which contained 40 percent 1,2-polybutadiene units, 31 percent 1,4-polybutadiene units and 29 percent random polystyrene units. The Mooney viscosity (ML-4) at 100° C. for this polymer was also determined to be 73.
EXAMPLE 10
[0091] In this example, a telechelic 30/70 styrene-butadiene rubber containing a silyloxy functional group at the beginning of the polymer chain and a alkoxysilyl sulfane finctional group at the end of polymer chain was prepared. The procedure described in Example 7 was utilized in this example except that a mixture of styrene and 1,3-butadiene in hexanes was used as the monomers. The ratio of styrene to 1,3-butadiene was 30:70. The telichelic SBR produced was determined to have a glass transition temperature (Tg) at −29° C. It was also determined to have a microstructure which contained 39 percent 1,2-polybutadiene units, 32 percent 1,4-polybutadiene units and 29 percent random polystyrene units. The Mooney viscosity (ML-4) at 100° C. for this polymer was also determined to be 89.
COMPARATIVE EXAMPLE 11
[0092] A 15/85 SBR was prepared, using a standard anionic polymerization technique, in a one gallon batch reactor with a TMEDA modified n-butyllithium (n-BuLi)catalyst at 70° C. The TMEDA/n-BuLi molar ratio was 0.85/1. It took 90 minutes to complete the polymerization. Tin tetrachloride in hexane (0.25/1 molar ratio to n-BuLi) was then added to the resulting polymer cement. The coupling reaction was carried out at a temperature of 70° C. for 30 minutes. The polymer was then stabilized with TMEDAIBHT. The coupling efficiency, the Tg, and the Mooney ML-4 viscosity of the polymer are listed in Table 3.
EXAMPLE 12
[0093] The procedure described in Example 11 was repeated in this example except that 3-(tributyltin)-1-propyllithium (Bu 3 Sn(CH 2 ) 3 Li), provided by Chemetall-Foote Co. was used as the initiator. The coupling efficiency, the glass transition temperature, and the Mooney ML-4 viscosity of the tin functionalized-coupled polymer are also listed in Table 3.
TABLE 3 Example Tg Base ML-4 Coupled ML-4 % Coupling* 11 44° C. 33 99 55 12 46° C. 34 120 79
[0094] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention.
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Rubbery polymers made by anionic polymerization can be coupled with tin halides or silicon halides to improve the characteristics of the rubber for use in some applications, such as tire treads. In cases where the rubbery polymer is synthesized by anionic polymerization utilizing a polar modifier it is difficult to attain a high level of coupling. This invention is based upon the unexpected finding that the coupling efficiency of rubbery polymers made with polar modifiers can be significantly improved by initiating the anionic polymerization with an alkylsilyloxy protected functional lithium initiator of the structural formula:
wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms. The present invention more specifically discloses a process for synthesizing and coupling a rubbery polymer that comprises (1) polymerizing at least one conjugated diolefin monomer in the presence of a polar modifier to produce a living rubbery polymer, wherein said polymerization is an anionic polymerization that is initiated with an alkylsilyloxy protected functional lithium initiator of the structural formula:
wherein n represents an integer from 1 to 10, wherein R represents alkyl groups that can be the same or different, and wherein the alkyl groups contain from 1 to about 8 carbon atoms, (2) reacting the living rubbery polymer with a coupling agent selected from the group consisting of tin halides and silicon halides.
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TECHNICAL FIELD
This invention pertains to methods for reducing print through, or surface irregularities generally corresponding to the scale of the fiber weave, in molded polymer composite structures with woven long fiber reinforcements.
BACKGROUND OF THE INVENTION
It is well known that the strength and stiffness of a material may be improved by addition of strong and/or stiff reinforcements such as particles, chopped fibers or long fibers to form a composite structure. This practice is applicable to many matrix materials including metals, ceramics and polymers, but is frequently employed with polymer matrices, which offer lesser strength and stiffness, but lower density, than either ceramics or metals. Thus such a reinforced polymer structure may offer good strength and stiffness in combination with low mass.
If low mass is of particular concern, the composite mass may be further minimized by using a higher strength and low density fiber reinforcement in addition to a low density polymer matrix. Minimizing the mass of the composite will increasingly depend on minimizing the mass of the reinforcing higher strength fibers as performance demands accelerate the trend toward increasing fiber volume fractions. One, commonly used, high strength, low density reinforcement is carbon fibers.
In some applications, consideration of only a limited number of engineering attributes, like stiffness, strength or mass of a reinforced polymer may be sufficient to determine whether or not it is suited for a particular purpose. In many more applications however, a much broader range of engineering properties, characteristics and behaviors must be taken into account. For example, in assemblies where multiple materials are employed, compatibility, in performance or appearance, with other, different materials may be an issue. A case in point occurs in some automotive applications, where an individual reinforced composite component or structure, for example a hood, may be located adjacent to a sheet metal component, for example a fender. It is intended that the painted appearance of all the components should match.
Reinforcing fibers may be used as discrete reinforcements but in many cases, the carbon fibers are arranged in organized groupings. For example, in some carbon fiber reinforced polymers the generally cylindrical carbon fibers are first organized into tows. These are assemblages of continuous or near-continuous, untwisted fibers loosely gathered together. Tows often adopt a ribbon-like configuration and may be generally elliptical in cross-section, and are, optionally, lightly secured using an epoxy sizing. Such tows may then be woven into any desired 2-dimensional pattern to form a reinforcing fabric or sheet. While individual fibers may have a diameter of at least a micrometer or so, a more typical dimension is between 10 and 20 micrometers. A tow, by contrast, which may contain from about 1 to 50 thousand fibers may range in width from between 1.0 to 10 millimeters, or, equivalently, of between 1000 and 10,000 micrometers. Typical weave patterns may be somewhat coarse with adjacent parallel tows being spaced between 1 and 5 millimeters apart.
Fabrication of a component begins with impregnating the woven sheets with a polymer resin, which, for ease of handling, is often partially cured or B-staged but remains flexible and conformable. Such a resin-impregnated sheet is termed a prepreg.
In volume production, heated multipart molds are frequently employed. Such molds are capable of receiving the prepreg and shaping it, under pressure, to the desired article shape before the mold is heated. The mold temperature may then be increased to raise the prepreg temperature and cure the resin and form a composite article. The mold parts are separable for loading the prepreg and for extracting the cured article and the various mold parts, when assembled into their operating configuration, define a die cavity corresponding to the desired article geometry.
Such mold may accept a single prepreg but, more frequently, multiple resin-impregnated sheets are placed one atop the other to form a layup. In assembling the layup, the sheets, and their associated reinforcements, may be displaced or rotated with respect to one another to reduce in-plane property directionality in the finished component. The layup may be fabricated in the mold or may be prepared off-line and placed in the mold only when fully assembled.
The coefficients of thermal expansion (CTE) of the polymer and reinforcement are significantly different. In addition, most carbon fibers have an anisotropic CTE, exhibiting one CTE along their axis and a second CTE across their diameter, assuring that there will be at least some mismatch in CTE between the fiber and the larger and more isotropic CTE of the polymer. During cool-down of the composite article this mismatch in CTE will induce stresses which will produce print through of the weave pattern, that is, surface distortions which mimic the weave pattern spacing. The regions between the fiber tows will be depressed compared to the more elevated regions overlying the fiber tows.
These surface distortions, or print through of the fiber pattern, are clearly visible, particularly on a painted surface, and are unacceptable on any ‘show surface’ which may be viewed by a customer. Thus many viewable fiber composite components require extensive finishing, typically priming and sanding, prior to final painting.
There is therefore a need for a method of suppressing or minimizing print through in fiber reinforced composite panels to minimize the need for remedial surface treatments prior to assembly and painting of the panels.
SUMMARY OF THE INVENTION
This invention provides a method for minimizing print through distortions in surfaces of woven fiber reinforced polymer composite articles. The invention is practiced so as to provide higher quality visible surface layers on polymer composite articles that otherwise benefit from the presence of extensive woven fiber reinforcement layers.
In accordance with embodiments of the invention, a preformed, moldable, polymer prepreg layer, reinforced with closely spaced, vertically oriented, carbon nanotubes is applied to an intended visible surface of the woven fiber-reinforced layup material. The woven fiber reinforced material makes up the body portion of the molded composite article, but the nanotube layer is sized and shaped to form one or more surfaces of the composite article. In contrast with the orientation of the woven fibers in the underlying polymer body layer(s), the carbon nanotubes are oriented transverse to the thickness of the comparatively thin applied covering polymer layer for the surface of the molded composite article. The woven fiber reinforced polymer portion and each covering polymer layer of oriented carbon nanotubes are shaped together and their polymer content cured together to form a durable composite article with smoother visible surfaces. The transverse orientation of the carbon nanotubes in the covering polymer layer reduces uneven shrinkage of surface regions and leaves a relatively smooth surface on the article that is mainly strengthened with the woven fibers. By addition of such a covering layer, the upper surface of the article is made more homogeneous, reducing the disparity in CTE and other properties between open and filled regions of the weave, which would otherwise lead to the observed print through.
Carbon nanotubes are hollow co-axial cylinders of carbon whose diameters are measured in nanometers or tens of nanometers, with lengths which may extend over tens of millimeters. They exhibit high strength and a low coefficient of thermal expansion (CTE) along their cylinder axis. Hence the thermal contraction of a vertically arranged carbon nanotube polymer composite will be greatly reduced compared to the thermal contraction of the polymer alone, further reducing the tendency for print through in the composite article.
Carbon nanotubes are commonly grown by a catalyzed gas-phase reaction. A substrate is prepared with a layer of metal catalyst particles of a predetermined size related to the desired nanotube diameter. Typically these particles contain nickel, cobalt, molybdenum, and iron, singly or in combination. The substrate is heated to approximately 750° C. in an atmosphere of an inert gas, for example ammonia, nitrogen or hydrogen and then exposed to a carbon-containing gas, such as acetylene, ethylene, ethanol or methane or a mixture of CO and hydrogen. Nanotubes grow at the sites of the metal catalyst, where it appears that the carbon-containing gas decomposes at the surface of the catalyst particle, liberating carbon which is absorbed by the catalyst particle and transported to the particle edges, where it forms the nanotubes.
An exemplary procedure for forming vertically-aligned carbon nanotube arrays is to fabricate, on a silicon wafer substrate with a 10 nanometer or so thick layer of Al 2 O 3 , a plurality of densely-packed iron catalyst particles, each ranging in size from about 10 to 20 nanometers. A suitable procedure is to deposit, from aqueous solution, an iron salt, which, when on evaporation of the water and exposure to suitably elevated temperatures under an inert gas atmosphere will decompose to form the iron catalyst particles. By flowing ethylene, at elevated temperature, over the silicon wafer-supported iron particles, carbon nanotubes may be formed. Under the following process conditions: a process temperature of 800° C.; a process temperature of 800° C.; an ethylene flow rate of about 1 mm/second linear velocity; and, a chamber pressure of about 1 atmosphere; carbon nanotubes of 3 to 5 millimeters in length and about 10 nanometers in diameter may be obtained in 2 to 4 hours. The nanotubes are present at a surface density of about 10 11 fibers/cm 2 and substantially uniformly distributed and commonly oriented with their long or cylindrical axis generally perpendicular to the surface of the supporting silicon wafer.
A surface density of 10 11 /cm 2 corresponds to uniformly spaced nanotubes about 30 nanometers apart. The desired nanotube density may be adjusted either by controlling the density of nuclei or, if greater densities are required, by compressing the nanotube array to any appropriate extent.
The nanotube array may be impregnated with polymer resin which should be selected to be compatible with the pre-preg resin. One exemplary resin is a bisphenol A-based epoxy resin, which may then be partially cured or B-staged so that the resin and cross-linking agent have reacted only to the extent of producing a viscoelastic solid. The B-staged resin/nanotube composite may be used as-prepared, or sliced, using a microtome or other devices, in a direction parallel to the surface of the silicon wafer support, to form composite layers of any desired thickness. By slicing the layers in this way the cylindrical axes of the cut-off nanotube segments are maintained generally perpendicular to the surfaces of the layer.
These B-staged resin/nanotube composite layers may then be placed as a surface layer on the stack of pre-pregs which make up the layup. Usually it will be necessary to apply the nanotube composite layer to only one surface of the layup, but in cases, where both sides of an article are visible, it may be appropriate to apply the nanotube composite layer to both surfaces.
Application of pressure to the layup, now including the nanotube-resin composite layer, will fuse the nanotube composite layer with the reinforcing fabric layers and drive the nanotubes into the surface while substantially maintaining their orientation generally normal to the article surface. Application of heat to cure the composite will permanently embed the oriented nanotubes into the article surface and establish a strong bond between the polymer and nanotube.
Now, the tendency for the polymer-rich regions of the component to shrink in the thickness direction of the article during cool-down from the cure temperature will be opposed by the low CTE and high strength of the nanotubes. Also, the surface composition will be homogeneous on a scale of down to tens of nanometers so that any inhomogeneity in shrinkage will be less visible.
The effectiveness of nanotube-polymer layer in controlling the distortion of the polymer will depend on the relative strengths of the nanotube-polymer composite and the polymer alone. It will also depend on the relative thicknesses of the nanotube-polymer layer and the polymer layer, generally equal to about 1.5 times the thickness of the tow after molding.
These and other aspects of the invention are described below, while still others will be readily apparent to those skilled in the art based on the descriptions provided in this specification.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B show a schematic view of a section of a woven fiber reinforced composite and a perspective view of the surface of the composite. In FIG. 1A the composite is at its elevated cure temperature and the composite surface is generally flat. In FIG. 1B , the composite has cooled from its curing temperature and the composite surface displays a regular arrangement of dips and rises which is related to the arrangement of the fibers in the mat reinforcement.
FIG. 2 shows a schematic view of a section of a woven fiber reinforced composite and a perspective view of the surface of the composite after addition of a nanocomposite resin layer incorporating, in a resin matrix, carbon nanotubes. The carbon nanotubes extend through the thickness of the nanocomposite resin layer and are oriented generally normal to the surface of the nanocomposite resin layer.
FIGS. 3A-3C show a schematic illustration for a sequence of steps required for fabrication of a vertically aligned carbon nanotube/polymer layer including: growing the nanotubes of a desired length on a substrate; infiltrating the substrate with a resin to form a resin/nanotube composite; and separating the resin/nanotube composite from the substrate to form a resin/nanotube layer.
FIG. 4 shows the schematic stress-strain behavior of a representative polymer matrix and compares it with the stress-strain behavior of an oriented nanotube reinforced polymer.
DESCRIPTION OF PREFERRED EMBODIMENTS
The following description of the embodiment(s) is merely exemplary in nature and is not intended to limit the invention, its application, or uses.
Carbon fibers ranging in diameter from about 1 micrometer to about 20 micrometers in diameter are popular reinforcements for high performance fiber reinforced polymer composites. Such fibers may be employed individually but, more commonly a number of such fibers will be gathered together to form a tow with a lateral dimension of between 500 micrometers to 1000 micrometers. A plurality of such tows may be arranged as warp and weft and woven together into a woven reinforcing mat. Such a mat may be impregnated with polymer resin or a B-staged polymer resin to form a prepreg and then assembled, with other prepregs, to form a layup. The layup may be shaped into a desired form, by application of pressure in a die, and cured, in the die, by application of heat to produce the desired carbon fiber reinforced polymer composite article.
But, conventional carbon fiber reinforced polymer composites often exhibit visible surface features which mimic the subsurface distribution of the fibers in the composite. These visible surface features, known as print through, are most visible when the fibers are placed in an organized or patterned fashion, such as the just-described woven mat.
Print through predominantly arises due to the difference in coefficient of thermal expansion (CTE) of the polymer and the carbon fiber reinforcement. FIG. 1A depicts a sectional view of a layer of prepreg 10 incorporating a woven reinforcement 11 and a thermosetting polymer resin 16 . Woven reinforcement 11 consists of a warp 12 and weft 14 which pass over and under one another in alternating fashion. Typically each of the warp 12 and weft 14 will consist of tows, each containing a plurality of individual fibers. It is intended that these prepreg layers, and possibly additional underlying layers 10 ′, 10 ″ (shown in gho st), will be assembled into a layup. The uppermost layer, layer 10 , will be positioned adjacent to a face of the mold cavity so that its surface 18 will form the surface of the composite article. As is common when fabricating a layup of several prepreg layers the carbon fiber weave of each of layers 10 , 10 ′ and 10 ″ has been slightly misaligned relative to its neighboring layer for better uniformity of in-plane properties in the finished article. The details of the weave and the misalignment are intended only to be illustrative, and should not be construed as either limiting or representative.
For clarity, the traces of warp 12 and weft 14 of surface layer 10 have been mapped onto surface 18 as dotted lines 20 and 22 . Three regions may be distinguished. In regions 24 which lies between the warp 12 ( 20 ) and the weft 14 ( 22 ) of the weave there is no reinforcing fiber so that at this location the prepreg is substantially resin. In regions 26 which overlie either of the warp 12 ( 20 ) or the weft 14 ( 22 ), the prepreg will consist of reinforcing fiber and resin in comparable proportions. At locations 28 the warp 12 ( 20 ) and weft 14 ( 22 ) overlie one another so that the prepreg at this location will predominantly consist of reinforcing fiber with minimal resin.
During cool-down after elevated temperature curing, the composite part will contract unequally in these different locations 24 , 26 , 28 due to the different proportions of resin and reinforcing fiber. A typical coefficient of thermal expansion of an epoxy, representative of many potential matrix materials, ranges from about 60-100×10 −6 /° C. Graphite fibers show a negative thermal expansion coefficient of about −1.4×10 −6 /° C. along their fiber axis and a thermal expansion coefficient of about 2.1×10 −6 ° C. in a direction transverse to the fiber axis. There will therefore be a significant difference in the extent of thermal expansion of a volume containing both fibers and polymer depending on the proportions of polymer and fiber. Locations which contain higher proportions of polymer will exhibit a much greater contraction on cooling.
The disparity in CTE and the wide variation in fiber/polymer contents occurring at locations 24 , 26 and 28 results in major difference in the elevations of the article surface in these locations. Of course, these locations 24 , 26 , and 28 repeat with the periodicity of the weave so that the variation in surface elevation will vary, in a regular and systematic manner across the entire surface 18 and will have a periodicity which reflects and mimics the periodicity of the weave. This phenomenon is known as print through, and is illustrated in FIG. 1B which shows an undulating periodic two-dimensional pattern of alternating peaks 32 and valleys 30 .
Print through therefore results from the differing proportions of polymer resin in different locations in the surface layer and the large difference(s) in CTE between the polymer and the reinforcing fiber. Both issues may be addressed by placing, as the uppermost layer of the layup, and hence on the article surface, a layer of more homogeneous composition which exhibits a lesser CTE.
Such a layer is schematically illustrated in FIG. 2 . The layup now contains at least two layers, the original woven carbon fiber layer 10 (and optionally 10 ′ and 10 ″) and a second layer 34 consisting of a compatible, B-staged resin 36 and a plurality of carbon nanotube reinforcements 38 extending through the layer thickness t′ and oriented generally normal to the layer surfaces 40 , 42 .
Carbon nanotubes are hollow co-axial cylinders of carbon whose diameters are measured in nanometers with lengths which may extend over tens of millimeters and exhibit high strength and a low coefficient of thermal expansion (CTE) along their cylinder axis. When the spacing of the nanotubes is small relative to the wavelength of visible light, layer 34 will appear as a homogenous layer. Also the high strength and low CTE of the carbon nanotubes will reduce the CTE of the nanotube reinforced polymer relative to the polymer alone. This greater homogeneity of the surface layer and its reduced CTE will cooperate to minimize the spatial variations in contraction exhibited by any of the woven fiber reinforced layers. In turn, this will thereby reduce the tendency for print through in the composite article. These benefits require that layer 34 be bonded to layer 10 so that it may be integrated into the prepreg. It is therefore important that the resin of layer 34 be at least compatible with, and preferably, identical to, the resin of layer 10 . It is also important that layers 10 and 34 be brought into intimate contact over their entire area. This may be accomplished by assuring that the prepreg thickness is modestly greater than the mold cavity thickness to ensure that die closure will enforce the desired relationship between layers.
One approach to forming a carbon nanotube reinforced resin or B-staged resin layer is illustrated in the steps shown in FIGS. 3 A-C. Catalyst particles may be formed or laid down on a suitable substrate. The particles may be laid down as a thin layer of metal salt deposited from solution for example a nitrate, and then reduced to form small metal droplets on the surface. Or a metal powder may be sprinkled on the substrate. Alternatively, the salt reduction process may be performed using a thin frangible layer, of say, aluminum oxide as a support. After forming the catalyst particles the particle-support combination may be crushed to form small particles with yet smaller associated metal catalysts. The crushed, catalyst-containing particles may then be laid down on the substrate. The substrate and catalyst particles are first conditioned by high temperature exposure to a process gas, for example, ammonia, nitrogen or hydrogen. After conditioning, particles are exposed to a slowly-flowing (about 1 mm/second) carbon-containing gas such as acetylene, ethylene, ethanol or methane at a temperature of approximately 750° C. and held at temperature for a period of several hours. This procedure results in the formation of nanotubes of predictable lengths and diameters whose diameters may measure in tens of nanometers with lengths of about a few millimeters. The nanotubes 38 , as illustrated in FIG. 3A , will be generally parallel to one another and oriented generally normal to surface 50 of substrate 52 .
In FIG. 1B the carbon nanotubes 38 of FIG. 3A , still associated with substrate 52 are infiltrated, with a flowable polymer resin such as an epoxy containing sufficient hardener to enable B-stage polymerization 54 and render a substantially filled composite carbon nanotube-resin block 56 attached to substrate 52 as shown in FIG. 3B . After polymerization has proceeded sufficiently to develop the desired B-staged resin, it may be removed from the substrate as a layer 56 ′ of carbon nanotube-resin composite with the nanotubes oriented generally normal to the substrate surface as shown in FIG. 3C . In an alternative approach, layers of any suitable thickness may be removed from block 56 ( FIG. 3B ) using a microtome, or other suitable cutting device.
In common with other composite materials, the strength and stiffness of a nanotube-polymer composite, that is the strength and stiffness of layer 56 ′ when fully cured, is greater than that of the polymer alone. This is shown in FIG. 4 which schematically compares the stress strain behavior of the nanotube composite, curve 60 with that of the polymer alone, curve 62 . The initial slope of the respective curves, is greater for the composite 64 than for the polymer 66 and the strength of nanotube is greater than the strength of the polymer
The addition and incorporation of carbon nanotube-reinforced layer 34 to the prepreg incorporating at least woven reinforcement layer 10 ( FIG. 1A ) imparts at least three attributes to the prepreg which cooperatively reduce print through. The scale of the inhomogeneity of the surface layer is dramatically reduced from the tow spacing of between 1 and 5 millimeters to the nanotube spacing of 300 nanometers or less; the low CTE of the nanotubes in combination with their close spacing acts to reduce the CTE of the nanotube-resin composite, narrowing the difference in CTE between the carbon fibers of the tow and the unreinforced resin; and the greater strength and stiffness of the nanotube polymer composite, shown in FIG. 4 , will resist the greater thermal contraction of the polymer.
To be effective the nanotube layer must be sufficiently strong to resist the stresses generated in the underlying layers. The relative strengths of the layers will generally depend on the product of the intrinsic strength of the layer and the layer thickness. So the nanotube-polymer composite layer, to exert appreciable influence on underlying carbon fiber mat reinforced polymer layer, should be of comparable thickness. The influence of the nanotube-polymer layer will increase with increasing thickness of the layer but further improvement in surface quality is minimal with nanotube-polymer layer thicknesses greater than about 1.5 times the thickness of the underlying woven carbon fiber mat reinforced polymer layer. In turn, the thickness of the fiber mat reinforced polymer layer will generally equal twice the thickness of the tow since its thickest location will be where the warp and weft cross over one another, location 34 in FIG. 1 . So it is preferred that the nanotube-polymer layer be between twice and three times the tow thickness after molding.
Print through is not restricted to only woven carbon fiber reinforcements in polymers. Any woven fiber reinforcement in which the fiber CTE differs substantially from that of the polymer matrix may also exhibit the phenomenon. For example glass has a CTE which ranges from about 4-9×10 −6 /° C. This is again very different from the 60-100×10 −6 /° C. of an epoxy and so may also lead to issues of print through. The practices of the invention are similarly applicable to woven glass fiber reinforced polymers, fabricated, for example, of E-glass or S-glass and any other woven reinforcement in addition to woven carbon fiber reinforcements.
The practice of the invention has been illustrated through reference to certain preferred embodiments that are intended to be exemplary and not limiting. The full scope of the invention is to be defined and limited only by the following claims.
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Polymer articles are often reinforced by addition of fibers which may be assembled into a structured reinforcement such as a woven mat or sheet and the mat or sheet serves as the reinforcement. Such woven fiber-reinforced polymer composite articles may exhibit undesirable variations in surface height which mimic the geometry of the underlying reinforcements, a phenomenon known as print through. By forming, on the surface of the article, a relatively thin, layer of a compatible polymer incorporating closely-spaced, short, carbon nanotubes more or less uniformly dispersed throughout the layer and oriented normal to the article surface, print through may be reduced or eliminated. Methods for fabricating such an article are detailed.
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TECHNICAL FIELD
The present invention relates to an apparatus, a kit of parts and a related method for use in a verbal communication between a speaker and a listener of a plurality of participants, where the listener cannot easily see who is speaking, the apparatus operable to provide the listener with a sensory output indicating the identity of the speaker.
BACKGROUND ART
There exist many circumstances requiring verbal communication between a speaker and a listener of a plurality of participants, where the separation of the speaker and the listener is such that it can be hard for the listener(s) to determine who spoke.
The difficulty can arise when the speaker and the listener(s) are located out of direct line of sight. One such example is the use of an audio conference call held over a telecommunications network between multiple participants located at different geographical locations. This is well-known as a means of conducting business communications. However, when the number of participants in a call is more than two, it can be difficult for the participants to work out who of them is speaking at any given time. This problem is a consequence of the participants not being in direct line of sight with each other and therefore having to rely solely upon an audio signal to identify who is speaking on the other end of the call. The problem is exacerbated when conducting a conference call over a conventional plain old telephone service (POTS) network, because the useable voice frequency band over a POTS network is limited to approximately 300 Hz to 3,400 Hz, i.e. a small proportion of the frequency band (around 20 Hz to 20,000 Hz) representative of the range of human hearing. Therefore, in addition to the listening participants having to rely solely upon their auditory sense to identify who is speaking, those same participants have to base the identification on an audio signal which is compressed. Speaker identification can be further hampered by any distortion in the speech of the speaking participant which may be introduced by transmission over a POTS network.
The same difficulty of the listener(s) identifying who is speaking can also arise in a conference or lecture having a plurality of participants located in a single room (such as a crowded lecture theatre). Where there are a large number of participants in a single room, it can be hard for those listening to determine who is speaking amongst the participants, even if the speaker is in direct line of sight with those listening.
The use of voice recognition systems which are able to identify who is speaking based upon recognising a given person's voice from their voice signature is known. However, such systems would require training to establish a voice profile sufficient to identify a given person, as well as a database containing the voice profiles of all persons on a given call. Such a system would therefore be costly in terms of both time and infrastructure.
Consequently, there is a need for an improved means of identifying who is speaking in a verbal communication scenario between a listener and a speaker where the listener cannot easily see who is speaking
SUMMARY OF INVENTION
Accordingly, an embodiment of the invention provides an apparatus for use in a verbal communication between a speaker and at least one listener, the speaker and the at least one listener forming all or part of a plurality of participants, wherein the speaker and the at least one listener are spatially separate from each other, the apparatus operable to provide the listener with a sensory output associated with the identity of the speaker; the apparatus comprising: an identification device, wherein the identification device is wearable or carriable by a speaker, the identification device comprising a vibration sensor for detecting vibrations associated with speech of the speaker, wherein the identification device is configured to store identification data representative of the identity of either or both of the speaker and the identification device, whereby the identification device is associatable with the identity of the speaker, wherein the identification device is operable such that in response to the vibration sensor detecting vibrations associated with speech of the speaker, the transmitter transmits an identification signal comprising or generated from the stored identification data; the apparatus further comprising a display device for use by a listener, the display device operable to receive such an identification signal and to generate from the received identification signal a sensory output indicating the identity of either or both of the speaker and the identification device.
For the purpose of the present invention, by “plurality” of participants is meant two or more participants. Further, the “speaker” and the “listener” may also be referred to within this text as the “speaking participant” and the “listening participant” respectively, with the terms used interchangeably.
Embodiments of the present invention have application in any verbal communication scenario between a speaker and a listener where the listener cannot easily see who is speaking, thereby hindering the listener's ability to establish the speaker's identity. Applications may include but are not limited to:
Use in a conference or lecture having a plurality of participants to help establish the identity of who is speaking at any given time. Where there are a large number of participants in a single room (such as a crowded lecture theatre), it can be hard for those listening (i.e. the “listeners”) to determine who is speaking amongst the participants even if the speaker is in direct line of sight with those listening. The apparatus of an embodiment provides a means of readily enabling a listener to determine the identity of who is speaking in a crowded space. Use in telecommunications or radio applications where the speaker and listener are not in direct line of sight with each other. The apparatus of an embodiment would be particularly useful in an audio communications conference undertaken over a telecommunications or radio network between a plurality of participants located at different geographical locations corresponding to different nodes of the network. Non-limiting examples of telecommunications networks with which the apparatus of an embodiment may be used include a plain old telephone service (POTS), a cellular telephone network and/or voice over internet protocol (VOIP). An embodiment would also be beneficial for use in radio communications between a pilot on an aircraft and an air traffic controller and/or other aircraft. Alternatively, an embodiment would be beneficial when used as part of a radio communications system for ground-based transport—such as for use by a taxi company or lorry haulage company.
When considering use of embodiments of the present invention in any such “verbal communication” scenario having a plurality of participants, it is worth highlighting that each participant may be speaking or listening at different times. Therefore, the roles of “speaker” and “listener” are not necessarily fixed. This can be understood more clearly when considering use of embodiments of the present invention during an audio communications conference over a telecommunications or radio network between a plurality of different participants—a given participant may be a “speaker” at one instance in the conference and a “listener” at another instance in the conference. Therefore, when describing the use of the identification device and the display device of embodiments of the present invention, the terms “speaker” and “listener” as used herein can apply to one and the same person (depending upon whether that person happens to be speaking or listening at a given point in time during the verbal communication).
Having the identification device configured to store identification data representative of the identity of either or both of the speaker and the identification device can be enabled in various different ways. Non-limiting examples may include the identification device provided in the form of an employee ID tag, with the tag containing a chip encoded with identification data representative of the identity of a given employee. The identification data may take the form of the name and employee number of the employee. Alternatively, the identification data may include one or both of a colour and a shape associated with a given identification device. Taking the non-limiting example of an audio communications conference conducted over a telecommunications or radio network between a plurality of participants at different nodes of the network, each of the participants to the conference may be provided with their own identification device configured with identification data representative of a visible marking uniquely linked to that identification device. This unique linkage may take the form of each identification device having a unique visible marking in the form of a colour, a shape or a combination thereof, with a different colour and/or shape provided on each identification device, and with the identification device including a chip or other storage means encoded with identification data representative of the colour and/or shape. The use of such colour and/or shape provides an example of where the stored identification data would be representative of the identity of the identification device itself and would provide the benefit of avoiding the need for the identification data stored on the identification device to contain any personal information (for example, name, date of birth and/or address) of any of the participants.
The sensory output, in an embodiment, comprises one or more of a visual output, a tactile output and an audible output. An audible output may take the form of an auditory voiceover providing the name of the speaker, although it is acknowledged that this may potentially impede the ability of the listener(s) to hear what the speaker is saying. For those reasons, a visual output is preferred. The visual output takes the form of any visual representation sufficient to establish the identity of either or both of the speaker and the speaker's identification device to the listener (based upon the information contained in the identification signal). For example, the visual output may simply be a text representation of the name of the speaker, or any alphanumeric identifier representative of either of both of the speaker and the identification device. Alternatively, the visual output may take the form of colour and/or shapes. For example, where each identification device is provided with its own unique visible marking in the form of a colour, a shape or combination thereof and the identification data is representative of the colour and/or shape (as outlined in a preceding paragraph), the sensory output provided on the display device may be a visual representation of the colour and/or shape. Alternatively, a tactile output may take the form of Braille (being suitable for blind participants) or vibrations (such as the output of different vibratory signals corresponding to the different identification signals transmitted from different identification devices).
In an embodiment, the identification device comprises input means operable for the speaker to pre-configure the identification device with the identification data. The provision of such input means for pre-configuring the identification device would allow a speaker to pre-configure a given identification device with identification data representative of their own identity. In use, in an embodiment, such pre-configuration would occur before commencement of the “verbal communication”. Explaining further, when considering use in air ground communications between a pilot in an aircraft and an air traffic controller, the pilot would, in an embodiment, pre-configure their identification device before take-off; when considering the example of an audio communications conference over a telecommunications or radio network between a plurality of participants, each participant would, in an embodiment, configure their identification device before the start of the conference. Conveniently, the input means comprises one or both of a keypad and an audio recording device. The speaker would therefore be able to pre-configure an identification device with identification data such as their name (or any other personal identifier) by way of a keyboard input and/or an audio input.
In an embodiment, the identification device is configured to be re-associatable with the identity of another person. This feature according to an embodiment of the present invention would ensure that the identification device is not limited to being permanently associated with a given person, thereby ensuring that the identification device could be used by another person at a future time. When considering the use of the apparatus of embodiments of the present invention within an organisation having a large number of employees, the feature of “re-associability” avoids having to provide every employee with their own identification device, with it being unlikely that all employees would be participating in the same “verbal communication” simultaneously. Further, the feature of re-associability also provides the ability to re-use a given identification device with any number of people over a period of time.
It is envisaged that in use during the “verbal communication” scenario, all of the participants would be provided with their own wearable or carriable identification device. This would thereby ensure that each participant possesses means suitable for generating an identification signal uniquely associated to them when they speak. The number of display devices necessary would be dependent upon the particular verbal communication scenario. Considering use of embodiments of the present invention during a conference or lecture having a number of participants in a single room, it may be sufficient for there to be only a single common display device which could be viewed by all of the participants. However, considering use of embodiments of the present invention during an audio communications conference undertaken over a telecommunications (or radio) network between a plurality of participants located at different geographical locations corresponding to different nodes of the network, it is envisaged that at least one display device would be provided at each node of the network. This would thereby provide the ability for those participant(s) present and listening at each node of the network to be given a real-time sensory indication of who is speaking at a different node, based upon an identification signal received over the network from the identification device of the participant who is speaking.
In an embodiment, the identification device is configured such that the transmitter only transmits the identification signal after a minimum duration of continuous speech from the speaker. This feature according to an embodiment of the present invention has the beneficial effect of avoiding the display device being triggered based upon the speaker coughing or sneezing, thereby helping to avoid false indications of a participant speaking during use of the apparatus. Conveniently, the minimum duration is between 0.5 and 2 seconds. Having too large a minimum duration would risk an unacceptable time lag between a) the speech of a speaker first being heard by the listener(s) and b) the display device (for the listener(s)) receiving the identification signal to generate the sensory output of the identity of who is speaking.
In an embodiment, the identification device is locatable adjacent the neck or chest of the speaker. This feature of the present invention assists in better ensuring that the vibration sensor is able to detect vibrations from use of the vocal chords of the speaker. The identification device may conveniently be attached to a necklace for wearing about the neck of a speaker. Conveniently, the identification device may be handheld, affixable to an item of clothing worn by a speaker, or affixable directly to a speaker's body (for example, by the use of straps or adhesive tape)—these all falling within the scope of the identification device being “wearable or carriable”.
Having the identification device so that it is worn or carried in use by a participant provides proximity of the identification sensor to that participant. This provides the advantage of more easily being able to calibrate the vibration sensor so that it only detects speech from the participant who is wearing or carrying the identification device. This advantage is especially relevant where other people are present in the same room as a particular participant, because it avoids the identification device being triggered by speech from people other than the participant who is wearing or carrying the particular identification device.
The transmitter of the identification device may be configured to transmit the identification signal as an audio signal having a frequency between 20 Hz and 20,000 Hz. Such a frequency range corresponds to the commonly accepted range of frequencies audible to human hearing. Conveniently the transmitter is configured to transmit the identification signal as an audio signal having a frequency within a narrower frequency band of between 300 Hz and 3,400 Hz. This narrower frequency band is particularly suitable for direct transmission of the identification signal over a telecommunications network in the form of a plain old telephone service (POTS), for which the transmissible audio frequency range represents only a portion of the frequency range commonly associated with the range of human hearing (20 Hz to 20,000 Hz).
Alternatively, the transmitter may be configured to wirelessly transmit the identification signal at a frequency above 20,000 Hz, the apparatus further comprising a first encoder communicatively couplable between the identification device and a telecommunications or radio network, the first encoder operable to receive and convert the transmitted identification signal to one of:
a) an audio signal having a frequency in the range 20 Hz to 20,000 Hz (or alternatively in the range 300 Hz to 3,400 Hz); or b) an encrypted digital signal, wherein for b) the display device comprises or is communicatively couplable with a decoder for decoding the encrypted digital signal.
The transmission of the identification signal from the identification device at a frequency above 20,000 Hz has the beneficial effect of ensuring that it is not heard by the speaker and therefore does not interfere with their concentration and affect their speech. Subsequent conversion by the first encoder to an audio frequency in the range 20 Hz to 20,000 Hz is beneficial when the identification device of the apparatus is used with a telecommunications or radio network able to transmit audio signals corresponding to the full range of human hearing; whereas conversion to an audio signal having a frequency in the range 300 Hz to 3,400 Hz is particularly beneficial when the apparatus is used with a telecommunications network in the form of a POTS.
In addition to the use of a first encoder as outlined above, the identification device may also be operable to encode the identification signal for transmission by the transmitter as a wireless Bluetooth signal, wherein the identification device and the first encoder are Bluetooth-pairable to each other. The use of the Bluetooth protocol provides a secure way to wirelessly connect and exchange information between the identification device and the first encoder.
Conveniently, the first encoder is integrated within a terminal connectable to a node of a telecommunications or radio network, the terminal operable for audio communications to and/or from the network. In one example, the terminal may be a telephone connectable over a POTS, the telephone having a microphone for detecting speech of one or more participants located in proximity thereto and a loudspeaker for conveying audio signals received over the POTS to anyone listening.
In an embodiment, apparatus further comprises a filter integrated within or communicatively connectable to the display device, wherein the filter is operable to receive a combined signal comprising both the identification signal and an audio signal of the speech of the speaker and is further operable to filter the combined signal to extract the identification signal from the combined signal prior to audio output of the filtered signal to the listener. The use of such a filter helps to ensure that the listener(s) hear the words spoken by a participant speaking at another node of the network without interference or distortion from the identification signal.
In an embodiment, the display device is integrated within a terminal connectable to a node of a telecommunications or radio network, the terminal operable for audio communications to and/or from the network. This feature according to embodiments of the present invention provides the advantage of providing a single integrated terminal which can serve for providing audio input and audio output to/from a telecommunications or radio network, whilst also serving the function of providing a visual indication of who is speaking at another node of the network. Alternatively or in addition, the identification device is integrated within a terminal connectable to a node of a telecommunications or radio network, the terminal operable for audio communications to and/or from the network; for example, the terminal may be a cellular telephone which may function as both the identification device and the display device.
In an embodiment of the present invention, there is provided a terminal operable for audio communications to and/or from a telecommunications or radio network, wherein the terminal comprises one or both of the identification device and the display device of embodiments of the present invention. In an embodiment, the terminal may be a cellular telephone.
In an embodiment of the present invention, there is provided a kit of parts comprising the identification device and the display device of embodiments of the present invention. Such a kit would be of value because it would provide a person with both:
a) the means (i.e. the “identification device”) necessary to generate an identification signal associated with their identity—being suitable for use by that person when being a speaker during the verbal communication; and b) the means (i.e. the “display device”) necessary to provide a visual output indicating the identity of who is speaking when that person is a listener during the verbal communication.
In an embodiment of the present invention, there is provided a method of identifying who is speaking in a verbal communication between a speaker and at least one listener, the speaker and the at least one listener forming all or part of a plurality of participants, wherein the speaker and the at least one listener are spatially separate from each other, the method providing the at least one listener with a sensory output associated with the identity of the speaker, the method comprising: providing an identification device, wherein the identification device is wearable or carriable by the speaker, the identification device comprising a vibration sensor for detecting vibrations associated with speech of the speaker, wherein the identification device stores identification data representative of the identity of either or both of the speaker and the identification device, whereby the identification device is associated with the identity of the speaker; detecting with the vibration sensor vibrations associated with speech of the speaker, the detecting performed when the speaker is wearing or carrying the identification device; in response to the detection of the vibrations, transmitting from the identification device an identification signal comprising or generated from the stored identification data; and providing a display device for use by the at least one listener, wherein the display device receives such an identification signal and generates from the received identification signal a sensory output indicating the identity of either or both of the speaker and the identification device.
The method of an embodiment of the present invention may also incorporate steps corresponding to the functionality provided by various possible features of the apparatus outlined above.
BRIEF DESCRIPTION OF DRAWINGS
Embodiments of the invention are described with reference to the following accompanying drawings:
FIG. 1 shows a representation of a telecommunications network having a number of different nodes.
FIG. 2 shows a first embodiment of the invention when used with the telecommunications network shown in FIG. 1 .
FIG. 3 shows a second embodiment of the invention when used with the telecommunications network shown in FIG. 1 .
FIG. 4 shows a third embodiment of the invention when used with the telecommunications network shown in FIG. 1 .
FIG. 5 shows an embodiment of the invention in which the housings of three different identification devices are each provided with their own unique visible marking.
Please note that the figures are not drawn to scale, and are intended to be non-limiting examples of various possible embodiments of the invention.
DESCRIPTION OF EMBODIMENTS
FIG. 1 shows a simplified representation of a telecommunications network 10 for use during an audio communications conference, the network having a number of different nodes 11 . Each of the nodes 11 corresponds to a different geographic location. In the embodiment shown in FIG. 1 , a terminal 20 is connected to the telecommunications network 10 at each respective node 11 , with the terminal providing for audio communications to and from the telecommunications network 10 . Examples of embodiments of the present invention are described in FIGS. 2 , 3 and 4 when the telecommunications network is a plain old telephone service (POTS), with the use of POTS systems remaining widespread for audio conferencing. However, as can be understood by earlier parts of the description, embodiments of the present invention are applicable for use with other forms of telecommunication network (for example, a cellular telephone network and/or voice over internet protocol (VOIP)).
In an alternative embodiment not shown in the drawings, the network 10 would be a radio communications network. One such radio communications network 10 is a radio network forming part of a radio communications system between an aircraft and a ground station, with the aircraft and ground station corresponding to different nodes 11 of the network.
During an audio communications conference between a plurality of participants 30 , one or more of the participants is located at each nodal location 11 (as illustrated in FIG. 1 ).
FIGS. 2 , 3 and 4 show an exemplary representation of embodiments of the present invention from the perspective of a participant who at one point in time is speaking during the audio communications conference (i.e. acting as a “Speaker”) and at another point in time is listening (i.e. acting as a “Listener”). The apparatus has an identification device 40 and a display device 70 .
Without seeking to limit the scope of the invention as outlined in the claims, the form and function of the identification device 40 and display device 70 is outlined below.
The embodiment of FIG. 2 shows an identification device 40 provided on a necklace 41 . In use, the necklace 41 would be worn around the neck of a given one of the participants 30 , so that the identification device is located proximate the neck and thereby the vocal chords of that participant. Each participant 30 to the audio communications conference is provided with their own identification device 40 to be worn or carried by them. The identification device 40 includes a housing incorporating a vibration sensor 42 , an input means 43 , a memory 44 , a processor 45 , and a transmitter 46 .
FIG. 2 also shows a terminal 20 in the form of a conference-enabled telephone connected to the telecommunications network 10 , the network having the form of a plain old telephone service (POTS). The terminal 20 has a microphone 21 and a loudspeaker 22 for enabling audio communication to and from the network 10 .
Prior to commencement of the audio communications conference, each participant 30 would use the input means 43 to input identification data into the memory 44 of their own respective identification device 40 . The identification data would be representative of the identity of that participant. The form of the input means 43 is not shown, but as outlined in earlier parts of the description it may include a key pad and/or an audio recorder. The identification data might take the form of the name of the participant, or another identifier uniquely associated with the participant's identity (for example, an employee staff number). The act of pre-configuration ensures that the identification device 40 is twinned (i.e. associated) with the identity of a given participant 30 until pre-configured with identification data of another person.
Upon the participant 30 commencing speaking (at which point they become a “Speaker” for the purposes of the present invention), the vibration sensor 42 detects vibrations ‘V’ (see FIG. 2 ) associated with the speech S of the Speaker 30 . The proximity of the identification device 40 to the vocal chords of the Speaker 30 assists the vibration sensor 42 in detecting the onset of speech S from the Speaker. However, in alternative embodiments not shown in the figures, the identification device 40 is handheld by the participant 30 , or attached to an item of clothing worn by the participant.
In response to the vibration sensor 42 detecting speech S of the Speaker 30 , the processor 45 and memory 44 cooperate with the transmitter 46 to cause the transmitter to wirelessly transmit an identification signal 50 . The identification signal 50 is generated from or comprises the identification data that was input during the pre-configuration step outlined above. In the embodiment shown in FIG. 2 , the processor 45 executes computer code stored in the memory 44 , the computer code operating upon the identification data to generate the identification signal 50 therefrom. The computer code is such as to ensure that the transmitter 46 only transmits the identification signal 50 after the vibration sensor 42 has detected a minimum duration of continuous speech S from the Speaker. For the embodiment of FIG. 2 , the identification signal 50 is an audio signal in the form of a “chirp” having a frequency in the range 300 Hz to 3,400 Hz, with the chirp representing a compressed form of the identification data.
The “chirp” 50 (i.e. the “identification signal”) is detected by the microphone 21 of the terminal 20 , with the microphone 21 also detecting the speech S of the Speaker 30 . The terminal 20 then sends a combined signal 550 containing both i) the chirp 50 and ii) an audio signal 500 representing the speech S of the Speaker 30 , across the network 10 to corresponding terminals 20 of the other participants 30 located at the other nodes 11 of the network. Each of these other participants 30 who receives the combined signal 550 becomes a “Listener” for the purposes of embodiments of the present invention.
For convenience, FIG. 2 is also used to describe embodiments of the present invention from the perspective of such a “Listener”.
FIG. 2 shows the display device 70 integrated into the terminal 20 , with the display device including a display screen 71 . Also integrated into the terminal 20 is a filter 80 . On the terminal receiving the combined signal 550 , the signal first passes through the filter 80 , which filters the combined signal 550 to extract the identification signal 50 from the combined signal 550 . After filtering, the extracted identification signal 50 is then conveyed to the display device 70 . As shown in FIG. 2 , the display device 70 includes a memory 72 and a processor 73 , with the processor 73 executing computer code stored in the memory 72 . The computer code operates upon the extracted identification signal 50 to generate a sensory output in the form of a visual representation of the identity of the Speaker, the visual representation being output to the display screen 71 . In the embodiment shown in FIG. 2 , the visual representation is the name of the Speaker. The speech signal 500 is then able to be conveyed to the loudspeaker 22 of the terminal 20 to enable the Listener to hear what the Speaker was saying.
An embodiment is shown in FIG. 3 , with those features in common with the embodiment of FIG. 2 having the same reference numerals. In the embodiment of FIG. 3 , the display device 700 is provided as a standalone module which is structurally distinct from the terminal 20 and connected in-line between the network 10 and the terminal 20 . The filter 800 is shown integrated into the display device 700 . The filter 800 functions in a similar manner to that of the filter 80 in the embodiment of FIG. 2 , thereby enabling a clean audio signal containing only the speech of the Speaker to be conveyed to the terminal 20 for output via the loudspeaker 22 to the Listener. Further, the identification signal 50 extracted from the combined signal 550 would be processed within the display device 70 to generate a visual representation on the display screen 710 of the identity of the Speaker. This alternative form of display device 700 would have the advantage over the embodiment of FIG. 2 of not necessarily requiring the terminal 20 to be modified, thereby permitting a conventional conference-enabled telephone to be used as the terminal.
For the embodiment of FIG. 3 , each participant would be provided with a kit of parts, the kit containing both the identification device 40 and the display device 700 , where the identification device and display device are usable with but structurally distinct from the terminal 20 .
An embodiment is shown in FIG. 4 . This embodiment is a variation of the embodiment of FIG. 3 . In contrast to the embodiments of FIGS. 2 and 3 , the embodiment of FIG. 4 includes an encoder 60 , where the encoder 60 is spatially distinct and separate from the identification device 60 and the terminal 20 , and connected to the terminal 20 by a wired connection. In an alternative embodiment not shown in the figures, the encoder 60 is integrated within the terminal 20 itself. The embodiment of FIG. 4 also differs from that of FIGS. 2 and 3 in that the identification signal 50 wirelessly transmitted by the transmitter 46 is a non-audible signal above 20,000 Hz. The non-audible identification signal 50 is received by the encoder 60 , with the encoder 60 acting to convert the identification signal 50 to an audio signal having a frequency in the range 300 Hz to 3,400 Hz, with the converted identification signal 50 then conveyed via the wired connection to the terminal 20 . The terminal 20 then sends the converted identification signal 50 across the network 10 along with an audio signal of the speech 500 of the Speaker 30 . An advantage of the embodiment of FIG. 4 over that of FIGS. 2 and 3 is that the wireless transmission of the identification signal 50 from the identification device 40 to the encoder 60 as a non-audible signal (i.e. having a frequency above 20,000 Hz) avoids the identification signal interfering with the concentration and speech of the Speaker 30 . In an embodiment not shown in the figures, the identification signal 50 may be wirelessly transmitted as a Bluetooth signal, with the identification device 40 and encoder 60 being Bluetooth-pairable.
FIG. 5 shows a view of the external view of the housing of three different identification devices 40 a , 40 b , 40 c . Each of the identification devices 40 a , 40 b , 40 c is provided with its own unique visible marking 90 a , 90 b , 90 c on the exterior surface of the housing. The embodiment shown in FIG. 5 shows these visible markings 90 a , 90 b , 90 c being in the form of a shape having a particular texture or colour. Each of the identification devices 40 a , 40 , 40 c has its memory 44 encoded with identification data representative of its respective visible marking 90 a , 90 b , 90 c . In use, the identification signal 50 transmitted from each identification device 40 a , 40 b , 40 c would correspond to each device's marking 90 a , 90 b , 90 c . Although not explicitly shown in any of the figures, the display device 70 , 700 would display a visual representation corresponding to the visual marking of the identification device belonging to whichever participant 30 spoke.
The description uses examples to disclose the invention and also to enable a person skilled in the art to make and use the invention. For the avoidance of doubt, the invention as defined in the claims may include within its scope other examples that occur to those skilled in the art which may differ from those examples indicated in the figures of this document.
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An apparatus for use in a verbal communication between a speaker and at least one listener, where the speaker and the at least one listener are spatially separate from each other, the apparatus provides the listener with a sensory output associated with the identity of the speaker, the apparatus including an identification device including a vibration sensor for detecting vibrations associated with speech of the speaker, is configured to store identification data representative of the identity of the speaker or the identification device, is associable with the identity of the speaker, and, in response to detecting vibrations, transmits an identification signal comprising or generated from the stored identification data, and a display device operable to receive the identification signal and to generate from the received identification signal a sensory output indicating the identity of either or both of the speaker and the identification device.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a recreational floating device and, more specifically, to a device for insertion in an inner tube for use in river rafting or "tubing".
2. Brief Description of the Prior Art
The sport of "tubing" has gained increasing popularity in recent years. An automotive inner tube is used as a floating seat to support a person in water. Normally, the person will place legs, arms and upper back over the top of the tube, and permit lower back and bottom to protrude through the tube into the water. When the body of water is a river, particularly one with small rapids, an exhilarating and enjoyable experience can be had.
Inner tubes are the chosen device for tubing for a number of reasons including their availability and their minimal cost, and floating on a body of water without using an inner tube cannot properly be called "tubing". As a consequence, the equipment used for tubing has remained fairly constant over the years, rarely comprising anything beyond an inner tube.
Several drawbacks to the use of an unadorned inner tube for tubing were identified in U.S. Pat. No. 4,795,387 to Morgan. These drawbacks include the possibility of tubes being too large or too small for comfortable use, the possibility of collisions of parts of the user, such as the user's lower back and bottom, with rocks or other obstacles. The common difficulty of finding sources of compressed air near remote bodies of water for inflating and deflating a tube in order to insert or detach a device capable of overcoming the other problems is also mentioned. Morgan addresses these problems by proposing a collapsible inner tube seat support that deforms an inner tube along a longitudinal axis. The solution offered by Morgan, however, risks puncturing the inner tube in use and decreases the stability of the device as deformation is increased. Further, the Morgan device appears to be rather spartan and not particularly well suited for comfort and relaxed enjoyment on extended length rides.
Using a tube insert to provide additional safety, comfort and support raises further problems of raft stability. When a plain inner tube in used, there is rarely any problem of stability because the combined center of gravity of the tube and passenger is low. However, as inserts deform an inner tube longitudinally, as in Morgan, or rise significantly above the water, as in U.S. Pat. No. 3,666,265 to Ammerman et al., which discloses a water seesaw device, the risk of an inadvertent tipping of the device is increased because the device's stability is decreased. This risk is increased when a passenger of a size not intended for the device uses the device, or a passenger positions him or herself in an unconventional manner on the craft. One solution proposed by U.S. Pat. No. 4,771,722 to Tihany is to provide a frame to support a seat and outrigger arms for outrigger devices. Tihany, of course, has the disadvantage of requiring a good deal of assembly and of requiring numerous additional parts. In addition to the foregoing difficulties, the devices described appear to be rather heavy, thus risking injury to an individual who is inadvertently struck by one of the devices. It is therefore desirable to have a tubing device that is normally light in weight, both for safety and for transportation purposes.
If a safe, comfortable and stable device is possible, long trips, such as weekend camping expeditions are made more possible, and it is therefore desirable to have a tubing device in which camping gear can be stored and carried along. With longer trips being possible, it is also therefore desirable to provide a variety of comfort-enhancing options. It will also be desirable to provide a device for use with larger inner tubes that can support one or more passengers comfortably, safely and with stability.
BRIEF SUMMARY OF THE INVENTION
An insert for an inner tube or similar device comprising a bottom portion with one or more contoured, concave surfaces adapted for contacting a portion of the surface of the inner tube radially disposed about an extended base adapted for fitting into the center opening of the inner tube and a seating portion disposed above the bottom portion. The insert has a center of gravity located substantially on a vertical axis passing substantially through the center of the base, whether the location of the center of gravity is determined based upon the insert alone or upon the insert and a normal sized passenger seated in the insert in a normal fashion. Further, when the insert is used in conjunction with an inner tube, the combination results in a flotation device that has positive stability. The seating portion is provided with or without armrests. The base is preferably circular, but may be any shape which fits or wedges into the center opening of the inner tube.
The present invention also provides ballasting means for adjusting the locations of the center of gravity and the center of buoyancy of the insert to accommodate different passenger requirements and positions. The ballasting means may comprise a number of separate compartments formed between the bottom portion and the seat. Preferably, the separate compartments are each provided with a means for a passenger or other person to fill or drain the compartments with water as needed for a desired ballast. The compartments can also be adapted to use solid ballast, such as sand, rocks or metal, if desired.
In another embodiment of the present invention, the insert is provided with a plurality of fastening means for fastening the insert securely to an inner tube. The fastening means are located radially around the periphery of the insert. Alternative fastening means can comprise the shape or size of the base which adequately secures the insert into the inner tube. For example, the base can be flared at the lower portion to engage the opposite side of the inner tube. The flared base may be a portion of or the entire perimeter of the base and can be sized and shaped so it can be popped into and out of the inner tube or can be sized and shaped for rugged use such that the inner tube would need be deflated and reinflated around the base member of the insert.
In further embodiments of the present invention, inserts are provided with one or more storage compartments between the seat backrest and the bottom portion, the storage compartments being waterproof in one embodiment. In other embodiments, inserts are provided with features such as beverage holders, umbrella holders, grips and/or oarlocks and radio or speaker holders.
In another embodiment of the present invention, the insert includes more than one seat. In a preferred embodiment, all seats face in the same direction. In another embodiment, the seats face, alternately, in opposite directions. An insert with more than one seat may include an armrest at left and right sides of the seating means with an armrest separating individual seats. Alternatively, no armrests are used. The seat arrangement can be side by side or can provide for in-line seating, e.g., like toboggan seating.
In another embodiment of the present invention, a bottom portion including one or more contoured, concave surfaces radially disposed about a circular base is covered with a top portion including an access means to form an interior portion suitable for storing equipment. This embodiment is used to transport articles in a tube separate from the tube in which an individual is seated.
This invention possesses many other advantages and has other purposes which will become apparent to other upon reading and understanding the following detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may take many forms. The drawings are only for purposes of illustrating preferred embodiments of the invention and are not to be construed as limiting it.
FIG. 1 shows a perspective view of an insert;
FIG. 2 shows a perspective view of an insert with several optional features;
FIG. 3 shows a cross-sectional side view of an insert;
FIG. 4 shows a bottom view of an insert with armrests;
FIG. 5 shows a perspective view of a flotation device including an insert and an inner tube;
FIG. 6 shows a perspective view of a flotation device;
FIG. 7 shows a perspective view of a multiseat flotation device;
FIG. 8 shows a perspective view of an insert for storing equipment or supplies;
FIG. 9 shows a bottom view of an insert without armrests;
FIG. 10 shows a cross-sectional view of an insert with a ballast compartment.
DETAILED DESCRIPTION OF THE INVENTION
An insert 1 for an inner tube is shown in FIG. 1. FIG. 2 shows an insert 1' with armrests 64 and several additional features such as an umbrella holder 51, a beverage holder 52, and two hand grips 53. The seating portion 6 and the bottom portion 2 comprise a single, molded piece. The insert 1 may be a hollow shell manufactured from a material such as polypropylene or polyethylene in a rotational molding process, or it may be a solid piece, manufactured in an injection molding process from a material such as styrofoam or some other material, preferably one with buoyant characteristics. Additional construction possibilities will be described in relation to other embodiments of the invention.
The seating portion 6 depicted in FIG. 3 is molded in the form of a reclining chair including a backrest 61, a seat 62, a legrest 63 and two armrests 64. The seating portion 6 is positioned over a bottom portion 2. The bottom portion 2 includes a circular base 21. The circular base 21 is a diameter to fit through a particular automotive inner tube's (not shown) center hole. The circular base will, of course, also fit through the center hole of a larger diameter inner tube, and inserts 1 are manufactured in a variety of sizes to accommodate different standard inner tube sizes and different sized passengers. FIG. 6 shows an insert 1 with four fastening straps 100 used in conjunction with an inner tube larger than the inner tube 200 for which the insert is designed.
Returning to FIG. 3, the bottom portion 2 further includes one or more contoured, concave surfaces 22 radially disposed about the circular base. The bottom portion 2 is of a cross-sectional shape similar to the underside of a mushroom and permits an inflated inner tube to be fitted around the circular base 21 and on the surfaces 22. The extent to which the concave, contoured surfaces 22 constitute a single surface or several surfaces is subject to multiple interpretations. Comparison of FIGS. 4 and 9 illustrate the definitional difficulty. FIG. 4 depicts the insert 1' with armrests 64, 64 from the bottom and FIG. 9 depicts the insert 1 without armrests from the bottom. It is also possible to construct an insert with structures (not shown) that merely define the outer edges of the seat 62 and the backrest 61 but are not armrests, yet extend radially outward from the circular base 21. The insert 1 without armrests appears to have two, discontinuous surfaces 22', 22" whereas the insert 1' with armrests appears to have a single, continuous surface 22. It is also possible to construct surfaces 22'", such as is shown by dashed lines in FIGS. 1 and 9, to extend radially from the insert for distributing loads about an inner tube more evenly.
The contoured, concave surfaces 22 permit easy installation of an insert 1 into the center-hole of a tube. Because the surfaces 22 conform to the shape of the tube, the insert 1 is usable in conjunction with a tube with or without means for fastening the insert to the tube, the insert being supported by and retained in the tube by means of gravity and/or friction. Further, the insert is supported by a tube without the necessity of deforming and possibly damaging the tube.
The insert of the present invention is easily mounted by a passenger because the weight distribution of the insert is such that the center of gravity of the insert is located on a vertical axis passing through or near the center of the circular base 24. When a flotation device is formed by placing an insert in the center hole of an inner tube, the flotation device remains in an upright position in water for easy mounting.
Further, the flotation device remains in substantially the same position after being mounted by a passenger (provided the passenger is within a certain range of weight and heights) as its position before mounting. This is because the insert is constructed such that the normally seated passenger's weight distribution, in conjunction with the weight distribution of the insert and the inner tube, provides a center of gravity of the flotation device with a passenger that is located on a vertical axis passing through or near the center of the circular base 24. Stability, and to some extent the center of gravity, can also be changed by inflating or deflating the inner tube, particularly relative to the size, weight and desired portion of the user.
A passenger may desire to recline further back, to sit further forward, or to otherwise adjust the location of the center of gravity and center of buoyancy of the flotation device, perhaps to accommodate a heavy load on one side of the flotation device or for any variety of reasons. An embodiment of the invention, depicted in part in FIG. 4, is provided with a ballast portion 70 comprising a number of compartments 71, which may be shaped in the form of segments of a circle, as shown in FIG. 4, or any other shape, such as a number of squares, that is desired. Each compartment 71 includes a draining and filling valve apparatus 72 with which the passenger can fill one or more of the compartments 71 with water as desired to relocate the center of gravity of the flotation device. Similarly, the passenger may use the draining and filing valve apparatus 72 to drain water from a compartment. While elaborate structures for a draining and filling valve apparatus 72 are possible, one simple structure consists of an upper valve 402 and a lower valve 401 mounted through the walls of the compartments, such as is shown in FIG. 10. When the lower valve 401 is opened it is difficult for water to enter the compartment 71 because of air pressure within the compartment. When the upper valve 402 is opened, air is released from the compartment 71 and water is allowed to flood the compartment until the upper valve 402 is closed, the water providing ballast for the insert. The center of gravity of a flotation device with a flooded compartment shifts toward that compartment. Water is drained from the compartment by removing the flotation device from the water and again opening the valves until the water drains out. While a manually operated valve apparatus 72 is described above, it is obvious to one skilled in the art to modify the above structure to be remotely operated, such as with a hand-held solenoid (not shown) for opening and closing the valves 401 and 402 and a hand or foot pump (not shown) or compressed air sources (not shown) for forcing air into the compartment 71 to drain the compartment more quickly and to drain the compartment while the device is in the water.
Normally the insert 1 fits snugly in an inner tube. However, a flotation device may be used under conditions that risk the tube and the insert becoming separated, or the insert may be used with a tube that is larger than the tube for which the insert was intended. To ensure that the insert remains properly seated in any size tube, fastening means are provided in another embodiment of the invention. FIG. 6 depicts an insert 1 used with a too-large tube 200. The insert 1 is secured to the tube with fastening means comprising a number of straps 100 disposed radially about the periphery of the insert. Four straps 100 are shown, and this quantity should be more than adequate for most uses, but additional straps are possible. Beside straps, other embodiments of fastening means include helically wound ropes or belts (not shown), clamps (not shown), and brackets (not shown).
The insert is also provided with a selection of one or more means for making the use of a flotation device a more pleasurable experience. Embodiments of the present invention, such as is depicted in FIG. 3, include an insert provided with a beverage holder 52 disposed at a convenient location on the seat portion 6 for holding a beverage, an umbrella holder 51 disposed at a top portion of the backrest 61 for holding an umbrella (not shown) for shading purposes, one or more handgrips 53 disposed along the seat portion 6 for gripping while the flotation device traverse rough water and for carrying the flotation device, and one or more recesses 55 for a stereo device and a storage compartment 81 disposed behind the backrest 61 between the seat portion 6 and the bottom portion 2 as shown in FIGS. 3 and 4. The storage compartment may be provided with an outwardly opening door 82 for making the storage compartment watertight. Additionally, the seat portion can be adapted to contain means for draining water from the seat so the user is not always sitting in a water filled seat.
The foregoing descriptions of an insert for an inner tube discuss an insert with a single seat, but are equally applicable to an insert comprising more than one seat for more than one passenger. FIG. 7 shows an insert 1" and a tube 200 where the insert 1" and a tube 200 where the insert 1" comprises two seats 2', 2'. In this embodiment, the two seats 2', 2' are separated from one another by a console 64'. The console 64' may be equipped with such options as beverage holders 52, stereo speaker or radio holders 55, umbrella holders 51 and grips 53, to list but a few options.
FIG. 7 depicts a two seat 2', 2' insert 1", however, other embodiments of the invention include multiseat inserts with more than two seats, wherein seats alternate in opposite directions (not shown), and multiseat inserts without consoles 64' (not shown). The size of the insert and the number of seats that it is capable of including is limited only by the size of the tube.
The foregoing descriptions of an insert for an inner tube describe inserts including seating portions for seating one or more passengers. However, in another embodiment of the present invention an insert for storage of equipment or supplies is provided. FIG. 8 shows an insert 500 for storage of equipment or supplies. In this embodiment of the invention, a bottom portion 2 and a top portion 300 have a hollow interior portion 301. The interior portion 301 is accessible by an access means such as a retractable door 302. FIG. 8 shows a top portion 300 with hemispherical shape, but other embodiments include conical, cylindrical, square and pyramidal shaped top portions, to illustrate the possibilities. The access means need not comprise a retractable door 302, but may alternatively comprise a hinged door (not shown) or a threaded cap (not shown).
While the present invention has been described with respect to its various and preferred embodiments, it is not intended to limit such invention by the description given. Various alternative embodiments not specifically described will be readily apparent to those skilled in the art, and it is intended that they be embraced within the scope of the invention, insofar as the appended claims may permit.
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An insert for an inflatable, buoyant toroid has a bottom portion with one or more contoured, concave surfaces radially disposed about a circular base and one or more seating portions above the bottom portion. The center of gravity of the insert is on a vertical axis passing substantially through the center of the circular base whether the insert contains a passenger or not. A flotation device comprising the insert and an inflatable, buoyant toroid has positive stability in water. The center of gravity of the insert is adjusted by a ballasting apparatus. The insert is provided with a variety of comfort enhancing options. The insert includes fastening devices for fastening the insert to an inflatable buoyant toroid. An insert can be provided with a top portion including an access door for using the insert as an equipment storage device.
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[0001] This application claims priority to U.S. Provisional Application Ser. No. 61/225,975 filed Jul. 16, 2009
FIELD OF INVENTION
[0002] This invention relates to bitumen additive mixtures, their use and application for the fabrication of asphalt mixtures. Examples of applications for the present invention are the production of asphalts mixtures with mineral aggregates used in pavement and waterproofing, and more specifically for construction, repair and maintenance of sidewalks, roads, highways, parking lots or airport runaways and service roads and any other rolling surfaces.
BACKGROUND
[0003] Bitumen or asphalt is the heaviest portion from the oil distillation process. Due to the different origins and distillations processes of such oils, the resulting bitumen may have a wide range of properties and characteristics. In the present invention, bitumen refers not only to the product from oil by direct distillation or from distillation of oil at reduced pressures, but as well to the products coming from the extraction of tar and bituminous sands, the products of oxidation and/or fluxation with carbonated solvents including paraffins and waxes of such bituminous materials, as well as blown or semi-blown bitumens, synthetic bitumens (such as those described for example in FR-A-2 853 647), tars, oil resins or indene-coumarone resins mixed with aromatic and/or paraffinic hydrocarbons and the mixtures of such, the mixtures of such bituminous materials with acids and the like.
[0004] The main application for bitumen is in asphalt mixtures where the bitumen is mixed with mineral aggregates that can be of different size, shape and chemical nature. These asphalt mixtures are particularly used for construction, repair and maintenance of sidewalks, roads, highways, parking lots or airport runaways and service roads and of any other rolling surfaces. In the present invention mineral aggregates are the product from quarries as well as aggregates recuperated from previous asphalt mixtures (Reclaimed Asphalt Pavement, RAP, as described for example in the AFNOR XP P98-135, December 2001, Asphalt Handbook, MS-4 7 th edition, published by the Asphalt Institute, USA), products from building demolition and their mixtures. Other common components in asphalt mixtures are organic and inorganic fibers, such as glass, metal or carbon fibers, as well as cellulose, cotton, polypropylene, polyester, polyvinyl alcohol and polyamide fibers.
[0005] The bitumens, as defined above, are however sparingly used as such for the production of asphalt mixtures, mainly because of the unsatisfying mechanical properties of such mixtures. A number of various additives have therefore been developed since many years to reach satisfying asphalt mixtures that can withstand traffic wear and atmospheric conditions.
[0006] Polyphosphoric acid (PPA) is a commonly used bitumen modifier, which is capable of enhancing the mechanical properties of the bitumen. The effect of PPA on bitumen is well documented in the literature as described for example in FR-A-2 065 076, and in the article by J. F. Masson in “Energy and Fuels”, (2008), vol. 22, page 2637. PPA is able to modify the specification grade of the bitumen towards a harder one. Its use increases the ring and ball temperature, viscosity and reduces the penetration grade. As a consequence, it is useful to reduce the rutting of the road and increase the mechanical modulus of the asphalt mixture. As another consequence, it is necessary to increase the process temperatures for mixing the modified bitumen with the aggregates, storing, transporting, laying and compacting in comparison with asphalt mixtures employing neat bitumen.
[0007] In the present invention, polyphosphoric acid refers to all different existing grades and designations of polyphosphoric acids including pyrophosphoric acid, triphosphoric and metaphosphoric acids with 2 or more repeating units. Polyphosphoric acid also refers to the blends of two or more different polyphosphoric acids grades. Polyphosphoric acids according to the invention may further include one or more of phosphorous-containing moieties such as orthophosphoric acid, phosphoric anhydride (P 2 O 5 ), phosphonic acid, pyrophosphates, and other similar compounds comprising at least one (OH—)P═O group.
[0008] Lately, there has been a lot of interest in reducing the production temperature of hot mix asphalts. Such interest in reducing the production temperatures of asphalt mixtures is not just driven by the energy savings and reduction of polluting emissions; it is also driven by the possibility to increase the asphalt mixture hauling time and the extension of the working season. Several solutions have been proposed, which consist in the addition of some kind of additives.
[0009] One of those solutions was exposed in U.S. Pat. No. 7,297,204 describing a method to produce an asphalt mixture at reduced temperatures by the addition of a water-in-oil dispersion. The water-in-oil dispersion includes one or several surfactants to allow for the dispersion of the water into the bitumen. Although this method provides a way to reduce the production temperature of an asphalt mix it would be incompatible with the polyphosphoric acid due to its great hygroscopic behavior. The contact of water with the polyphosphoric acid would break the chains of the acid into its elemental units, chains which are though responsible for it beneficial effects (J. F. Masson, ibid.). Further more, the PPA might be incompatible with many of the surfactant chemistry described in the text based on their basic nature.
[0010] In WO 2006/106222 and WO 2007/141458 different types of additives for the production of asphalt mixtures at reduced temperatures are described. The therein claimed additives do not lead to a change of the bitumen classification (penetration and ring and ball temperatures remain substantially unchanged). Actual field test are used as examples, showing that a reduction of about 40° C. up to 55° C. in the production and in the compaction of the asphalt mixture is possible, while achieving a good compaction level. The described additives are easy and simple to mix into the bitumen.
[0011] The procedures described in these documents also include waterless processes, which should be advantageous for the combined use with polyphosphoric acid. However, their combined use with polyphosphoric acid is not mention or described. The combined effect of such additives admixed with the highly reactive polyphosphoric acid cannot be easily predicted, in particular since the real mechanism of how the polyphosphoric acid enhances the bitumen properties is not fully understood. (J. F. Masson, ibid.).
[0012] Several advantages result from the reduction of production temperature, as described in many of the works cited above. These advantages include, among others:
Reduction of the fuel used in the production process. Reduction of polluting emissions, related to the fuel consumed and the lower to temperature of the asphalt mixture. Improving of the workers conditions during the laying off and compaction operations. Better joint sealing between lanes posed at different times. Decreasing of the bitumen oxidation during production of the asphalt mixture, extending the pavement life.
[0018] In addition, the ability to lay off and compact an asphalt mix at lower temperatures can compensate for the supplementary cooling encountered when the hauling time is longer or/and when the weather conditions are cooler.
[0019] There is still a need for bitumen additives that can combine the beneficial effects and the advantageous properties of both:
[0020] the above mentioned additives for the production of asphalt mixtures at reduced temperatures, and
[0021] polyphosphoric acid for its final mechanical performances it confers to asphalt mixtures in wear conditions during the whole life of the rolling surfaces.
BRIEF DESCRIPTION OF THE INVENTION
[0022] The invention described here consists in an additive mixture comprising polyphosphoric acid and at least another selected chemical additive. The additive mixture (briefly referred to as “additive mix”) described in this invention is capable of enhancing the mechanical properties of bitumen and at the same time capable of allowing the production at reduced temperatures of an asphalt mixture produced with such additive mix-containing bitumen. Another object of the present invention is a bituminous composition prepared with this additive mix, its use to produce asphalt mixtures and its applications.
[0023] Examples of applications of the additive mix of the present invention are the production of asphalts mixtures with mineral aggregates used in waterproofing, construction or maintenance of sidewalks, roads, highways, parking lots or airport runaways and service roads, as well as any other rolling surfaces.
DETAILED DESCRIPTION OF THE INVENTION
[0024] According to a first aspect, the present invention relates to an additive mixture comprising:
a) at least one polyphosphoric acid and, b) at least one compound comprising at least one alkylene oxide repeating unit, and/or comprising at least one (P═O) moiety.
[0027] It has been surprisingly discovered that the compounds defined under b) above, which are generally known to be used for the production asphalt mixtures at reduced temperatures, are particularly well compatible with phosphoric acid(s), without the properties of polyphosphoric acid(s) and of the said compounds b) being substantially altered. This results in a particularly efficient additive mix for bitumen, as described further in the description and as illustrated by the examples.
[0028] Preferably, the compound as defined under b) above comprises from 2 to 1000 propylene oxide (PO) and/or ethylene oxide (EO) repeating units, even more preferably from 4 to 500 propylene oxide (PO) and/or ethylene oxide (EO) repeating units.
[0029] The additive mix of the present invention comprises from 0.3% to 97.5% by weight, and preferably from 4% to 66% by weight, of one or more additives defined under b) above, the remaining part to 100% being a polyphosphoric acid (PPA), or a mixture of different PPA grades. In the additive mix according to the present invention, the molar ratio [polyphosphoric acid (or mixture of different PPA grades)]/[compound comprising at least one alkylene oxide repeating unit defined under b) above] advantageously ranges between 2 and 4, this molar ratio preferably being of about 3.
[0030] According to a preferred aspect, the additive mix of the present invention comprises at least one polyphosphoric acid and at least one compound defined under
[0031] b) above, said at least one additive b) being of formula (A1) or formula (A1 B ):
[0000]
[0000] wherein
A is chosen from among hydrogen and a group G or
[0000]
G represents a linear or branched, saturated or unsaturated, C 1 -C 30 hydrocarbon chain, optionally containing at least one aromatic cycle, and optionally substituted by at least one phosphate group, preferably one phosphate group,
B represents a divalent group containing at least one alkylene oxide repeating unit,
d represents 1 or 2, and
Z represents a radical of formula B1:
[0000]
wherein P represents phosphorus, R is hydrogen or linear or branched C 1 -C 6 alkyl, f is 0 or 1 or 2, e is 0 or 1, d+e+f is 3,
provided that when d is 2, then e is 0 and P is linked to two identical or different, preferably identical, groups [A-O—B—] or [A-O—], as defined above, and only in the case where d is 1, Z may also represent hydrogen or a group G or
[0000]
[0000] wherein G is as defined above.
[0037] In the present invention alkylene oxide preferably means butylene oxide (BO), propylene oxide (PO) or ethylene oxide (EO), it being understood that a “divalent group containing at least one alkylene oxide repeating unit” is a divalent group that may comprise BO and/or PO and/or EO repeating units.
[0038] More preferably, B represents a divalent group containing propylene oxide (PO) and/or ethylene oxide (EO) repeating units, generally statistically arranged or in blocks, preferably in blocks. Even more preferably B is a statistical or block copolymer of ethylene oxide and propylene oxide with 4 to 500 repeating units, with a mass ratio (ethylene oxide/copolymer) between 1% and 70%.
[0039] According to another embodiment of the present invention, the said PO and/or EO repeating units are bonded to Z by a single bond or by a linear or branched hydrocarbon chain with, preferably, one, two or three carbon atoms. Preferably, the PO and/or EO repeating units are directly bonded to Z (single bond), the oxygen atoms of OP or OE repeating units are bonded to Z. Preferably, B comprises, and preferably represents, —(CH 2 CH(CH 3 )O) g —(CH 2 CH 2 O) h —, block or statistically arranged, where g is between 0 to 10, and h is comprised between 0 and 80, preferably between 8 and 80, and more preferably between 20 and 60. In this case, A1 may be represented by formula A1 O :
[0000]
[0000] wherein A, R, d, e, f, g and h are as described above.
[0040] Alternatively, when the PO and/or EO repeating units (block or statistically arranged) are bonded to Z by a hydrocarbon chain, component A1 can advantageously be described by the following formula A1 C :
[0000]
[0000] wherein A, R, d, e, f, g and h are as described above.
[0041] According to a preferred embodiment, in the additive of general formula A1, g represents 0, when A contains at least 10 carbon atoms. Still according to a preferred embodiment, in the additive of general formula A1, g is comprised between 8 and 80, preferably between 20 and 60, when A contains less than 10 carbon atoms.
[0042] According to another aspect of the present invention, B may represent a single bond, and in this case A1 may be represented by formula A1 B :
[0000]
[0000] where A, R, d, e and f are as described above.
[0043] According to still another embodiment of the present invention, A and Z each represent hydrogen and B is a statistical or block copolymer of ethylene oxide and propylene oxide with 4 to 500 repeating units, with a mass ratio (ethylene oxide/copolymer) between 1% and 70%. Preferably, B is a triblock copolymer with the propylene oxide forming the middle block. In this case A1 may be represented by formula A1 H :
[0000] H—O—(CH 2 CH 2 —O) x —(CH 2 —CH(CH 3 )O) y —(CH 2 CH 2 —O) z —H (A1 H )
[0000] where x, y and z are the number of repeating units of each kind, the sum x+y+z ranging from 4 to 500 and the ratio 44(x+z)/(44(x+z)+57y) ranging from 0.1 to 0.7.
[0044] According to a further embodiment of the present invention, A represents hydrogen, d is 1, Z represents a group G or
[0000]
[0000] wherein G represents a linear or branched, saturated or unsaturated, C 1 -C 30 hydrocarbon chain, optionally containing at least one aromatic cycle, and B represents a divalent group containing at least one propylene oxide repeating unit (PO) and/or at least one ethylene oxide repeating unit (EO).
[0045] According to still another aspect of the present invention, the additive A1 is as defined above, wherein d is equal to 1, Z represents B1, B is as defined above, and A represents
[0000]
[0046] The compound of formula [A-O—B—] d Z, in which d is 1, Z is
[0000]
[0000] wherein R is hydrogen or linear or branched C 1 -C 6 alkyl, f is 0 or 1 or 2, e is 0 or 1, it being understood that d+e+f=3, B represents a divalent group containing at least one alkylene oxide repeating unit, and A represents
[0000]
[0000] is new and thereby forms a further object of the present invention.
[0047] Preferred is the above compound in which e=0, f=2 and B represents a divalent group containing at least one ethylene oxide (OE) and/or propylene oxide (OP) repeating unit as defined above.
[0048] According to still a further aspect of the present invention, the additive mix comprises at least one additive A1, wherein d is 2, in which case said additive A1 may be represented by formula A1 2 :
[0000]
[0000] wherein the two groups (A-O—B—) may be identical or different, preferably identical, A and B being as defined above.
[0049] In a preferred embodiment, the additive A1 of the present invention has not more than 3 phosphorous atoms.
[0050] Non limiting examples of additives of formula A1 described above include the additives disclosed in WO 08/148,974, the products from the reaction between a polyalkylene glycol and a phosphorous oxychloride or phosphorous pentoxide, the Pluronic®, Radiasurf® 7480 and 7417, and the like.
[0051] All additives A1 defined herein before, including A1 O , A1 C , A1 B , A1 H , A1 2 , are known compounds and are readily available from known suppliers, or alternatively are easily prepared from known procedures, which are available in patents or non-patent literature, in scientific publications, in the Chemical Abstracts, and on the Internet.
[0052] The additive mix of the present invention as defined above may be prepared by mixing the at least one polyphosphoric acid together with the at least one compound of general formula A1, in the proportions stated above. When one or more components, or all components are in solid form, mixing may be realized in one solvent or a mixture of solvents.
[0053] Suitable solvent(s) may be of any kind known in the art, preferably organic or hydro-organic solvent(s). As the additive mix is intended for use in bitumen, without the further addition of water, water or hydro-organic solvent(s) are less preferred for the preparation of the additive mix of the present invention. Alternatively, the additive mix can be in the form of an emulsion with the polyphosphoric acid dispersed in or as the continuous phase.
[0054] Another object of the present invention is a bituminous composition comprising at least one bitumen and from 0.05 to 10% by weight of at least one additive mix as defined above. Preferably, the bituminous composition of the invention comprises at least one bitumen and from 0.5 to 5% by weight of at least one additive mix as defined above.
[0055] In the present invention “bitumen” means a bituminous material resulting from the distillation of oil under atmospheric or reduced pressure, the product resulting from the extraction of tar and bituminous sands, the product of oxidation and/or fluxation of such bituminous materials with carbonated solvents including paraffins and waxes, as well as blown or semi-blown bitumens, synthetic bitumens (such as described in FR 2 853 647), tars, oil resins or indene-coumarone resins mixed with aromatic and/or paraffinic hydrocarbons and the mixtures of such.
[0056] The bituminous composition described in this invention may further comprise one or more other additives such as those commonly used in the field of bitumen and asphalts.
[0057] These may include anti-stripping agents, generally anionic, cationic, zwitterionic or amphoteric surfactants, preferably anionic surfactants, or quaternary ammonium surfactants or zwitterionic surfactant. Non-limiting examples of such anti-stripping agents are: sulfated surfactants, sulfonated surfactants, alkyl or aryl carboxylic acids, fatty acid esters of quaternary alkanol amines, alkyl amido polyamines, alkyl imidazolines and alkyl imidazo polyamines, the products from the reaction between polyamines and fatty carboxylic acids, the products from the reaction between alkyl polyamines and fatty carboxylic acids, and in a similar manner, the products from the reaction between fatty acids or vegetable oil and diethanolamine, followed by the reaction with polyamines. Non-limiting examples of quaternary alkanol amines are betain salts and N,N,N-trialkyl choline salts with strong organic or inorganic acids, such as for example (methane)sulfonic acid. The polyamines are, as non-limiting examples, dimethyl amino propylamine, N-amino ethyl piperazine, diethylene triamine, triethylene tetramine and tetraethylene pentamine.
[0058] Other additives that may be advantageously added to the bituminous composition described in this invention are chosen from among phosphoric anhydride (P 2 O 5 ), phosphonic acid, pyrophosphates, and other similar compounds comprising at least one (OH—)P═O group, polymers, generally used in order to improve the mechanical performance of the bitumen and the asphalt mixture, paraffins, for example Fischer-Tropsch paraffins described in U.S. Pat. No. 6,588,974, fluxants, esters of fatty acids and functionalized wax, dialkyldiamides as for example those cited in WO 2007/73378, fluxant oils from vegetable or mineral sources and derivatives thereof, as well as mixtures of two or more of the above additional additives.
[0059] Other additives that may be advantageously added to the bituminous composition described in this invention are chosen from among those used to reduce the production temperature of an asphalt mixture described in WO 2006/106222.
[0060] Non-limiting examples of polymers generally used in order to improve the mechanical performance of the bitumen and the mixture, i.e. commonly used in the modification of bitumen are: styrene butadiene rubbers, styrene/butadiene block copolymers, ethyl vinyl acetate copolymers, polyethylene and other alpha-polyolefins (as disclosed in “Asphalt binder testing manual”, Asphalt Institute 2007).
[0061] The bituminous composition may be prepared by direct addition of the additive mix, as a mixture or as separate components, into the storage tank of bitumen or by direct in-line addition of the additive mix into the bitumen pipe before its use for asphalt mixture production.
[0062] It is as well in the scope of this invention to add the additive mix, as a mixture or as separate components, directly during the preparation process of the asphalt mixture (mixing bitumen and mineral aggregates).
[0063] It might be advantageous to prepare the bitumen composition containing the additive mix according to the invention, and store it for a given period of time, generally ranging from a few or several days to several weeks before its use, for example for the production of asphalt mixtures. Such stored bituminous composition may further enhance the workability of the asphalt mixture at a reduced temperature, resulting in an even more effective compaction, leading to even better final mechanical properties of the asphalt mixture.
[0064] Surprisingly, the additive mix described in this invention improves the mechanical properties of the bitumen in a similar manner to an equivalent amount of pure polyphosphoric acid. In addition, the additive mix provides a better workability of asphalt mixtures produced with the bituminous composition containing the invention.
[0065] The great majority of known adhesion agents generally improve only the cohesion at the aggregate-bitumen interface, without providing sufficient workability for allowing an asphalt mixture production and paving temperature reduction.
[0066] The additive mix of the invention allows for the complete coverage of the mineral aggregates and provides adequate workability to allow a temperature reduction in the production and paving of asphalt mixtures. This improvement of workability provided by the additive mix of the invention allows the production of asphalts mixtures at temperatures of 20° C., preferably of 30° C., more preferably of 40° C., and even up to 50° C., below the standard production temperatures for each kind of bitumen while enhancing the mechanical properties of the bitumen.
[0067] Without the use of the additive mixture of the invention and keeping the temperature lower than the standard temperature for the asphalt mixture, problems may arise such as mixing with uncomplete aggregates coverage, bad workability leading to defects of paver screed feeding, bad compaction, and defects in paved rolling surfaces.
[0068] By “standard temperature” is meant a temperature generally ranging from 100° C. to 260° C., preferably 100 to 200° C. As indicated above, this standard temperature depends on the nature of the bitumen, as is well known to the skilled in the art. For example NF EN 13108-1 of February 2007 indicates the following temperature ranges:
160° C. to 200° C. for bitumen type 20/30 (1/10 mm); 155° C. to 195° C. for bitumen type 30/45 (1/10 mm); 150° C. to 190° C. for bitumen type 35/50 or 40/60 (1/10 mm); 140° C. to 180° C. for bitumen type 50/70 or 70/100 (1/10 mm); 130° C. to 170° C. for bitumen type 100/150 or 160/220 (1/10 mm); and 120° C. to 160° C. for bitumen type 250/330 or 330/430 (1/10 mm).
[0075] The bituminous composition described here can be used to prepare, in combination with mineral aggregates, asphalt mixtures by any asphalt production method. These methods may include other processes for asphalt mixture production at reduced temperatures (where production temperature is above room temperature but below that in regular hot mixing process), for example as described in U.S. Pat. No. 5,910,212 and WO 97/20890 which uses a hard bituminous binder combined to the mixture of a soft bituminous binder and aggregates, or in US 2005/0076810 that uses a high desorption capacity additive, or in EP 1 469 038 in which a part of the aggregates is heated and dried and mixed with bitumen and then after mixed with wet aggregates, or in US 2006/00236614 in which the aggregates are dried and mixed with bitumen but with the drying step, so that a fraction of the initial humidity of the aggregates remains, or else in US2008/0259714 where a particular bitumen foaming device is described to achieve the coverage of the mineral aggregates.
[0076] Preferably, the process to produce an asphalt mixture at reduced temperatures by using the bituminous composition described above is as follow:
i) heating of the mineral aggregates to a reduced temperature compared to standard hot mix asphalts, i.e. of 20° C., preferably of 30° C., more preferably of 40° C., and even up to 50° C., below the standard temperature required for the bitumen grade used. ii) mixing the heated mineral aggregates with the bituminous composition containing 0.05% to 10% by weight of the additive mix described in this invention (bituminous composition that is stored hot, at the standard temperature for each bitumen grade). iii) obtaining an asphalt mixture
[0080] According to an alternative of the above process, the at least one polyphosphoric acid and the at least one component b) may be added separately, typically by means of two separated feed lines, into the bitumen and the mineral aggregates, the all four items being thoroughly mixed together.
[0081] The asphalt mixtures comprising mineral aggregates and at least one bituminous composition as defined above also form another object of the present invention.
[0082] The mineral aggregates used to fabricate asphalt mixtures according to the present invention are not limited in chemical nature, shape or size and may be the products from quarries, aggregates recuperated from previous asphalt mixtures (reclaimed asphalt pavement, RAP for example defined in the French Standard AFNOR XP P98-135 of December 2001, or in Asphalt Handbook, MS-4 7 th edition, published by the Asphalt Institute, USA), products from building demolition and mixtures of any of the above.
[0083] Asphalt mixtures prepared with at least one bituminous composition prepared according to the preparation process of the present invention may comprise other common components of asphalt mixtures such as organic fibers (for example: cellulose, cotton, polypropylene, polyester, polyvinyl alcohol and polyamide fibers) and/or inorganic fibers (for example: glass, metal or carbon fibers).
[0084] The reduction in the production temperature by using the bituminous compositions comprising the additive mix described in this invention has many advantages, among others a reduction in the consumed energy during asphalt mix production since the mineral aggregates do not have to be heated as much as in the production with regular bitumen. In addition, this reduction of energy also implies a reduction in CO 2 and other greenhouse effect gas emissions.
[0085] The main application for the asphalt mixture preparation process described in this invention is the construction of a rolling surface, such as roads, parking lots, bridges, motorways, highways, airport runaways or any similar rolling surface, and also any surface requiring bituminous or asphalt coating, such as pavements, side walks, playgrounds and the like.
[0086] Other uses of the described invention may also include the preparation of roofing and other waterproofing applications.
[0087] The invention is further illustrated with the following examples which do not intend to limit the scope of the present invention, the scope of which is as defined in the annexed claims.
Example 1
[0088] Bituminous compositions were prepared by adding different additive mixtures into a bitumen with a penetration grade of 50/70 [1/10 mm]. The bitumen was preheated to 160° C. and the different additive mixes were added into it while gently stirring for 15 minutes.
[0089] Composition 1 was prepared by mixing 100 g of 50/70 bitumen with 1.3 g of an additive mix of the following composition: 77 wt % polyphosphoric acid (115% H 3 PO 4 basis Sigma Aldrich) and 23 wt % of an additive with chemical formula (A-O—(CH 2 CH(CH 3 )O) g —(CH 2 CH 2 O) h ) d —P(═O)—OH f with a value of d between 1 and 2, d+f equal to 3, g equal to 0, h equal to 4 and A being a linear hydrocarbon chain having between 16 and 18 carbon atoms, commercialized by CECA under the trade name Beycostat® A684.
[0090] Composition 2 was prepared by mixing 100 g of 50/70 bitumen with 1.3 g of an additive mix of the following composition: 77 wt % polyphosphoric acid (115% H 3 PO 4 basis Sigma Aldrich) and 23 wt % of an ethylene oxide and propylene oxide block copolymer with a total molar mass of about 3400 g/mol and a mass ratio ethylene oxide/propylene oxide of 20%, commercialized by BASF under the trade name Pluronic® L92.
[0091] Composition 3 was prepared by mixing 100 g of 50/70 bitumen with 1.3 g of an additive mix of the following composition: 77 wt % polyphosphoric acid (115% H 3 PO 4 basis Sigma Aldrich) and 23 wt % of an ethoxylated fatty acid diamine commercialized by CECA under the trade name Dinoramox S12®.
[0092] The rheological properties of Compositions 1, 2 and 3 were measured at 60° C. by means of the Multiple Stress Creep and Recovery test as described in ASTM D7405-08. The percentage recovery and compliance values at 3.2 kPa for each composition are shown in Table 1. The values for the pure 50/70 bitumen and the bituminous composition prepared by mixing 100 g of 50/70 bitumen with 1 g of polyphosphoric acid are also shown for comparison.
[0093] The beneficial effect of the PPA to the bitumen is evidenced by the increase of its % recovery and significant reduction of its compliance. Almost identical effects were obtained with compositions 1 and 2 by the addition of the respective additives mixes. However, composition 3, containing an additive mix that is not according to the present invention, result in a significant decreased effect of the PPA in the composition, both in % recovery and compliance.
[0000]
TABLE 1
MSCR tests of bituminous compositions at 60° C.
% Recovery at
Compliance at
3200 Pa
3200 Pa
Pure bitumen
~0
0.323
Bitumen + 1% PPA
16.6
0.056
Composition 1
15.7
0.056
Composition 2
16.8
0.057
Composition 3
7.8
0.095
Example 2
[0094] An asphalt mixture using the additive mix and procedure described in this invention was produced. A specific asphalt mixture named BBSG 0/10 (Beton Bitumineux Semi-Grenu, France) was produced using the following mineral formula:
[0095] Calcareous filler 1.5%
[0096] Sand 0/4 48.5%
[0097] Aggregates 4/6 14.0%
[0098] Aggregates 6/10 36.0%
[0099] An amount of 5.6 g of bituminous composition for 100 g of mineral formula described above was used. The temperature of the mineral aggregates was 120° C. and for the bituminous composition it was 160° C. The resulting asphalt mixture was compacted, using a gyratory press. The compacted sample was then cooled down and kept at constant temperature (20° C.) for 24 hours before testing.
[0100] Samples were carried out using the bituminous compositions 4 and 5. Composition 4 was prepared by mixing 100 g of 35/50 bitumen with 1.3 g of an additive mix of the following composition: 77 wt % polyphosphoric acid (115% H 3 PO 4 basis Sigma Aldrich) and 23 wt % of an additive with chemical formula (A-O—(CH 2 CH(CH 3 )O) g —(CH 2 CH 2 O) h ) d —P(═O)—OH f with a value of d between 1 and 2, d+f equal to 3, g equal to 0, h equal to 4 and A being a linear hydrocarbon chain having between 16 and 18 carbon atoms, commercialized by CECA under the trade name Beycostat® A684. Composition 5 was prepared by mixing 100 g of 35/50 bitumen with 1.3 g of an additive mix of the following composition: 77 wt % polyphosphoric acid (115% H 3 PO 4 basis Sigma Aldrich) and 23 wt % of an ethoxylated fatty acid diamine commercialized by CECA under the trade name Dinoramox S12®. In both cases, the bitumen was preheated to 160° C. and the different additive mixes were added into it while gently stirring for 15 minutes.
[0101] A reference sample using pure bitumen, instead of a bituminous composition containing the additive mix was also done in an identical manner. Another reference sample was carried out with the addition of 1% polyphosphoric acid (115% H 3 PO 4 basis Sigma Aldrich) into the bitumen before mixing with the aggregates.
[0102] Indirect tensile tests measurements were carried out on all samples using an Instron universal testing machine on compression at a 50 mm/min rate. Values for the maximal force obtained from the compression curves are shown in Table 2.
[0103] As can be observed, the sample done using the composition described in this invention (composition 1) shows a larger value of fracture force than the one done with pure bitumen and with the one where 1% polyphosphoric acid was used. Sample done with composition 5 shows the lowest value observed in this test.
[0000]
TABLE 2
Fracture force values of tested samples
Asphalt mixture
Max force
with 5.3% of:
attained (kN)
Pure bitumen
32.9
Bitumen + 1% PPA
33.2
Composition 4
35.2
Composition 5
29.4
[0104] From these examples, it can be observed that the additive mix according to the present invention allows the production of an asphalt mixture at lower processing temperatures, while preserving the advantages of polyphosphoric acid alone.
|
The present invention relates to bitumen additive mixtures, their use and application for the fabrication of asphalt mixtures used in pavement and waterproofing, and more specifically for construction, repair and maintenance of sidewalks, roads, highways, parking lots or airport runaways and service roads and any other rolling surfaces.
| 2
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FIELD OF THE INVENTION
[0001] The invention relates to a method and arrangement for generating a color video signal from a light sensitive image sensor having a mosaic color filter array, comprising interpolating a new pixel value of a particular color from the color pixel values of color pixels of said particular color in a rectangular kernel by multiplying said color pixel values with a set of coefficients and summing the results of said multiplication to obtain the new pixel.
BACKGROUND OF THE INVENTION
[0002] In usual image sensors for video- or photo-cameras the pixels for the colors red, green and blue lie in a “mosaic” pattern, also called Bayer pattern. Most common is the GRGB pattern comprising quadruplets of one red, one blue and two green pixels. The result is that only one quarter of the pixels provide red information, one quarter provides blue information and the remaining half of the pixels provides green information. To obtain a full (digital) signal for each of the colors, the missing pixels have to be interpolated by means of a so called “demosaicing algorithm”.
[0003] Many different methods for demosaicing exist, mostly by means of horizontal and vertical low pass filters used for interpolating the missing components. Another method is the “nearest neighbor replication” in which each interpolated output pixel is assigned the value of the nearest pixel in the input image. The nearest neighbor can be anyone of the upper, lower, left and right pixels. Still another method is the “bilinear interpolation” in which the average of two adjacent red or blue pixel values is assigned to the interpolated pixel at an originally green position there between, in which the average of four adjacent diagonal red/blue pixel values is assigned to the interpolated pixel at an originally blue/red position there between and in which the average of the upper, lower, right and left green pixel values is assigned to the interpolated pixel at an originally red or blue position there between. In the US Patent Application Publication US 2005/0031222 a not explained algorithm is used which is said to be “block shift invariant”.
[0004] A problem with all known interpolation algorithms however is that they operate satisfactorily only when the Bayer pattern is uniform i.e. when the pixel-phase is constant. However, if the Bayer data are subjected to a decimation or scaling operation, most importantly by pixel-binning, then the resulting Bayer pattern is not anymore uniform and then the prior art interpolation algorithms do not operate satisfactorily. Pixel binning is a process that reduces the number of pixels while the field of view (FoV) of the image is maintained. It enhances the sensitivity of a CCD or CMOS sensor in terms of the speed of image acquisition. This process involves taking groups of pixels of one color and combining such group of pixels into one “super” pixel. The pixel binning may take place in the analog domain whereby the charge of the group of pixels is combined so that the “super” pixel is capable of holding much more light. This has the effect of reducing the required exposure time. The pixel binning can also be done in the digital domain either by summing or by averaging the pixel values. Pixel binning may e.g. be used when a mega pixel sensor (>1.3 Mega-pixel) is used in video mode (720×576 pixels). Pixel binning provides a reduction of image resolution. However, a drawback of pixel binning is the loss of uniformity of the Bayer pattern with the result that the usual demosaicing algorithms give inferior results.
SUMMARY OF THE INVENTION
[0005] It is an object of the present invention to provide an improved color video signal generation. The invention is defined by the independent claims. The dependent claims define advantageous embodiments. The method according to the present invention is characterized in that the coefficients are derived by a non-linear two-dimensional interpolation function. In one embodiment, the set of coefficients Cik substantially equals
[0000]
C
ik
=
∏
n
j
=
1
j
≠
i
(
x
-
x
j
x
i
-
x
j
)
·
∏
l
=
1
l
≠
k
m
(
y
-
y
l
y
k
-
y
l
)
,
[0000] in which m and n are the number of rows and columns of the color pixels of said particular color in the selected rectangular kernel, in which xi, yk are the coordinates of said color pixels and in which x,y are the coordinates of the new pixel to be interpolated. This formula represents a two dimensional extension of the one dimensional Lagrange interpolating polynomial, see INTERPOLATION OF FUNCTIONS, by J. Szabados & P. Vértesi (Hungarian Acad. of Sci.), page 6, formula (1.3), ISBN: 9971509156—World Scientific. See also Eric W. Weisstein et al. “Lagrange Interpolating Polynomial.” From MathWorld—A Wolfram Web Resource, http://mathworld.wolfram.com/LagrangeInterpolatingPolynomial.html.
[0006] The binning scheme is usually characterized as “binning by N” wherein N is any positive integer larger than 1. In a “binning by N” scheme the pixel reduction is N2 and the pixel distance (the pixel phase) varies by 1, 2N-1, 1, 2N-1,1 . . . . In an embodiment of the invention the “binning by 2” scheme is preferred because it provides a practical pixel reduction by factor 4. Moreover with this binning scheme the digital multiplication by the coefficients is simpler because then all have denominators that are integer powers of 2.
[0007] The rectangular kernel of color pixels that is used for calculating a new pixel may have any suitable magnitude. Preferably, in a “binning by 2” scheme each kernel has a magnitude of 9×9 fields with 5×5 color pixels.
[0008] For the interpolation of a further new pixel the kernel may be shifted so as to keep the pixel to be interpolated approximately in the center of the kernel. However, when the Bayer pattern is non-uniform the risk exists that some kernels have less pixels than others. Therefore in an embodiment, it is preferred that the kernel is so selected that each of the kernels has the same (maximum) number of pixels.
[0009] It is often desirable to have a possibility to to increase the sharpness of the reproduced picture. Therefore the method according to the invention may be further characterized by multiplying the color pixels with a set of sharpening coefficients S ik that complies with a derivative of said non-linear two dimensional interpolation function, by summing the result of said multiplying and by using the result of the summing to modify the value of the new pixel. Preferably the set of sharpening coefficients S ik substantially complies with ΔC ik wherein Δ represents the two-dimensional Laplacian operator.
[0010] The invention also relates to an arrangement for generating a color video signal comprising a light sensitive image sensor having a mosaic color filter array with a Bayer pattern of color filters positioned on top of the sensor which is characterized by a video signal processor that is arranged to perform a non linear bi-dimensional interpolation algorithm by selecting kernels of the pixels read from the image sensor, multiplying the pixels of a particular color of a kernel by coefficients and adding the so multiplied pixels to constitute a new pixel of the color video signal. Such arrangement may be further characterized by a video signal processor that is arranged to perform a bi-dimensional sharpening algorithm by selecting kernels of pixels read from the image sensor, multiplying the pixels of a particular color of a kernel by sharpening coefficients and adding the so multiplied pixels to constitute sharpening information for a new pixel of the color video signal.
[0011] These and other aspects of the invention will be apparent from and elucidated with reference to the embodiments described hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 shows a part of a usual RGBG Bayer pattern of color pixels resulting from a 4-color image sensor,
[0013] FIG. 2 shows an explanation of the “binning by 2” process,
[0014] FIG. 3 shows the Bayer pattern of FIG. 1 after being subjected to the “binning by 2” process shown in FIG. 2 ,
[0015] FIG. 4 shows the result of the demosaicing algorithm according to the present invention on a kernel of pixels of the Bayer pattern of FIG. 3 ,
[0016] FIG. 5 shows a first arrangement for carrying out the present invention, and
[0017] FIG. 6 shows a second arrangement for carrying out the present invention.
DESCRIPTION OF EMBODIMENTS
[0018] FIG. 1 schematically represents (part of) the Bayer pattern of a color filter array (CFA) that is usually placed in front of a CCD or CMOS image sensor to filter out the red, green and blue components of the light falling into it. The pattern consists of quadruplets of one red (R), one blue (B) and two green pixels (Gr, Gb) each. The two types of green pixels Gr and Gb respectively belong to the lines with the red and the blue pixels. Of course the Bayer pattern of FIG. 1 also represents the color pixels generated by the image sensor when light falls upon it through the color filter array.
[0019] The columns of the Bayer pattern are indicated by lower case reference characters a . . . p and the horizontal lines of the pattern are indicated by reference numerals 1 . . . 16 . These reference characters and numerals allow indicating a block of pixels by its upper-left and lower-right pixels. E.g. the entire block of pixels shown in FIG. 1 may be indicated as the block [a 1 , p 16 ].
[0020] FIGS. 2 and 3 illustrate the pixel “binning by 2” scheme that is here supposed to be done in the analogue domain. Of a 3×3 block of pixels the four corner pixels have the same color and the charge of these four pixels is accumulated and stored in the center of the corresponding block of a similar array. This is shown in FIG. 2 a for a block with Gr-corner pixels, in FIG. 2 b for a block with R-corner pixels, in FIG. 2 c for a block with B-corner pixels and in FIG. 2 d for a block with Gb-corner pixels. The result of this binning process is shown in FIG. 3 . It may be noted that e.g. the block [c 1 , e 3 ] of the array of FIG. 1 cannot give a Gr-super pixel on location d 2 of the array of FIG. 3 because the pixels c 1 and c 3 are already used in the block [a 1 ,c 3 ] and the pixels e 1 and e 3 are to be used in the block [e 1 ,g 3 ]. A pixel can only be used in one block, because the binning process “empties” the pixel in the original array. This is the reason why the array of FIG. 3 has a lot of fields without a color pixel. The result is that the array is non-uniform with a pixel phase 1 - 3 - 1 - 3 - 1 . The pixel phase indicates that going from one pixel to the next pixel needs in turn 1 step, 3 steps, 1 step etc.
[0021] An alternative pixel-binning scheme is “binning by 3” in which, in a block of 5×5 pixels, all 8 pixels, that have the same color as the central field, have their charge transferred to that central field. An advantage of this binning scheme is that the original sensor array can be used to store the binned pattern, because the central field keeps its own charge and receives the charge from the 8 equally colored pixels. A drawback of “binning by 3” is that the number of fields without pixel is larger than with “binning by 2”. With “binning by 2” 75% of the fields of the Bayer pattern become empty whereas with “binning by 3” this percentage increases to nearly 89%.
[0022] The pixels of the Bayer pattern of FIG. 3 have to be scanned to derive there from the signal that has to be used to reproduce the picture. Because the one-color pixels of the Bayer pattern are scanned sequentially and the video signal has to contain the entire color information in parallel (simultaneously) the missing colors have to be filled in by means of a “demosaicing” algorithm.
[0023] In the Bayer pattern of FIG. 3 circles indicate the (part of the) pixels that have to be generated by the demosaicing algorithm. These new pixels not only contain the four colors in parallel but also have the property that their distribution over the entire Bayer pattern is uniform with pixel phase 2 - 2 - 2 - 2 . It is further noted that these “new” pixels are not part of the Bayer pattern of FIG. 3 but they are shown therein to indicate their position in the generated video signal in relation to the one-color pixels Gr, R, Gb, B of the physical Bayer array.
[0024] Demosaicing algorithms usually perform their calculations onto a block of pixels (a Bayer kernel) around the pixel to be calculated. Such kernel is a square group of pixels whose size is usually [3×3], [5×5],[6×6]. The larger the size of the kernel is, the higher is the demosaicing complexity i.e. the number of additions and multiplications needed to calculate one pixel gets bigger.
[0025] FIG. 4 shows the 5×5 pixel (9×9 field) kernel [c 2 , k 10 ] that is selected for the calculation of the new pixel at location h 6 . Because it is of importance to have the new pixel approximately in the center of the kernel, the position of the kernel changes with the pixel to be calculated. The sequence hereafter represents the location of the new pixels shown in FIG. 3 to be calculated and the position of the kernel used for that calculation: f 6 ,[b 2 ,j 10 ]; h 6 ,[c 2 ,k 10 ]; j 6 ,[f 2 , n 10 ]; 16 ,[g 2 ,o 10 ] - - - f 8 ,[ 3 ,j 11 ]; h 8 ,[c 3 ,k 11 ]; j 8 ,[f 3 ,n 11 ]; 18 ,[g 3 ,o 11 ] - - - f 10 ,[b 6 ,j 14 ]; h 10 ,[c 6 ,k 14 ]; j 10 ,[f 6 ,n 14 ]; l 10 ,[g 6 ,o 14 ] - - - f 12 ,[b 7 ,j 15 ]; h 12 ,[c 7 ,k 15 ]; j 12 ,[f 7 ,n 15 ]; l 12 ,[g 7 ,o 15 ].
[0026] It can be easily ascertained that with this choice of the kernels each kernel contains the maximum of 5×5=25 color pixels. If, for instance, the kernel would be shifted uniformly with the new pixel to be calculated, the non-uniform distribution of the color pixels would cause some kernels to have less color pixels than other kernels.
[0027] The new pixel is calculated from the color pixels of the kernel by means of a demosaicing algorithm that is based on the non-linear and two dimensional equation:
[0000]
C
ik
=
∏
n
j
=
1
j
≠
i
(
x
-
x
j
x
i
-
x
j
)
·
∏
l
=
1
l
≠
k
m
(
y
-
y
l
y
k
-
y
l
)
.
(
I
)
[0028] Herein is n the number of columns in the kernel that contain pixels of a particular color and m the number of rows containing pixels of that color. The subscripts i and k indicate the rank number of a color pixel in its column and row respectively. x and y define the location in the kernel of the new pixel to be calculated and xi and yk define the location of each particular color pixel in the kernel. Cik is the coefficient with which the value (Pik) of color pixel i,k is multiplied to define its contribution in the value P(x,y) of the color component of the new pixel according to:
[0000]
P
(
x
,
y
)
=
∑
i
=
1
n
∑
k
=
1
m
C
ik
P
ik
.
(
II
)
[0029] By way of example the coefficients for the new pixel on h 6 in the kernel [c 2 , k 10 ] of FIG. 4 are calculated with the above given equation (I). In this calculation the position of the origin of the x,y-coordinates can be chosen arbitrarily. In this example the origin is chosen in the field c 10 for all the four colors R, Gb, B and Gr. Therefore the coordinates of the new pixel on h 6 are x=5 and y=4.
[0030] From FIG. 4 it may be seen that for the red color pixels of the kernel the following applies:
n=3 m=3 x 1 =0 y 1 =0 x 2 =4 y 2 =4 x 3 =8 y 3 =8
[0035] With equation (I) the coefficients Cik are then as follows:
[0000]
C
13
C
23
C
33
C
12
C
22
C
32
C
11
C
21
C
31
=
0
0
0
-
3
/
32
30
/
32
5
/
32
0
0
0
[0036] From this matrix it follows that the red-component of the new pixel has 30/32 of the value of the red pixel on g 6 (which lies close to the new pixel) plus 5/32 of the value of the red pixel on k 6 (which lies farther from the new pixel) minus 3/32 of the value of the red pixel on c 6 (which lies still farther from the new pixel with the g 6 -pixel in between. The other red pixels do not contribute to the new pixel because the pixels c 6 , g 6 and k 6 lie on the same horizontal line with the new pixel.
[0037] The same calculation can be done for the other color pixels of the kernel. For the Gb pixels of the kernel the following holds:
n=3 m=2 x 1 =0 y 1 =3 x 2 =4 y 2 =7 x 3 =8
[0042] This gives the coefficients:
[0000]
C
12
C
22
C
32
C
11
C
21
C
31
=
-
3
/
128
30
/
128
5
/
128
-
9
/
128
90
/
128
15
/
128
[0043] It is noted that the sum of all coefficients is always equal to 1. This implies that, when all the kernel pixels of a particular color have the same value, also the new pixel will get that value for this color.
[0044] The values for the blue color pixels are:
n=2 m=2 x 1 =3 y 1 =3 x 2 =7 y 2 =7
giving the coefficient matrix:
[0000]
C
12
C
22
C
11
C
21
=
2
/
16
2
/
16
6
/
16
6
/
16
[0000] and the values for the Gr color pixels are:
n=2 m=3 x 1 =3 y 1 =0 x 2 =7 y 2 =4
y 3 =8
giving the matrix:
[0000]
C
13
C
23
C
12
C
22
C
11
C
21
=
0
0
1
/
2
1
/
2
0
0
[0052] The arrangement of FIG. 5 comprises a sensor array S that receives incoming light through a color filter array C. The pixel information read from the sensor is “binned by 2” and stored in a second array T and the so binned pixels are subsequently converted to digital signals of e.g. 10 bits per pixel in an analog to digital converter A. The digital signals are subsequently processed in a demosaicing processor D. When the binning operation is performed digitally then the array T will be placed after the AD converter A. The binning can also be performed “on the fly” when the pixel data are sent line-by-line and pixel-by-pixel to the processor D. In the processor D the signals are subjected to the demosaicing algorithm described above to generate the four parallel color video signals. Averaging the signals Gr and Gb deliver the green signal G.
[0053] The processor D may obtain the new pixels by repeatedly calculating the equation I for each pixel. However it is more convenient to have the once calculated coefficients Cik stored in a memory M of the processor D, to multiply the value of the color pixels with these stored coefficients and to add the so obtained contributions from each color pixel to obtain the value of the new pixel. The number of coefficients to be stored in the memory M is limited because there are only four kernel types. These kernel types are shown in FIG. 3 in their respective new pixels circles by the roman numerals I, II, III and IV. Kernel type II is subject to FIG. 4 and it has been shown above that this kernel needs 25 coefficients (9 for the R-pixels, 6 for the Gb-pixels, 4 for the B-pixels and 6 for the Gr-pixels). Each of the other three kernel types also needs 25 (other) coefficients so that for carrying out the demosaicing algorithm 100 coefficients need to be stored.
[0054] As shown above the coefficients are all fractions with a denominator that is a power of 2. This makes digital calculation relatively easy. The denominator stems from the fact that in a “binning by 2” pattern the distance between rows or columns of one color is always an integer power of 4. This advantage does not exist when “binning by 3” is applied because then the distance between rows or columns of one color is 6 or a multiple of 6.
[0055] A further embodiment of the invention relates to the feature of image sharpening. For this purpose sharpening coefficients are present that, just like the interpolation coefficients, have to be multiplied with the pixel-values of the selected kernel. The results of this multiplication are added together and the so obtained sum of the contributions of the color pixels is used to modify the respective color of the new pixel.
[0056] The required sharpening coefficients S ik are calculated by taking the first or second order derivative of the two dimensional function (I) that is given above for calculating the interpolation coefficients C ik . With a first order derivative the edges of the image will be enhanced whereas a second order derivative may serve to increase the details of the image. A preferred example of the latter sharpening method is to use the well-known Laplacian operator Δ, which provides a second-order two-dimensional partial-derivative operation. This operator Δ, exercised on the above given interpolation function (I), gives:
[0000]
S
ik
=
∂
2
∂
x
2
(
∏
j
=
1
j
≠
i
n
(
x
-
x
j
x
i
-
x
j
)
·
∏
l
=
1
l
≠
k
m
(
y
-
y
l
y
k
-
y
l
)
)
+
∂
2
∂
y
2
(
∏
n
j
=
1
j
≠
i
(
x
-
x
j
x
i
-
x
j
)
·
∏
l
=
1
l
≠
k
m
(
y
-
y
l
y
k
-
y
l
)
)
or
S
ik
=
∂
2
∂
x
2
(
∏
j
=
1
j
≠
i
n
(
x
-
x
j
x
i
-
x
j
)
)
·
∏
l
=
1
l
≠
k
m
(
y
-
y
l
y
k
-
y
l
)
+
∏
j
=
1
j
≠
i
n
(
x
-
x
j
x
i
-
x
j
)
·
∂
2
∂
y
2
(
∏
l
=
1
l
≠
k
m
(
y
-
y
l
y
k
-
y
l
)
)
(
III
)
[0000] For n=3 and m=3 this equation gives then for the coefficient S 11 :
[0000]
S
11
=
(
x
-
x
2
)
(
x
-
x
3
)
+
(
y
-
y
2
)
(
y
-
y
3
)
(
x
1
-
x
2
)
(
x
1
-
x
3
)
(
y
1
-
y
2
)
(
y
1
-
y
3
)
.
[0000] For the other coefficients S 12 , S 13 , S 21 , S 22 , S 23 , S 31 , S 32 and S 33 similar expressions with changed indices apply.
For n=3, m=2 the equations for the sharpening coefficients become simpler; e.g. for S 11 :
[0000]
S
11
=
(
y
-
y
2
)
(
x
1
-
x
2
)
(
x
1
-
x
3
)
(
y
1
-
y
2
)
and
for
n
=
2
,
m
=
3
S
11
=
(
x
-
x
2
)
(
x
1
-
x
2
)
(
y
1
-
y
2
)
(
y
1
-
y
3
)
[0000] For n=2, m=2 all the sharpening coefficients are 0.
With these equations the sharpening coefficients for the pixel-kernel of FIG. 4 can be calculated with the following result:
[0000]
For
the
red
pixels
:
S
13
S
23
S
33
S
12
S
22
S
32
S
11
S
21
S
31
=
-
3
/
1024
30
/
1024
5
/
1024
38
/
1024
-
124
/
1024
22
/
1024
-
3
/
1024
30
/
1024
5
/
1024
For
the
Gb
pixels
:
S
12
S
22
S
32
S
11
S
21
S
31
=
1
/
128
-
2
/
128
1
/
128
3
/
128
-
6
/
128
3
/
128
For
the
Gr
pixels
:
S
13
S
23
S
12
S
22
S
11
S
21
=
2
/
128
2
/
128
-
4
/
128
-
4
/
128
2
/
128
2
/
128
For
the
blue
pixels
:
S
12
S
22
S
11
S
21
=
0
0
0
0
[0000] It is noted that the sum of all coefficients in a matrix is always equal to 0. This implies that, when all the pixels of a particular color in the kernel have the same value, no sharpening will take place.
[0057] The storage of the sharpening coefficients and the multiplication of these coefficients with the respective pixel values may be done in the same processor D described above with reference to FIG. 5 . In that case this processor may include means to multiply the pixel values with the interpolation coefficients C ik , means to sum the results of this multiplication to create the interpolated new pixel, means to multiply the same pixel values with the sharpening coefficients S ik , means to sum the results of this multiplication to create the sharpening information for the new pixel and finally means to add the sharpening information to the interpolated (new) pixel. It is also possible to store the sum of the two coefficients C ik +S ik in a single memory location and to multiply the pixel values with the so summed coefficients. A drawback of both solutions however is that it is not possible to add post-processing features of the sharpness information such as noise coring, sharpness gain adjustment and soft sharpness. An arrangement that allows such sharpness post-processing is shown in FIG. 6 .
[0058] The arrangement of FIG. 6 contains a sharpening processor E which contains a memory Ms for holding the sharpening coefficients S ik . The sharpening-processor E receives from the AD converter A the same pixel data as the processor D, multiplies these pixel data with the sharpening coefficients C ik and adds the result of this multiplication to obtain the sharpening color components Rs, Gbs, Grs and Bs. Preferably these sharpening color components are combined to a sharpening luminance component Ys e.g. according to the equation Ys=0,3Rs+0,3Gbs+0,3Grs+0,1Bs. Subsequently the sharpening luminance component Ys is applied to a post-processing unit F in which desirable post-processing such as noise coring, sharpness gain and soft sharpness are performed. The then obtained component Y's is subsequently added to the luminance component of an RGB-to-YUV matrix.
[0059] It is noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word “comprising” does not exclude the presence of elements or steps other than those listed in a claim. The word “a” or “an” preceding an element does not exclude the presence of a plurality of such elements. The invention may be implemented by means of hardware comprising several distinct elements, and/or by means of a suitably programmed processor. In the device claim enumerating several means, several of these means may be embodied by one and the same item of hardware. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
|
Method and apparatus for demosaicing a mosaic pattern of a color picture. To improve the picture quality, especially in case of a non-uniform mosaic pattern, a kernel of the mosaic pattern is selected, and the pixel values of the kernel are multiplied by coefficients that comply with a non-linear bi-dimensional interpolation algorithm. Additionally the pixels of the selected kernel may be multiplied by sharpening coefficients that comply with a derivative of the non-linear bi-dimensional interpolation algorithm.
| 7
|
FIELD OF THE INVENTION
[0001] The present invention relates to musk aroma-imparting, augmenting and enhancing mixtures of oxomacrocyclic compounds containing greater than about 40 weight % Δ 3 -cyclotetradecen-1-one and greater than about 40 weight % cyclo-tetradecanone and less than about 5 weight % Δ 2 -cyclotetradecen-1-one and a process for preparing such mixtures by means of a chemo-selective catalytic hydrogen of mixtures containing greater than 15% by weight of the Δ 2 -cyclotetradecen-1-one and greater than 45% by weight of the Δ 3 -cyclotetradecen-1-one.
[0002] There has been considerable work performed relating to substances which can be used to impart, alter, modify or enhance fragrances to or in various consumable materials. These substances are used to diminish the use of natural materials particularly in the musk aroma area where the use of natural materials is being replaced by the use of synthetic materials which provide more uniform and predictable properties in the finished product. Strong, substantive, sweet, warm, natural “animal-musk” aromas with an absence of oily and waxy nuances in the topnotes, middle notes and undertones, heretofore have been highly sought after by those skilled in the perfumery arts.
BACKGROUND OF THE INVENTION
[0003] Thus, prior art “animal-musk” aroma-imparting, augmenting and enhancing mixtures containing significant concentrations of cyclotetradecanone, Δ 2 -cyclo-tetradecen-1-one and Δ 3 -cyclotetradecen-1-one, for example, those disclosed in U.S. Pat. No. 4,183,965 issued on Jan. 15, 1980, the disclosure of which is incorporated herein by reference, and those disclosed by Stork and Macdonald at pages 1264 and 1265 of the Journal of the American Chemical Society, Volume 97, No.5, Mar. 5, 1975 which have desirable musk aromas all have the undesirable oily and waxy nuances present in their topnotes, middle notes and undertones, and impart these nuances to finished products produced therefrom.
[0004] Thus, nothing in the prior art discloses or suggests cyclotetradecanone/mono-unsaturated cyclotetradecen-1-one mixtures which have desirable natural “animal-musk” aromas but which have no oily and waxy nuances present in the topnotes, middle notes or undertones thereof. We have now discovered that the direct cause of the presence of such waxy and oily notes is the presence in the aroma-imparting, augmenting and enhancing mixture of significant concentrations, greater than 15 weight % on a solvent-free basis, of the isomer, Δ 2 -cyclotetradecen-1-one; but if the concentration, on a solvent-free basis, were to be reduced to less than 5 weight % of the mixture, the existence of the oily and waxy nuances becomes imperceptible.
[0005] Accordingly, there exists a need for a practical method to produce cyclotetradecanone/Δ 3 -mono-unsaturated cyclotetradecen-1-one mixtures which have the aforementioned desirable aroma properties but which have insignificant concentrations, less than 5 weight % on a solvent-free basis, of Δ 2 -cyclotetradecen-1-one.
SUMMARY OF THE INVENTION
[0006] Our invention is directed to strong, substantive, sweet, warm, natural “animal-musk” aroma-imparting, augmenting and enhancing macrocyclic musk compositions which are mixtures consisting essentially of oxocarbocyclic compounds containing greater than about 40 weight % Δ 3 -cyclotetradecen-1-one and greater than about 40 weight % cyclotetradecanone, less than 5 weight %, of Δ 2 -cyclotetradecen-1-one.
[0007] More specifically, our invention is directed to macrocyclic musk compositions of matter consisting essentially of:
[0008] (a) from about 40 up to about 60 weight %, on a solvent-free basis, of cyclotetradecanone;
[0009] (b) from about 40 up to about 60 weight %, on a solvent-free basis, of Δ 3 -cyclotetradecen-1-one; and
[0010] (c) less than 5 weight %, on a solvent-free basis, of Δ 2 -cyclotetradecen-1-one, the weight ratio of cyclotetradecanone: Δ 3 -cyclotetradecen-1-one being from about 6:4 down to about 4:6.
[0011] A preferred composition of our invention consists essentially of:
[0012] (a) about 50% by weight, on a solvent-free basis, of cyclotetradecanone;
[0013] (b) about 45% by weight, on a solvent-free basis, of Δ 3 -cyclotetradecen-1-one; and
[0014] (c) less than 5 weight %, on a solvent-free basis, of Δ 2 -cyclotetradecen-1-one.
[0015] The process of our invention for producing the macrocyclic musk compositions of our invention comprises the steps of:
[0016] (a) admixing a cyclotetradecenone reactant mixture comprising greater than 45% by weight of Δ 3 -cyclotetradecen-1-one and greater than 15% by weight of Δ 2 -cyclotetradecen-1-one with a hydrogenation reaction solvent to form a solvent-reactant mixture, with the weight ratio of solvent:cyclotetradecenone reactant mixture being from 20:70 up to 70:20;
[0017] (b) treating the resulting solvent-reactant mixture with hydrogen in the presence of a chemo-selective hydrogenation catalyst in a concentration of from about 0.1% up to about 0.5% by weight of the reaction mixture, at a temperature in the range of from about 15° C. up to about 35° C. and at a pressure of from about 0 psig up to about 100 psig thus forming a hydrogenated product reaction mass, whereby a composition comprising, on a solvent-free basis, greater than about 40% by weight of cyclotetradecanone, greater than about 40% by weight of Δ 3 -cyclotetradecen-1-one and less than about 5% by weight of Δ2-cyclotetradecen-1-one is produced; and
[0018] (c) recovering the resulting macrocyclic musk composition from the hydrogenated product reaction mass (preferably by means of vacuum distillation).
DETAILED DESCRIPTION OF THE INVENTION
[0019] Several techniques for the preparation of the cyclotetradecenone reactant mixtures may be used in the practice of our invention, for example:
[0020] (a) The process described in Example I at columns 11-14 of U.S. Pat. No. 4,183,965 issued on Jan. 15, 1980, the disclosure of which is incorporated herein by reference, or
[0021] (b) A process, as more particularly described herein in detail in Example I, infra, comprising the steps of (i) treating 3-hydroxycyclotetradecan-1-one in the vapor phase with a dehydrating quantity and concentration of anhydrous aluminum oxide particles, preferably from about 4 mesh up to about 8 mesh, at a dehydrating temperature, preferably from about 360° C. up to about 400° C., and pressure, preferably from about 1 mm Hg up to about 20 mm Hg, to form a dehydration product reaction mass and then (ii) recovering the cyclotetradecenone reactant mixture from the dehydration product reaction mass, preferably by means of vacuum distillation.
[0022] Preferably, the chemo-selective hydrogenation catalyst is a supported palladium catalyst containing from about 2 weight % palladium up to about 10 weight % palladium such as palladium on carbon, palladium on calcium carbonate and palladium on barium sulfate.
[0023] The hydrogenation reaction solvent is non-reactive with any reactant or reaction product, and is preferably methanol, ethanol, 2-propanol, 1-propanol, acetone, methylethylketone, methylisobutylketone, tetrahydrofuran or mixtures thereof.
[0024] A preferred set of hydrogenation reaction conditions is specifically set forth herein in Example II, infra.
[0025] Also, a preferred set of hydrogenation reaction conditions is as follows:
[0026] (i) Chemo-selective hydrogen catalyst: 5 weight % palladium on carbon;
[0027] (ii) Solvent: 2-propanol;
[0028] (iii) Hydrogenation reaction pressure: 100 psig;
[0029] (iv) Hydrogenation reaction temperature: 35° C.
[0030] (v) Weight ratio of solvent:reactant mixture: 50:50.
[0031] In carrying out the hydrogenation reaction of our invention, treatment of the solvent-reactant mixture with hydrogen causes the percentage P of Δ 2 -cyclotetradecen-1-one in the composition to be reduced over the period of time, θ (minutes) during which the hydrogenation takes place, according to either of the algorithms:
P=A ( exp )(−θ K /α)+ B (1)
[0032] or
θ={α ln A ( P−B ) −1 } 1/K (2)
[0033] wherein θ represents the time in minutes as measured from the commencement of the hydrogenation reaction; and α, A, B and K represent constants; and wherein:
[0034] P≧0
[0035] θ≧0;
[0036] 15≦A≦30;
[0037] 0≦B≦5;
[0038] 2.8≦K≦4.0; and
[0039] 2×10 3 ≦α≦40×10 3 .
[0040] In addition, the rate of change with respect to time of the percentage of Δ 2 -cyclo-tetradecen-1-one, dP/dθ, in the reactant-solvent mixture being hydrogenated is according to the algorithm:
dP/dθ=−AKθ K−1 α −1 ( exp )(−θ K α −1 ).
[0041] The macrocyclic musk compositions of our invention and one or more auxiliary perfume ingredients, including, for example, alcohols, aldehydes, nitrites, esters, cyclic esters, ketones other than the ingredients of the macrocyclic musk compositions of our invention, hydrocarbons and natural essential oils may be admixed so that the combined odors of the individual components produce a pleasant and desired fragrance particularly and preferably in musk and “animal-like” fragrances. Such perfume compositions usually contain (a) the main note or the “bouquet” or foundation stone of the composition; (b) modifiers which round off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation and substances which retard evaporation; and (d) topnotes which are usually low boiling fresh smelling materials.
[0042] In the perfume composition, it is each of the individual components which contribute to its particular olfactory characteristics, but the over-all effect of the perfume composition will be the sum of the effects of each of the ingredients. Thus, the macrocyclic musk compositions of our invention can be used to alter the aroma characteristics of a perfume composition, for example, by utilizing or moderating the olfactory reaction contributed by at least one other ingredient in the composition.
[0043] The amount of macrocyclic musk composition of our invention which will be effective in perfume compositions depends on many factors including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 0.01% of the macrocyclic musk compositions of our invention and even less (e.g., 0.005%) can be used to impart sweet, warm, natural, “animal musk” aroma nuances (without oily and waxy notes) to soaps, anionic, cationic, nonionic and zwitterionic detergents, fabric softener articles, fabric softener compositions, hair preparations, cosmetics and other products. The amount employed can range up to 10% of the fragrance components and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.
[0044] The macrocyclic musk compositions of our invention are useful, taken alone or in perfume compositions as olfactory components in anionic, cationic, nonionic and zwitterionic detergents, soaps, fabric softener compositions, fabric softener articles for use in clothes dryers (e.g., BOUNCE®, Procter & Gamble Company of Cincinnati, Ohio, U.S.A.), space odorants and deodorants, perfumes, colognes, toilet water, bath preparations such as bath oils and bath solids; hair preparations such as lacquers, brilliantines; creams; deodorants; hand lotions; sun screens; powders such as talcs, dusting powders, face powders and the like. When used as an olfactory component in perfume compositions or perfumed articles, such as anionic, cationic, nonionic and zwitterionic detergents, and in fabric softener compositions and fabric softener articles (e.g. for use in clothing dryers) as little as 0.05% of the macrocyclic musk compositions of our invention will suffice to impart a sweet, warm, natural “animal-musk” aroma, without the undesireable oily and waxy nuances. Generally no more than 5% of the macrocyclic musk composition of our invention is required in the perfume composition or in the perfumed article.
[0045] In addition, the perfume composition or fragrance composition of our invention can contain a vehicle or carrier for the macrocyclic musk compositions of our invention. The vehicle can be a liquid such as a non-toxic alcohol (e.g., ethanol) a non-toxic glycol (e.g., propylene glycol) or the like. The carrier can also be an absorbent solid, such as a gum (e.g., gum arabic, or xanthan gum) or components for encapsulating the composition (such as gelatin) as by means of coacervation. The carrier can be a microporous polymer for use in conjunction with particulate microporous polymer delivery systems, as disclosed in U.S. Pat. No. 6,213,409 issued on Apr. 10, 2001, the disclosure of which is incorporated herein by reference, or for use in conjunction with fiber delivery systems, as disclosed in U.S. Pat. No. 6,207,274 issued on Mar. 27, 2001, the disclosure of which is incorporated herein by reference.
[0046] It will thus be apparent that the macrocyclic musk compositions of our invention can be utilized to alter the sensory properties of a wide variety of consumable materials.
[0047] The following examples are illustrative and the invention is to be restricted thereto only as indicated in the appended claims. All parts and percentages given herein are by weight unless otherwise specified.
EXAMPLE I
Preparation of Mixture of Δ 2 -and Δ 3 Cyclotetradecen-1-Ones
[0048] An one liter distillation flask, equipped with a heating mantle, containing 425 gm.2-hydroxycyclotetradecan-1-one is connected directly to a 12″×1″ inside diameter quartz pyrolysis tube containing 75 gm. of aluminum oxide particles having a particle size in the range of 4-8 mesh. A vacuum distillation (rushover) unit is connected directly to the quartz pyrolysis tube at the end opposite to that of the one liter distillation flask. The pyrolysis tube is heated using a high temperature Lindberg heavy duty split laboratory furnace.
[0049] The distillation flask is slowly heated to a temperature in the range of 180-200° C. thereby causing the evolution of 2-hydroxycyclotetradecan-1-one vapors. The resulting 2-hydroxycyclotetradecan-1-one vapors are thus passed into the quartz tube which is maintained at a temperature in the range of 390-400° C. under 2 mm Hg. pressure, and over the heated aluminum oxide bed thereby effecting a dehydration reaction.
[0050] The resulting reaction product is then fractionally distilled at 2.16-2.20 mm Hg at a vapor temperature of 90-140° C. using reflux ratios of 3:1 to 4:1, yielding 27 fractions. NMR, IR and mass spectral analyses confirm the following components in bulked distillation fractions 14-19:
[0051] (i) 20.7% Δ 2 -cycotetradecen-1-one;
[0052] (ii) 63.2% Δ 3 -cyclotetradecen-1-one;
[0053] (iii) 13.4% cyclotetradecanone
[0054] The resulting product has a musk aroma with waxy and oily topnotes, middle notes and undertones having a ‘musk’ intensity, on a scale of 1-10 of 6.5; and a substantivity on a scale of 1-10 of 8.0.
EXAMPLE II
Preparation of Mixture of Cyclotetradecanone and Δ 3 -Cyclotetradecen-1-One
[0055] Into a 1 liter zipper autoclave equipped with a hydrogen feed line, the following ingredients are placed:
[0056] (i) 250 grams of bulked distillation fractions 14-19 of the distillation of the reaction product of Example I;
[0057] (ii) 250 grams of 2-propanol; and
[0058] (iii) 0.7 grams of a 5% palladium on carbon catalyst.
[0059] The autoclave is sealed and heated to 35° C. and pressurized with hydrogen to 100 psig. Pressurization with hydrogen is maintained at 100 psig at the temperature of 35° C. for a period of 51 minutes. The autoclave is then cooled to room temperature and opened and the contents are removed and filtered. The resulting reaction mass is then admixed with 6 gm. of Primol and fractionally distilled under reduced pressure, yielding 11 fractions distilling 115-122° C. at 1.00-1.19 mm Hg pressure. Fractions 5-10 distilling at 115-122° C. are bulked. NMR, IR and mass spectral analysis confirm that the resulting product consists of: (a) 1.63% Δ 2 -cyclotetradecen-1-one; (b) 45% Δ 3 -cyclotetradecen-1-one; and (c) 50% cyclotetradecanone. The percentage of Δ 2 -cyclotetradecen-1-one and corresponding time of hydrogenation reaction transpired is as follows:
TIME (MINUTES) PERCENTAGE 0 20.71 14 15 18 9.8 23 2.9 51 1.3
[0060] The resulting product has a sweet, warm, natural “animal-musk” aroma (without oily or waxy topnotes, middle notes or undertones) and has a substantivity of “9.5” on a scale of 1-10, and musk intensity of 9.8 on a scale of 1-10.
EXAMPLE III
Musk Perfume Formulation
[0061] The following musk perfume formulation is prepared:
Ingredients Parts by Weight Musk Ambrette 200 Musk Ketone 200 GALAXOLIDE 50 ® 140 Beta Ionone 50 Vetiveryl Acetate 50 Sandalwood Oil 100 Benzyl Benzoate 300 Macreocyclic musk composition of 250 Example II, infra, bulked distillation fractions 5-10
[0062] The macrocyclic musk composition of Example II imparts to this musk perfume formulation sweet, warm, natural “animal musk” undertones and topnotes (without any oily or waxy nuances).
EXAMPLE IV
Preparation of Cosmetic Compositions
[0063] A cosmetic powder is prepared by mixing in a ball mill 100 grams of talcum powder with 0.15 grams of the macrocyclic musk composition prepared according to Example II. The resulting powder has an excellent sweet, warm, natural “animal-musk” aroma (without any oily or waxy topnotes, middle notes or undertones).
[0064] A second cosmetic powder is prepared by mixing in a ball mill 100 grams of talcum powder with 0.20 grams of the perfume composition of Example III. The resulting powder has an excellent musk aroma with sweet, warm, natural “animal-musk” topnotes and undertones (without any oily or waxy nuances).
EXAMPLE V
Preparation of Soap Cake
[0065] 100 grams of soap chips are prepared according to Example V of U.S. Pat. No. 4,058,490 issued on Nov. 15, 1977, the specification for which is incorporated by reference herein. The soap chips are blended in a chip mixer with 40 grams of water and 4 grams of titanium dioxide The resulting blend is then admixed with one gram of the macrocyclic musk composition of Example II until a homogeneous blend is obtained. The resulting blend is formulated into a soap cake and dried under 150 mm Hg. absolute pressure. The perfumed soap cake manifests an excellent, substantive, intense sweet, warm, natural “animal-musk” aroma (without the presence of any oily or waxy nuances).
|
Described are mixtures consisting essentially of oxomacrocyclic compounds containing greater than about 40 weight % Δ 3 -cyclotetradecen-1-one and greater than about 40 weight % cyclotetradecanone and less than about 5 weight %, of Δ 2 -cyclo-tetradecen-1-one, perfumery uses thereof and chemo-selective catalytic hydrogen process for preparing same by hydrogenating mixtures containing significant concentrations, greater than 15 weight %, of Δ 2 -cyclotetradecen-1-one. The oxocarbocyclic compound-containing mixtures have advantageous musk aroma imparting, augmenting and enhancing perfumery properties causing the mixtures to be useful in perfume compositions, perfumed articles and perfumed polymers, including particles and fibers produced therefrom.
| 2
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for electrolytically producing amalgam from metal salt.
2. Background of the Invention
Amalgams are alloys of mercury with alkali metals, alkaline-earth metals or transition metals. They are widely used in industry. In dental technology, tin/copper/noble-metal amalgams are used as tooth fillings. Gold amalgam and silver amalgam can be used to purify mercury-containing gases and liquids. The use of alkali-metal amalgams as reducing agents in the chemical industry, for example for producing alkali-metal alcoholates, is well-known. Sodium amalgam is an important intermediate in chlor-alkali electrolysis. The amounts of amalgam used on a large industrial scale for reactions are normally obtained by this process. The desired amalgam is obtainable at a mercury cathode by electrolysis. Alkali-metal amalgams are usually produced as intermediates in the amalgam process of chlor-alkali electrolysis. In this process, aqueous sodium chloride solution is decomposed by electrical energy to form sodium hydroxide solution, chlorine and hydrogen:
2NaCl+2H 2 O→2NaOH+H 2 +Cl 2
The anode product chlorine is separated from the cathode product amalgam. The amalgam flows in the recirculating system via a so-called decomposer connected downstream and is electrolytically further decomposed in aqueous solution in the latter to form sodium hydroxide solution with simultaneous evolution of hydrogen. Mercury is used as cathode and a graphite anode or an activated titanium anode is usually used as anode.
The use of chlorine in industry is restricted because of a potential safety and health risk of chlorine gas and of chlorinated reaction products, such as, for example, CFCs, vinyl chloride and tetrachloromethane. It is therefore not always economically expedient to produce large amounts of chlorine as a byproduct of the electrolysis
Already known from the 1940's is a process in which alkali-metal sulfate is subjected to electrolysis in order to produce alkali-metal amalgam without the formation of chlorine. The alkali-metal sulfate is electrolyzed between mercury and lead with silver added in an electrolysis cell which is divided by a porous rubber membrane. The amalgam is produced at the cathode and oxygen and sulfuric acid at the anode. The sulfate solution is fed into the cathode space and forced through the diaphragm. The current efficiency in this process is, however, very low and, in addition, the sulfuric acid produced on the anode side is contaminated with sodium sulfate.
To summarize, it can be stated that, in the production process of amalgam using the conventional chlor-alkali electrolysis,. chlorine is produced as a troublesome by-product and this process is furthermore restricted to alkali chlorides as starting material. The chlorine-free process results only in low current efficiencies and a contamination of the reaction products.
SUMMARY OF THE INVENTION
Proceeding from the above mentioned disadvantages of the respective processes, it is an object of the present invention to provide a process for the chlorine-free electrolytic production of amalgam from metal salt. The process should at the same time ensure a high degree of purity of the final products and advantageous parameters, such as a low cell voltage and high current efficiencies.
This object is achieved with a process in which an anion exchanger membrane is used in the electrolytic production of the amalgam. Accordingly, the present invention provides a process for producing a metal-mercury amalgam, by applying an electric current to an electrolysis cell containing:
a cathode comprising mercury metal,
an aqueous solution of a metal salt in contact with the cathode,
an anode, and
an anion exchanger membrane between the cathode and the anode.
The present invention also provides an electrolytic cell for conducting the inventive process that includes the anode, the cathode, and the anion exchanger membrane between the cathode and the anode.
Surprisingly it was found that the process according to the invention has the properties required above and is consequently an improvement on the existing production processes.
DETAILED DESCRIPTION OF THE INVENTION
The electrode reaction is similar to the abovementioned process. If, for example, sodium sulfate is used as the metal salt, the electrolysis can be described by the following equation:
Consequently, the amalgam is produced at the cathode and sulfuric acid and oxygen at the anode.
Generally, the electrolysis is carried out as follows:
The anion exchanger membrane divides the electrolysis cells into a cathode space and an anode space. Initially, the anode space contains a dilute acid solution in a concentration of 0.01 M-0.20 M, which contains the acid-radical ion of the metal salt. The aqueous metal-salt solution, which is in a concentration of 5.0-0.5 M, preferably 2.0-0.5 M, is pumped into the cathode space. When current passes through this electrolyte solution, decomposition of the metal salt occurs. In this process, the metal ions migrate towards the cathode and the electrode reaction results in the formation of the desired amalgam. The anions pass through the anion exchanger membrane and thus enter the anode space. They are present in aqueous solution as anions of the corresponding acid and form the anolyte. At the anode, decomposition of the water also occurs and, consequently, protonization of the acid anions occurs with simultaneous evolution of oxygen. The metal salt in aqueous solution, also referred to as catholyte, and the anolyte are circulated and fed back again to the electrolysis cell.
Amalgams can be produced with alkali metals, alkaline-earth metals and noble metals, zinc, cadmium, tin, lead and copper. Preferably, alkali metals are used for the purpose of amalgamation in the process according to the invention. Particularly preferably, sodium or potassium is used as alkali metal for the purpose of amalgam production. All the usual anions can be used as anionic constituent (acid-radical ions). Preferably, nitrate, sulfate, phosphate, phosphite and carbonate ions are used. Sulfates are particularly preferred as the anions.
Initially pure mercury may serve as the cathode in the present process. Activated titanium which contains a noble-metal or noble-metal oxide coating is preferably used as anode. Platinum is preferably used as noble metal. The anode obtained in this way is remarkable for a low over-voltage for the oxygen evolution. The purpose of the noble metal coating is to catalyze the passage of electrons for the oxygen evolution. The use of titanium has proved advantageous as an anode material because of its good chemical stability. However, the anode material is not limited to this embodiment and other materials having adequate chemical stability may be used if an equally high or higher exchange current density exists for the oxygen evolution.
To perform the process according to the invention, all the obtainable anion exchanger membranes can be used. The anion exchanger membrane used for the process according to the invention contains a polymer which preferably has amino groups. The amino groups contained in the polymer arc preferably terminal, positively charged ammonium groups. The freely mobile counterions contained in the polymer can be exchanged for other anions and are consequently responsible for the selective charge transfer. Anion exchanger membranes of the Neosepta® type are preferably used as membrane. These are commercially obtainable. Particularly preferably, membranes of the Neosepta® types AMX, AMA-2 and ACLE-5 P are used.
The anion exchanger membrane is preferably a thin film approximately 0.1 to 0.6 mm thick with adequate strength and chemical stability. It is permeable only to anions under the influence of a potential difference. The anion exchanger membrane used for the process according to the invention is remarkable for being very stable with time, with a constant exchange capacity and chemical stability.
The process according to the invention for electrolytically producing amalgam with the aid of an anion exchanger membrane is generally carried out as follows:
The current density at the cathode is adjusted to 1.5 to 3.5 kA m −2 . A current density of 2.0 to 3.0 kA m 2 is preferred. The temperature is 30 to 90° C. during the electrolysis. A temperature of 50 to 70° C. is preferred. Depending on the system, a run of 5 to 8 hours leads to a current efficiency of over 95% and up to 99%. The process may proceed continuously or discontinuously.
Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.
EXAMPLES
Example 1
An electrolysis of sodium sulfate is carried out at 60° C. in an electrolysis cell divided by an anion exchanger membrane (Neosepta® ACLE 5 P). Initially pure mercury serves as cathode. The current density at the cathode is adjusted to 2.6 kA m −2 . Catholyte (1.3 M Na 2 SO 4 ) and anolyte (0.12 M H 2 SO 4 ) are circulated. After 5.5 hours, sodium amalgam has been produced at the cathode with a current efficiency of 98%. Corresponding amounts of sulfuric acid and oxygen are produced at the anode.
Obviously, 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.
This application is based on German Patent Application No. 198 121 05.9, filed on Mar. 19, 1998, and incorporated herein by reference in its entirety.
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A process for electrolytically producing an amalgam from metal salt, using an anion exchanger membrane. The chlorine-free process provides amalgam produced from metal salt and having a high degree of purity, and ensures advantageous parameters, such as a low cell voltage and high current efficiencies.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. application Ser. No. 10/540,328, filed on Jun. 21, 2005.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] Technical Field This invention relates to connecting to the internet via a data connection which connection is remotely configurable as to access permissions. The connection may be via a modem or via a direct network connection.
[0004] 2. Description of the Related Art
[0005] Connection of network devices to a network typically require the attendance of a person on site to carry out the initial configuration of the device. For example, connection of a users business to the internet for access by internal parties may be by ADSL (Asymmetric Digital Subscriber Line) or some other connection protocol.
[0006] Such a connection is typically via an ADSL modem and may include a router to route incoming data packets and a firewall to stop attempts to intrude into the users data.
[0007] Typically the configuration of the router and firewall is done on site and will need to be changed on site to cater for variations over time in the users business. This involves a smaller user in expense as it requires specialized IT personnel to come on site to carry out the configuration.
[0008] Connections for higher volume users also typically include routers and firewalls connected via a plurality of modems for internet access. Currently these are mainly configured on site by the users skilled personnel. It is known, once the initial configuration is carried out, that the device may be remotely connected to via the network and final configuration carried out.
[0009] Typically such a network device will include an operating system of some sort which will be accessible by using an external name and password. Once the correct name and password is entered the remote user may modify the device settings, including settings for any router and firewall. This provides security problems, since it is possible for someone with knowledge of the name and password to alter the modem settings without authority.
[0010] It is therefore an object of the present invention to provide a network device which does not require any on site attendance for configuration of the network device but which is secure or which will at least provide the public with a useful choice.
[0011] It is known to provide remotely configured routers to avoid attendance on site, for instance U.S. Pat. No. 6,012,088 shows one such router, however such routers may provide a security problem in that if access is gained to them from one of the networks the router configuration can be changed, and may be changed in such a manner as to compromise security.
[0012] It is therefore an object of the present invention to provide an internet connection which does not require on site attendance for configuration of router or firewall but which does provide complete security of the configuration or which will at least provide the public with a useful choice.
SUMMARY OF THE INVENTION
[0013] Accordingly, the invention may broadly be said to consist in a network device having operating software but no configuration data allowing it to carry out its intended purpose which network device is remotely programmable with configuration data as a whole but which network device or operating software has no facility to allow any incremental change of configuration data.
[0014] Preferably the device configuration data is held in random access memory (RAM) and is lost when no network device supply voltage is present.
[0015] Preferably the device software contains a routine which on initialization attempts to contact a remote verification authority to authorize retrieval of configuration data from a configuration authority.
[0016] Preferably the device software contains only the routine for contacting the remote verification authority and receiving data from the remote configuration authority.
[0017] Preferably the contact with the remote verification authority is subject to encryption.
[0018] Preferably the device initially contains an input filter which will only receive configuration data from a specified remote configuration authority address.
[0019] Preferably the device is a router which is integral with a modem.
[0020] Preferably the modem is an asymmetric digital subscriber line (ADSL) modem.
[0021] Alternatively the invention may be said to lie in the method of configuring a network device which loses its configuration data on power loss comprising providing a network device without user configuration data, providing within the network device a routine which securely contacts a remote verification authority, and downloading from a remote configuration authority authorized by the remote verification authority the entire configuration data.
[0022] Preferably the network device is a router.
[0023] Preferably the router is part of an ADSL modem.
[0024] Preferably the network device is capable of being configured only by remote download of the complete configuration data.
[0025] Preferably the network device routine which contacts the remote verification authority carries out any information transfer using secure encryption.
[0026] Preferably the secure encryption uses a public key encryption method.
[0027] Preferably the private key for the network device is provided by a device temporarily connected to the network device.
[0028] Preferably the temporarily connected device is a USB memory device.
[0029] Preferably the configuration data is also lost from the network device on any intrusion attempt.
[0030] Alternatively the invention may be said to consist in a method of providing communication between two network devices of unknown network address wherein each device is required to download its configuration parameters from a server at a known network address each time the device is initialized, the devices allocated network addresses are stored at server, the server may be queried for the allocated network addresses of the two network devices, and wherein communications can be initiated between the two network addresses from this data.
[0031] Preferably the two network devices are routers.
[0032] Preferably the routers form part of ADSL modems.
[0033] The invention may also broadly be said to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more of the parts, elements or features, and where specific integers are mentioned herein which have known equivalents, such equivalents are incorporated herein as if they were individually set forth.
BRIEF DESCRIPTION OF DRAWINGS
[0034] One preferred form of the invention will now be described with reference to the accompanying drawings in which,
[0035] FIG. 1 shows a block diagram of one form of network device.
[0036] FIG. 2 shows a flow diagram of the initial mediation procedure which downloads to the network device.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0037] With reference to FIG. 1, the diagram shows a network device consisting of an ADSL connection via a modem 101 to a firewall 102 and router 103 which distributes the data to devices such as PC's 104. The modem acts to convert packets from the firewall router into a form suitable for carrying information over the internet. The firewall 102 acts to restrict what information packets may be transferred into the users system and the router 103 acts to distribute packets to an internal user in accordance with the packet address.
[0038] In practice the modem, firewall and router may be combined into a single item of equipment with the configuration data held in a common internal location.
[0039] According to the current invention the modem, or firewall or router, has configuration information, which is internally held, but this information is not capable of being changed by any routine or subroutine held in the modem. The only way in which this information can be altered is to download an updated configuration from a remote authority. The only remote authority which the modem recognizes are ones which are hard coded into the internal software, and the only action the modem can take as regards configuration is to contact the remote authority in a secure manner. This action can occur either at power on or if an intrusion is detected, or it can be triggered by a specific remote query.
[0040] Thus the modem may have instructions in read only memory (ROM) which instruct it to call an address such as 203.17.209.32 upon initial power on, but to otherwise provide no routing of incoming or outgoing data packets. Once the designated address is called and a verification established for the network device from a verification service a secure connection between the modem and the address is set up, preferably by the exchange of encrypted passwords through a secure sockets layer (SSL) and the modems' required configuration is downloaded from a configuration server. This provides the routing configuration required and leaves the modem in a secure state.
[0041] The configuration may include any connection data and passwords for connecting the modem to an internet service provider (ISP), and the modem may automatically carry out the connection once configured.
[0042] Where the connection between the modem and the server is such that it does not support full public key encryption the authentication for the modem may be provided by a removable key, for instance a USB key.
[0043] Should an attempt be made to configure or reconfigure the modem without using the correct encryption from the correct address the modem initialization software is intended to be re-triggered, resulting in a complete download of the required configuration.
[0044] FIG. 2 shows how the equipment on powering on at 201 searches for an internet connection at, and on detecting one sends a particular data stream to the remote verification authority at 202,203 which detects the identity of the calling equipment, and from this can look up the customers identity, the equipments current state, and its desired state as required by the customer. The remote authority then connects a configuration server and initiates the procedure to securely update the equipment at 204 with the desired configuration changes and with the software required to carry out the desired functions. The remote configuration authority can then continue to receive operation reports from the equipment at scheduled intervals.
[0045] In accordance with the present invention the modem, firewall and router are normally provided as a single equipment item which may also include a hub or switch. This item is installed on the users premises, provided with a connection to the internet and powered up. On detecting the internet connection the equipment identifies itself to the remote verification authority, the only action it is capable of taking.
[0046] The remote authority will detect the identification of the calling equipment and validate this against a database of equipment whose setups are stored. If the equipment ID is found the remote authority may then, in secure mode, connect the calling equipment to a configuration service and download to the equipment such configuration details and software as will allow it to perform the desired router/firewall functions.
[0047] Preferably the equipment configuration template is held by the remote authority, who may either make changes in it or allow the user to make changes in it via secure internet access. Such changes may be downloaded to the equipment in the same manner as the initial configuration data, though in most instances the remote authority will send a code to the equipment which forces it to reload the configuration.
[0048] The firewall and router may maintain the normal statistics of packets passed, addresses sent to or received from, intrusion attempts etc. and may, either on prompting or on schedule, send these details to the configuration authority for storage and possible analysis.
[0049] The firewall or router may be set up to pass information through desired ports and may be set to configure these ports on call. Thus if a client requires a VPN connection between two locations which do not have a specific allocated IP address (as for instance a small office served by an ADSL without a fixed address) the client requests the VPN connection from the remote authority, which will have stored the network address of any modem of the inventive type. The remote authority then notifies the network devices of the required connection and the devices then create the VPN connection. Thus a VPN connection can be established between two modems which did not initially know each others addresses.
[0050] While the invention is described in relation to an ADSL modem the invention is equally as applicable to the configuration of a PC, a router of any type, a mobile phone or PDA or other similar equipment.
INDUSTRIAL APPLICABILITY
[0051] The invention is applicable to the guaranteeing of the configuration of a network device, to prevent the compromising of data passing through that device, or the extraction of data in an unintended manner by that device.
[0052] Thus it can be seen that at least the preferred form of the invention provides an item of equipment which can be remotely configured for network device set up purposes.
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A network device initially has no configuration data and is permitted only to query a known network address. From this address a server verifies the connection and authorizes another server to download to the network device the necessary configuration to carry out its purpose. This configuration may not be amended and is not retained on power loss. Any updates are carried out by a complete reload of configuration data.
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BACKGROUND OF THE INVENTION
The present invention relates to an oven. In particular the present invention relates to a development of the type of oven described in the applicants International patent application published as WO 01/98092 A1, the content of which is hereby incorporated by reference in its entirety.
There is an increasing requirement to recycle materials such as aluminium, magnesium and other metals and non-metals. Often such materials will be coated in paint, oil, water, lacquers, plastics, or other volatile organic compounds (V.O.C.s) which must be removed prior to re-melting the materials. For materials which are capable of being processed at relatively high temperatures without melting, such impurities are typically removed using a thermal process which is sometimes known as de-coating. Such thermal de-coating processes can also be used to dry and/or sterilize materials prior to remelting.
For example, aluminium is often used in the production of beverage cans which are typically coated in paint, lacquers and/or other V.O.C.s. Before used beverage cans (U.B.C.s) or scrap material produced during the manufacture of beverage cans can be melted down for recycling, any coatings or other impurities must be removed in order to minimize metal loss.
Thermal de-coating, however, is not limited to application to aluminium but can be used to clean or purify any metal or non-metallic materials which are capable of withstanding the temperatures present in the thermal de-coating process. Thermal de-coating can be used to de-coat or purify magnesium or magnesium alloys for example.
Known thermal de-coating processes involve exposing the material to be treated to hot gases in order to oxidise the coatings and/or impurities which are to be removed. This exposure takes place in a closed and controlled environment in which the temperature and oxygen content of the hot gases can be controlled during the de-coating process. Temperatures in excess of 300 C are required to remove most organic compounds and an oxygen level in the range of 6% to 12% is normally required.
If the temperature and oxygen levels of the hot gases are not carefully controlled this can lead to oxidation of the metal as the V.O.C.s which are released during the thermal stripping are combusted. This can result in an uncontrolled increase in the temperature of the hot gases which leads to further metal loses and can be very dangerous.
The material will usually be shredded before treatment and it is important for effective de-coating that all the surfaces of the shredded material are exposed to the hot gases. If this does not occur then the treatment becomes less effective and, in the case of U.B.C.s in particular, a black stain may be left on the surface of the treated material. It is also desirable for the material to be agitated during the treatment to physically remove lose coatings or impurities from the material.
At present there are three main systems which are used on an industrial scale for thermal de-coating, these are:
1. Static Oven
In a static oven, the material is stacked on a wire mesh and hot gases are recirculated through the oven to heat the material to the required process temperature.
This arrangement is not efficient because the hot gases do not come in to contact with the materials that are enclosed within the stack of materials on the mesh. As discussed previously, it is important in de-coating that all the surfaces of the materials being treated are exposed to the hot gases. Also there is no agitation of the material being treated.
2. Conveying Oven
This system uses a mesh belt conveyor to transport materials for treatment through an oven. Hot gasses are passed through the material on the belt as it passes through the oven. The problems with this method are as follows:
The depth of materials on the belt limits the process. The materials are stacked, causing similar problems to those found with the static oven in which materials at the centre of the stack do not come into contact with the hot gases There is no agitation of the materials, so loose coatings are not removed. The conveyor belt life is short. The materials have to be constantly fed. The process is not suitable for low volume or continuously changing product.
3. Rotating Kiln
A large kiln is inclined to the horizontal so that material fed or charged into the kiln at its highest end travels towards the lowest end, where it is discharged, under the influence of gravity. The kiln is rotated so that material within the kiln is agitated and a flow of hot gases is provided to heat up the material as it travels through the kiln. A number of problems are associated with this method:
The material has to be constantly fed. The process is not suitable for low volume or continuously changing product. The continuous process requires air locks at both ends, materials charge end and materials discharge end. The kiln requires a rotating seal leading to a high level of maintenance.
WO 01/98092 A1 describes a pivotable or tiltable oven that overcomes many of the disadvantages of the previously known apparatus and methods for thermal de-coating. For a detailed description of the construction and operation of the oven, the reader should refer to WO 01/98092 A1. However, briefly, the oven has a charging portion for receiving material to be treated and a changeover portion. Incorporated within the changeover portion is a heat treatment chamber through which a stream or flow of hot gasses can be passed. The oven is pivotally moveable between a first position in which the changeover portion is higher than the charging portion and a second position in which the charging portion is higher than the changeover portion. The arrangement is such that the oven can be repeatedly moved between the first and second positions so that material within the oven falls from one portion to the other portion, passing through the stream of hot gasses in the heat treatment chamber. A method of using the apparatus is also disclosed.
The above known oven has the advantage that it can be used to treat comparatively low volumes of material in a batch process. A further advantage is that by controlling the movement of the oven, the material being treated can be brought into and out of the heat treatment chamber at will, enabling the oven to be operated safely without the process going autothermic in an uncontrolled manner and allowing a very fine degree of control of the treatment process.
The oven described in WO 01/98092 A1 has been found to work well, providing a commercially and technically acceptable means of thermally de-coating relatively low volumes of materials. However, when treating light weight materials, such as powders or materials that have been shredded into very small pieces, there can be a tendency for some of the material being treated to become entrained in the flow of hot gasses passing through the heat treatment chamber. Whilst some of the entrained material can be filtered out of the gas flow and recollected, there is an overall reduction in the efficiency of the process.
It is an object of the present invention is to provide an improved oven in which the problems of the known oven are overcome or at least reduced.
SUMMARY OF THE INVENTION
In accordance with the invention, there is provided an oven comprising;
a charging portion for receiving material to be treated; a rotatable changeover portion comprising an outer chamber and an inner treatment chamber within the outer chamber; and means to heat the inner treatment chamber externally thereof; the oven being moveable between a first position in which the changeover portion is generally higher than the charging portion and a second position in which the charging portion is generally higher than the changeover portion; the inner treatment chamber being adapted to receive material from the charging portion as the oven moves from the first position to the second position.
It is an advantage of an oven in accordance with the invention, that the material treated in the inner treatment chamber can be heated indirectly by virtue of the external heating of the inner treatment chamber. A further advantage of an oven in accordance with the invention is that the walls of the inner treatment chamber are heated by the external heating means. When the material being treated enters the inner treatment chamber, some will come into contact with the hot walls, helping to heat the material and so reducing processing times.
In a preferred embodiment, the external heating means comprises a flow of hot gasses through the outer treatment chamber and which passes over at least part of the external surface of the inner treatment chamber.
It is a particular advantage of the invention that the material being treated is separated from the flow of gasses through the outer chamber by the inner treatment chamber. As a result, the material does not become entrained in the flow of gasses through the outer chamber.
In a particularly preferred embodiment the oven further comprises an inlet means for introducing a flow of hot gases into the inner treatment chamber and outlet means through which the flow of hot gasses can exit the inner treatment chamber.
In an oven in accordance with the preferred embodiment a flow or stream of hot gases can be generated through the inner treatment chamber. Material entering the inner treatment chamber will be introduced into the flow of hot gases in the inner treatment chamber to be heated in much the same way as with the prior art oven described in WO 01/98092 A1. However, because the inner treatment chamber can also be heated externally, the flow of hot gasses through the inner treatment chamber can be reduced when treating lightweight materials, so reducing the likelihood of the material becoming entrained. When treating heavier materials, the flow of hot gases through the inner treatment chamber can be increased to ensure effective treatment. The balance of the flow of hot gases through the inner treatment chamber and the external heating of the chamber can be adjusted to suit any particular material to the treated.
Preferably, the means for introducing a flow of hot gases comprises an array of inlet nozzles.
Advantageously, the array of nozzles are located adjacent a first side wall of the inner treatment chamber.
Preferably, the means for introducing a flow of hot gases through the inner treatment chamber further comprises an outlet vent through which the gasses can exit the inner treatment chamber. The outlet vent may be located in a second side wall of the inner treatment chamber opposite from the first wall. Preferably, the outlet vent is positioned such that, in use, as the oven moves between the first and second positions, the material passing between the charging box and the inner treatment chamber does not fall through the outlet vent.
Preferably, the oven is rotated in a first direction as it moves from the first position to the second position and is rotated in the opposite direction as it moves from the second position to the first position.
Preferably, the oven further comprises a control means for regulating the flow and/or the oxygen content of gasses passing through the outer treatment chamber. In which case, the control means may also adapted to regulate the flow and/or oxygen level of the gasses flowing through the inner treatment chamber independently of the gases flowing through the outer treatment chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
An embodiment of the invention will now be described, by way of example only, with reference to the following drawings in which:
FIG. 1 is a front elevation of an oven in accordance with the invention;
FIG. 2 is an end elevation of the oven of FIG. 1 , shown in a first position;
FIG. 3 is a view similar to that of FIG. 2 but showing the oven in a second, inverted position;
FIG. 4 is a perspective view of the oven of FIG. 1 , showing various features in hidden detail;
FIG. 5 is a perspective view of an inner treatment chamber forming part of the oven of FIGS. 1 to 4 , shown connected to a charging box of the oven; and
FIG. 6 is a schematic diagram showing an oven in accordance with the invention connected with a second afterburner and an air pollution control unit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
An oven 10 comprises a charging portion 12 and a changeover portion 14 . The oven is mounted to a support 16 so as to be movable between a first position in which the changeover portion is generally higher than the charging portion (as shown in FIG. 2 ), and a second position in which the charging portion is generally higher than the changeover portion (as shown in FIG. 3 ).
The charging portion 12 is in the form of a charging box which is removably mountable to the changeover portion 14 . The charging box 12 is substantially rectangular in shape. The end of the box which is uppermost when the oven is in the first position has an opening 18 through which material can enter and exit the box 12 .
The changeover portion 14 has an outer treatment chamber 20 and an inner treatment chamber 22 located within the outer treatment chamber. The inner treatment chamber is generally rectangular in shape though tapering inwardly towards a base 24 . The inner treatment chamber 22 has an opening 26 in a face opposite to the base 24 , which face is lowermost when the oven is in the first position. The opening 26 of the inner treatment chamber is substantially the same size as the opening 18 of the charging box 12 . When the charging box 12 is mounted to the changeover portion 14 , the openings 18 , 26 of the charging box and the inner treatment chamber are aligned face to face so that material can pass between the charging box 12 and the inner treatment chamber 22 as the oven is moved between the first and second positions.
The oven has means for recirculating a flow of hot gases, which may be a mixture of air and volatiles, through the inner and outer treatment chambers 22 , 20 in a manner similar to that described in WO 01/98092 A1, to which the reader should refer for a detailed description. To this end, as can be seen from FIG. 4 in particular, on one side of the oven there is a recirculation chamber 28 into which the recirculated gases 30 are drawn from the outer treatment chamber 20 by a recirculating fan 32 . An air mixing jacket 34 guides the gases from the recirculation chamber 28 into an afterburner chamber 36 in which the gasses are heated by a burner 38 . The walls of the afterburner chamber 36 can be air cooled stainless steel walls or may be lined with a suitable refractory material.
The burner 38 which heats the gasses may be designed to run on either a gaseous or a liquid fuel or both. In a preferred embodiment the burner is also designed so as to be able to burn the V.O.C.s which are thermally stripped from the materials in the inner treatment chamber 22 . These V.O.C.s are drawn out of the inner treatment chamber 22 and the outer treatment chamber 20 with the gases 30 by the recirculating fan 32 and are mixed with the gases in the mixing jacket 34 . The air mixing jacket 34 is designed to ensure that the gasses enter the afterburner with a helical flow, as indicated by the arrows 40 , which ensures that V.O.C.s have a maximum residence time and exposure to the hot zone of the burner flame.
By burning the V.O.C.s the overall thermal efficiency of the oven is increased since less fuel need be supplied to heat the gases 30 to the required operating temperature. If sufficient V.O.C.s are present, no additional fuel need be added to heat the gases to the required temperature so that the process can operate autothermically but in a controlled manner.
Burning the V.O.C.s also improves the control of emissions by removing these pollutants from the re-circulating gases and reducing the need for further and expensive treatment of gases which are exhausted from the afterburner chamber as is described in WO 01/98092 A1.
From the afterburner chamber 36 , the hot gases enter a pre-treatment chamber 42 from where they are feed into the outer treatment chamber 20 on the opposite side of the oven from the recirculation chamber 28 . As the gases pass through the outer treatment chamber from the pre-treatment chamber 42 to the recirculation chamber 28 , they flow around most of the outer surfaces of the walls of inner treatment chamber. The walls of the inner treatment chamber are made of a suitable material, such as stainless steel, and are heated by the hot gases passing over them. A certain amount of this heat is also conducted through the walls into the air within the inner treatment chamber.
In order to provide a flow of hot gases through the inner treatment chamber 22 , the inner treatment chamber 22 is provided with an array of gas inlet nozzles 44 (indicated schematically in FIG. 5 ). The nozzles may be located adjacent to a first side wall 46 of the inner treatment chamber 22 . An opening or outlet vent 48 is provided in a second side wall 50 of the inner treatment chamber opposite from the first. A further recirculating fan 52 draws gases from the pre-treatment chamber 42 and supplies the gases to the nozzles 44 from where they flow across the inner treatment chamber 22 and are drawn out through the outlet vent 48 . The gases exiting the outlet vent join with the gasses flowing through the outer treatment chamber 20 and are drawn into the recirculating chamber 28 by the first recirculating fan 32 . If required, more than one recirculating fan 52 can be provided.
A further set of inlet nozzles (not shown) can be provided between the first and second side walls 46 , 50 of the inner chamber if required.
A control system (indicated schematically at 54 in FIG. 2 ) monitors and controls the level of oxygen and the temperature of the gases individually in both the outer treatment chamber 20 and the inner treatment chamber 22 to ensure the system operates within safe and effective limits for thermal de-coating of the material being treated. Typically, the oxygen level will be maintained below 16% whilst temperatures in excess of 300 C are required to remove most organic compounds. A lance 56 , regulated by the control system, supplies fresh air into the afterburner chamber 36 so as to control both the required level of oxygen and temperature of the gases. The afterburner chamber 36 exhausts combustion gases through an exhaust pipe 58 . The flow of exhaust gases being controlled via temperature and pressure controlled damper (not shown).
An auxiliary fresh air inlet 60 is also provided in the recirculation chamber 28 . The auxiliary inlet 60 allows air to enter the recirculation chamber to mix with the hot gases and to cool the fan 32 . The control system monitors the temperature of the fan and operates a valve to control the flow of air through the auxiliary inlet to maintain the temperature of the fan below its maximum permitted operating temperature. The control system balances the flow of air through the lance 56 and the auxiliary inlet 60 in order to maintain the required oxygen content and temperature of the gases in the inner 22 and outer 20 treatment chambers.
The oven 10 is pivotably mounted to the support structure 16 . Means 62 are provided for automatically moving the oven between the first and second positions under the control of the control system 54 for the oven. This means can be of any suitable form and may, for example, comprise one or more electric or hydraulic motors. The motors may act through a gearbox if required. Alternatively the means may comprise one or more hydraulic or pneumatic rams. The means could also comprise a combination of motors and rams.
The oven is arranged to rotate in the direction indicated by arrow A in FIG. 2 when moving from the first position to the second position. When the oven 10 reaches the second position, rotation is stopped. To move the oven 10 from the second position to the first position, the oven is rotated in the opposite direction.
As the oven 10 moves from the first position towards the second position, the first side wall 46 of the inner treatment chamber 22 remains below the opposing second side wall 50 in which the outlet vent 48 is provided. Similarly when the oven moves in the reverse direction from the second position to the first position, the wall 46 of the inner treatment chamber will again remain below the opposing wall 50 in which the outlet vent 48 is provided. As the oven is moved from the first position to the second position, the material being treated will tend to fall from the charging box 12 onto the first side wall 46 of the inner treatment chamber and then downwards on to the base 24 of the inner treatment chamber. Similarly when the oven is moved in the reverse direction from the second position to the first position the material will tend to fall from the base 24 of the inner treatment chamber onto the first side wall 46 and then back into the charging box 12 . By positioning the outlet vent 48 in the wall 50 opposite to the wall 46 which remains lowermost during the rotary movement of the oven, it can be ensured that none of the material will fall through the outlet vent as the oven moves between the first and second positions.
In an alternative embodiment, rather than the oven being rotated reciprocally between the first and second positions, the oven could be adapted so that it is rotated through 360 degrees in the same direction to move from the first position through the second position and back to the first position. In this alternative arrangement, the outlet vent 48 in the inner chamber can be provided with a suitably sized mesh to prevent the material being treated from passing through the vent. This arrangement would be most suited for use in treating materials having a relatively large size and which can be retained in the inner treatment chamber 22 by the mesh.
Operation of the oven will now be described.
The material to be processed is loaded into the charging box 12 which is then transported to the oven by means of a fork lift truck or other means. Once the charging box 12 is in position it is locked to the changeover portion. The treatment process can then be initiated under the control of the control system 54 .
The gases passing through the inner 22 and outer 20 chambers of the changeover portion are heated. The oven is then rotated from the first position as shown in FIG. 2 until it reaches the second position shown in FIG. 3 in which the oven is inverted.
As the oven is rotated, the materials in the charging box 12 will fall under the influence of gravity into the inner treatment chamber 22 . As they do so, the materials enter the stream of hot gases in the inner treatment chamber 22 . Also, some of the material will come into direct contact with the wall 46 and base 24 of the inner treatment chamber 22 which will be at an elevated temperature. This heat will be conducted in to the material to assist in the heat treatment.
The rotary movement of the oven can then be reversed, until the oven is returned to the first position. During this reverse rotary movement, the materials will fall from the inner treatment chamber 22 back into the charging box 12 . The reciprocal rotary movement of the oven between the first and second positions is repeated a number of times as required by the process control until the material is fully treated.
As the oven is repeatedly moved between the first and second positions, the materials being treated are mixed so that at some point most of the material will have come into contact with the heated walls and base 24 of the inner treatment chamber 22 . This helps to speed up the treatment process by increasing the temperature of the materials.
The treatment process goes through a number of phases or cycles: a heating cycle during which the hot gases and the materials are brought up to the required treatment temperature, a treatment cycle in which the temperature of the gasses and materials is maintained at the treatment temperature, and finally a cooling cycle during which the temperature of the gases and the treated material is brought down to a level at which the material can be safely removed.
Once the treatment process is completed, the oven is returned to the first position and the charging box 12 removed so that the treated material can be transported for cooling, storage or further processing as required.
The rotary motion of the oven ensures that the material to be treated passes through the stream of gases in the inner treatment chamber 22 in a controlled manner. The falling action of the material also ensures that all the surfaces of the material become filly exposed to the gases in the inner chamber 22 promoting an efficient and effective de-coating and/or decontamination.
The control system controls the speed and frequency of the rotary movement of the oven along with the temperature and oxygen level of the gases in the inner and outer treatment chambers 20 , 22 in order to oxidize coatings or impurities on the material whilst ensuring the process is carried out safely and efficiently with minimum loss of the material being treated.
Any V.O.C.s or other volatiles given off during the treatment of the material are removed from the inner treatment chamber 22 with the gasses as they flow out of the outlet 48 and rejoin the gases 30 flowing through the outer treatment chamber to be recirculated through the afterburner chamber 36 where most of the V.O.C.s are incinerated.
When a light-weight material is to be treated, the flow of gases through the inner treatment chamber 22 can be reduced to the minimum necessary to remove the volatiles thermally without entraining the material in the gas flow. To ensure the material is brought to a high enough temperature to be successfully de-coated or otherwise treated, the flow of gases through the outer treatment chamber 20 around the inner treatment chamber 22 can be increased and/or the temperature of those gases increased.
When the material to be treated is relatively heavy, the flow of gases through the inner treatment chamber 22 can be increased and the flow of gases through the outer treatment chamber 20 decreased to the point where most of the heating of the material is effected by the gasses flowing through the inner treatment chamber and directly impinging on the heavy coated material.
The control means can be set to regulate the flow and temperature of the gases through the inner and outer treatment chambers independently as required for any particular material.
The oven may also be provided with a second afterburner and cooling system as shown schematically in FIG. 6 , if required. The second afterburner system 64 can be located next to the rotating oven 10 and is connected via ducts 66 , which may be stainless steel and/or insulated, that transfer some of the hot gases with the volatiles 67 from the inner treatment chamber 22 into the second afterburner 64 .
Inside the second afterburner 64 the volatiles are incinerated with the aid of a second burner 68 . The exhaust gasses from the second afterburner 64 are cooled in a separate cooling system 70 which may be located adjacent the second afterburner system 64 . After passing through the cooling unit 70 , the exhaust gasses, which now contain no fuel or oxygen and so are inert, can be recirculated back into the first afterburner chamber 36 and/or the second afterburner 64 via further ducts 74 in order to help reduce the combustion process further. The hot gasses are circulated through the second afterburner 64 and the cooling system 70 by a second recirculating fan 76 . The cooling system 70 uses indirect cooling, for example a heat exchanger system, to provide a controlled cooling which yields a temperature level that is acceptable to the air pollution control unit 72 .
A separate stream of exhaust gasses from the oven is taken via another series of ducts 78 , which may be stainless steel and/or insulated, directly to an air pollution control unit 72 such as a bag or reverse jet filtration system. Preferably, the air pollution control unit comprises high temperature ceramic filters that are capable of receiving gasses having a temperature greater than 120 degrees Celsius and preferably gasses having a temperature above 300 degrees Celsius. This means that the gasses do not require dilution with air before entering the air pollution control unit and prevents reformation of dioxins. The gasses leaving the air pollution control unit into the atmosphere can be subject to rapid gas quenching in a known manner.
Where the second afterburner and cooling system are not required, they can simply be omitted, in which case all the exhaust gasses from the first afterburner chamber can be directed to the air pollution control unit 72 .
Whereas the invention has been described in relation to what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed arrangements but rather is intended to cover various modifications and equivalent constructions included within the scope of the invention as defined by the claims. For example, whilst it is preferred that the external heating of the inner treatment chamber is effected by means of recirculating hot gasses through of the outer treatment chamber, this need not be the case and other suitable means of externally heating the inner chamber may be used. In one example, the inner chamber could be heated by means of external electrical heating elements. The oven in accordance with the invention could also be provided with means for separating the inner treatment chamber 22 from the charging portion 12 so that the material being treated can be retained in the inner chamber 22 or the charging box 12 as the oven is rotated. A suitable means for separating the inner treatment chamber 22 may be a series of flaps or dampers similar to those described with reference to FIG. 5 in WO 01/98092 A2 positioned to close the opening 26 of the inner treatment chamber or the opening 18 of the charging box to control movement of the material between the charging portion and the inner treatment chamber.
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An oven ( 10 ) has a rotatable portion ( 12, 14 ) comprising an outer chamber ( 20 ) and an inner treatment chamber ( 22 ) within the outer chamber. The inner treatment chamber is adapted to receive material for treatment and the oven has means ( 28, 32, 34, 36, 38, 42 ) to heat the inner treatment chamber externally. Preferably, the inner treatment chamber is heated by means of a flow of hot gases through the outer chamber, which passes over the external surfaces of the walls of the inner treatment chamber. The oven may also include means ( 44, 48 ) for introducing a flow of hot gasses through the inner treatment chamber. The flow rate of the hot gasses passing through the inner and outer chambers can be varied according to the nature of the material being treated. The oven is particularly suited to thermally de-coating scrap materials.
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CROSS REFERENCE TO RELATED APPLICATION
The present invention constitutes a novel and unique improvement to copending U.S. Patent Application Ser. No. 949,000, filed Oct. 5, 1978, entitled "SWASH PLATE COMPRESSOR", which is assigned to the same assignee as this application.
BACKGROUND OF THE INVENTION
The present invention relates to an improved swash plate compressor. This type of compressor generally includes a cylinder which is formed with a plurality of axial bores. Double acting pistons are slidably disposed in the bores. A swash plate diagonally mounted on a shaft is connected to the pistons in such a manner that rotation of the shaft and swash plate causes reciprocation of the pistons to compressively displace a fluid. Swash plate compressors are often used as refrigerant compressors for automotive air conditioning systems and the like.
In order to lubricate the swash plate, pistons etc. a lubricant chamber or sump is generally provided in the lower portion of the cylinder containing oil in which the swash plate is partially immersed. The swash plate spashes the oil onto the internal components of the compressor to provide lubrication.
However, since a substantial amount of oil must be splashed about for effective lubrication, a problem has existed in providing a lubricant chamber of sufficient volume to contain the required amount of oil.
One expedient has been to provide a large volume lubricant chamber extending downwardly from the body of the cylinder. Whereas this increases the volume of the lubricant chamber to the required size, the protruding lubricant chamber increases the overall size of the compressor and makes mounting difficult.
In consideration of efficient manufacturing and other considerations, it is desirable for the cylinder to a have circular cross section. Although swash plate compressors having lubricant chambers completely contained in the lower portions of circular cylindrical bodies have been manufactured and used, the lubricant oil volume is only marginally sufficient and failure of such compressors under maximum load conditions has occured due to lack of lubrication. The problem is especially critical during start-up of the compressor.
This problem is overcome in the above identified copending patent application by providing cylinder heads at the ends of the cylinder which are formed with chambers which communicate with and constitute extensions of the lubricant chamber in the cylinder.
However, another problem has remained unsolved in the present type of compressor which is caused by the basic operation of the compressor itself. Due to the fact that the pistons are reciprocated in the respective bores, the inlet and outlet pressures of the compressor fluctuate in a pulsating manner. This leads to excessive mechanical stress and generally degraded operation of the other components of the refrigeration system which are connected to the compressor as well as the compressor itself.
SUMMARY OF THE INVENTION
In accordance with the present invention a swash plate compressor includes a circular cylinder formed with at least one axial bore, at least one piston slidably disposed in the at least one bore respectively and a swash plate supported within the cylinder for reciprocating the at least one piston upon rotation of the swash plate. A lubricant chamber is formed in a lower portion of the cylinder and axially extends through an end of the cylinder. A cylinder head is attached to said end of the cylinder and formed with a lubricant chamber in a lower portion thereof which communicates with and constitutes an extension of the lubricant chamber of the cylinder.
In order for the compressor to operate effectively, the portion of the swash plate which is immersed in the lubricant oil in the lubricant chamber must not exceed one-half the radius of the swash plate. If the oil level is increased beyond this point the viscous frictional drag on the swash plate will increase greatly and the power required to rotate the swash plate will become excessive. In addition, such an arrangement will result in excessive oil consumption.
Due to this fact, the upper portion of the lubricant chamber is not filled with lubricant and constitutes wasted space in the prior compressor.
The present invention overcomes the problem of excessive pulsations in the inlet and outlet pressures of the compressor by utilizing the heretofore wasted upper space in the lubricant chamber in an effective manner. More specifically, one or more partitions are formed in the lubricant chamber to define separate secondary chambers which do not communicate with the remainder of the lubricant chamber. Instead, these secondary chambers are communicated with inlet or outlet chambers formed in the cylinder heads and constitute extensions thereof. The generally increased effective volume of the inlet and outlet chambers and the positions of the secondary chambers reduce the inlet and outlet pressure pulsations by a major extent.
It is an object of the present invention to provide an improved swash plate compressor which utilizes heretofore wasted space in an effective manner.
It is another object of the present invention to provide an improved swash plate compressor comprising novel and unique means for reducing pulsations in inlet and outlet pressures.
It is another object of the present invention to provide a swash plate compressor comprising inlet and outlet chambers of increased size and improved shape.
It is another object of the present invention to provide an improved swash plate compressor which is more compact and easier and less costly to manufacture on a commercial production basis than swash plate compressors known heretofore.
It is another object of the present invention to provide a generally improved swash plate compressor.
Other objects, together with the foregoing, are attained in the embodiment described in the following description and illustrated in the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a longitudinal sectional view of a swash plate compressor embodying the present invention;
FIG. 2 is a perspective view of a cylinder of the compressor;
FIG. 3 is a perspective view of a valve plate of the compressor;
FIG. 4 is a perspective view of a cylinder head of the compressor;
FIG. 5 is a perspective view of an inlet valve plate of the compressor; and
FIG. 6 is a longitudinal sectional view of another embodiment of the present swash plate compressor.
DESCRIPTION OF THE PREFERRED EMBODIMENT
While the swash plate compressor of the present invention is susceptible of numerous physical embodiments, depending upon the environment and requirements of use, substantial numbers of the herein shown and described embodiment have been made, tested and used, and all have performed in an eminently satisfactory manner.
Referring now to FIG. 1 of the drawing, a swash plate compressor embodying the present invention is generally designated by the reference numeral 11 and comprises a circular cylinder 12. The cylinder 12 is formed in two halves which are designated as 13 and 14. With reference also being made to FIG. 2, the cylinder half 13 is formed with a central circular bore 16 for a drive shaft 17 and three circumferentially spaced circular bores 18, 19 and 21 which extend completely through the cylinder half 13.
The cylinder half 14 is formed with a central bore 22 for the drive shaft 17 and three bores identical to the bores 18, 19 and 21, although only one of these bores is visible in the drawing and designated as 23.
A diagonal swash plate 24 is fixed on the drive shaft 17 for integral rotation. The drive shaft 17 and swash plate 24 are rotatably supported in the cylinder 12 by means of thrust bearings 26 and 27 and radial bearings 28 and 29. The axially inner portions of the cylinder halves 13 and 14 are cut away as indicated at 31 and 32 to allow the swash plate 24 to pass between the openings of the bores 18, 19, 21, and the bore 23 and two non-illustrated bores of the cylinder halves 13 and 14.
A double acting piston 33 is slidably disposed in the bores 18 and 23. The piston 33 is formed with two heads, designated as 34 and 36, which are joined together. The heads 34 and 36 are formed with pockets 37 and 38 for balls 39 and 41 respectively. Shoes 42 and 43 are slidably disposed between the left and right faces of the swash plate 24 and the balls 39 and 41 respectively. Essentially similar pistons are provided in the other two sets of bores, although not illustrated.
Attached to the left and right ends of the cylinder 12 are valve plates 44 and 46 respectively. The valve plate 44 is shown in FIG. 3 as being formed with radially inner inlet ports 47, 48 and 49 and radially outer outlet ports 51, 52 and 53 which open into the bores 18, 19 and 21 respectively. An inlet valve plate 101 shown in FIG. 5 is attached to the valve plate 44 and allows fluid flow through the inlet ports 47, 48 and 49 only into the bores 18, 19 and 21 respectively. Outlet flapper valves 58, 59 and 61 are also mounted on the valve plate 44 and allow fluid flow through the outlet ports 51, 52 and 53 only out of the bores 18, 19 and 21 respectively. The valve plate 46 is formed with an essentially similar valve arrangement including an inlet valve plate 100, although not shown in detail. The valve plate 46 is further formed with an opening 62 for the drive shaft 17.
The compressor 11 further comprises a left cylinder head 63 which is shown in FIG. 4. The cylinder head 63 is basically a cap which is attached to and seals the left end of the cylinder 12. However, the cylinder head 63 is formed with a curved partition 64.
As shown in FIG. 2 the cylinder 12 is formed with axial passageways 66 and 67 which extend completely through both cylinder halves 13 and 14. The partition 64 is formed as shown to define an inner inlet chamber 68 which communicates with the bores 18, 19 and 21 through the inlet ports 47, 48 and 49 and also with the passageway 67 through a hole 69 formed through the valve plate 44. The partition 64 also defines an outer outlet chamber 71 which communicates with the bores 18, 19 and 21 through the outlet ports 51, 52 and 53 and also with the passageway 66 through a hole 72 formed through the valve plate 44.
The compressor 11 further comprises a right cylinder head 73 formed with a partition 74 identical to the partition 64. The partition 77 defines an inlet chamber 76 and an outlet chamber 77 which communicate with the bores of the cylinder half 14 through the valves of the valve plate 46. In addition, the inlet and outlet chambers 76 and 77 communicate with the inlet and outlet chambers 68 and 71 through holes (not shown) formed through the valve plate 46 and the passageways 67 and 66 respectively. The inlet chamber 68 is connected to an evaporator of an air conditioning system (not shown) or the like through an inlet connector 78. The outlet chamber 71 is connected to an expansion valve of the air conditioning system through a condensor (not shown). Further illustrated is a seal 79 for the shaft 17.
In operation, the shaft 17 is rotated. Since the swash plate 24 is rigidly mounted on the shaft 17 it also rotates. This causes the piston 33 and the other two non-illustrated pistons to reciprocate once per revolution of the swash plate 24.
As the swash plate 24 approaches the position illustrated in FIG. 1, the piston head 36 displaces refrigerant fluid out of the bore 23 whereas the piston head 34 sucks refrigerant fluid into the bore 18. The inlet valve plate 101 allows fluid flow into the bore 18 whereas the corresponding non-illustrated valve provided to the valve plate 46 allows fluid flow out of the bore 23. As the swash plate 24 is rotated 180° the piston 33 is moved leftwardly so that the piston head 34 displaces fluid out of the bore 18 whereas the piston head 36 sucks fluid into the bore 23. This action causes fluid to be compressively displaced from the inlet chambers 68 and 76 through the bores into the outlet chambers 71 and 77 and thereby through the compressor 11.
The cylinder 12 is also formed with a lubricant chamber 81 which extends completely through the lower portions of the cylinder halves 13 and 14. The chamber 81 is circumferentially spaced between the lowermost two bores 19 and 21. The cylinder 12 is cut away at the upper wall of the chamber 81 to allow the swash plate 24 to be partially immersed in lubricant oil or the like contained in the chamber 81. The swash plate 24, upon rotation thereof, picks up and splashes oil all around the interior of the cylinder 12 to lubricate the pistons, etc. which constitute the moving parts of the compressor 11.
The cylinder head 63 is formed with another partition 82 which separates the outlet chamber 71 from a lubricant chamber 83 defined in the lower portion of the cylinder head 63 aligned with the chamber 81. The vlave plate 44 is formed with a passageway 84 therethrough which communicates the chamber 83 with the chamber 81.
In an essentially similar manner, the cylinder head 73 is formed with another partition 86 which separates the outlet chamber 77 from a lubricant chamber 87 defined in the cylinder head 73. The chamber 87 communicates with the chamber 81 through a passageway 88 formed through the valve plate 46. The chambers 83 and 87 constitute extensions of the chamber 81.
Further illustrated is a drain plug 89 provided to the chamber 83 to allow oil to be drained from the chambers 81, 83 and 87.
As shown in FIG. 5, the flapper valve plate 101 is provided at the valve plate 44 rightwardly thereof and is formed with holes 102, 103 and 104 conjugate to the holes 69 and 72 and passageway 84 respectively. The plate 101 is further formed with holes 106, 107 and 108 conjugate to the outlet ports 51, 52 and 53 respectively.
U-shaped holes 109, 111 and 112 are formed through the plate 101 to defined inlet flapper valves 113, 114 and 116 which normally cover the inlet ports 47, 48 and 49 respectively.
The plate 101 is formed of a resilient material such as spring steel or the like. Thus, the inlet flapper valves 113, 114 and 116 are deformable by inlet suction to uncover the inlet ports 47, 48 and 49.
In accordance with an important feature of the present invention, the cylinder half 13 is formed with a partition 121 which sealingly defines a secondary outlet chamber 122 occupying space in the upper portion of the lubricant chamber 81. The partition 121 seals the chamber 122 from the chamber 81. The valve plate 44 is further formed with a hole 123 which communicates the secondary outlet chamber 122 with the outlet chamber 71. Where the valve plate 101 is used, it is formed with a hole 124 which serves the same function as the hole 123.
In an essentially similar manner, the cylinder half 14 is formed with a partittion 126 which defines another secondary outlet chamber 127 in the lubricant chamber 81. The valve plate 46 is formed with a hole 128 which communicates the secondary outlet chamber 127 with the outlet chamber 77. It will thus be seen that outlet fluid is contained in the compressor 11 within a closed passageway which comprises the outlet chambers 71 and 77 which are connected by the passageway 66 and also the secondary outlet chambers 122 and 127 which communicate with the outlet chambers 71 and 77 through the holes 123 and 128 respectively.
The secondary outlet chambers 122 and 127 occupy heretofore unused space in the lubricant chamber 81 although they do not communicate with the lubricant chamber 81. The chambers 122 and 127 not only increase the overall volume of the outlet passageway, but also due to their positions function to reduce outlet pressure pulsations by acting as mufflers or dampers.
FIG. 6 illustrates another swash plate compressor 131 embodying the present invention in which like elements are designated by the same reference numerals and corresponding but modified elements are designated by the same reference numerals primed.
The difference between the compressor 131 and the compressor 11 is in the configuration of the cylinder heads 63' and 73'. More specifically, the partitions 64' and 74' are formed in such a manner that the holes 123' and 128' and thereby the chambers 122 and 127 communicate with the inlet chambers 68' and 76' rather than with the outlet chambers 71' and 77'. With this construction, the chambers 122 and 127 serve as secondary inlet chambers rather than secondary outlet chambers.
In summary, it will be seen that the present invention provides an improved swash plate compressor which uses heretofore wasted space to define secondary inlet or outlet chambers which increase the overall inlet or outlet chamber volume and reduce pressure fluctuations. Various modifications will become possible for those skilled in the art after receiving the teachings of the present disclosure without departing from the scope thereof. It will be understood that the present invention may provide two secondary chambers defined by partitions in the lubricant chamber. The two chambers may constitute secondary inlet chambers. Alternatively, the two chambers may constitute secondary outlet chambers. As yet another alternative one chamber may constitute a secondary inlet chamber while the other chamber may constitute a secondary outlet chamber. Although the illustrated embodiments show two secondary chambers, it is also within the scope of the present invention to provide only one secondary chamber which may be either a secondary inlet chamber or a secondary outlet chamber.
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A circular cylinder (12) is formed with a plurality of bores (18), (19), (21), (23) in which double acting pistons (33) are slidably disposed. A diagonally oriented swash plate (24) reciprocates the pistons (33) for compressively displacing fluid through the bores (18), (19), (21), (23). A lower portion of the cylinder (12) defines a lubricant sump or chamber (81) in which a lubricant oil is contained. The swash plate (24) is partially immersed in the oil for spash lubrication.
Cylinder heads (63), (73) are fixed to the opposite ends of the cylinder (12) and are each formed with an inlet chamber (68), (76) and an outlet chamber (71), (77). Partitions (121), (126) formed in the cylinder (12) sealingly define secondary chambers (122), (127) in the lubricant chamber (81) which may communicate with either the inlet chambers (68), (76) or the outlet chambers (71), (77) to constitute extensions thereof.
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This application is a continuation of International Application No. PCT/JP2008/053387 filed on Feb. 27, 2008, the entire content of which is incorporated herein by reference. This application is also based on and claims priority under 35 U.S.C. §119(a) with respect to Japanese Application No. 2007-072803 filed on Mar. 20, 2007, the entire content of which is incorporated herein by reference.
TECHNICAL FIELD
The disclosure here generally pertains to medical devices. More specifically, the disclosure here involves coating a medical device such as a stent.
BACKGROUND DISCUSSION
A stent is a kind of medical device and generally speaking is a tube shaped appliance used for medical purposes such as maintaining a state in which a stenosis portion occurring in a blood vessel or other tubular lumen inside a living body is dilated, reinforcing a lumen and the like.
For example, in case of using a stent to maintain the extended/enlarged portion after a percutaneous transluminal coronary angioplasty (PTCA), the re-stenosis ratio is lower compared with that of the case of only the PTCA. However, re-stenosis can occur approximately 20% to 30% of the time. A main cause of the re-stenosis after the stent placement is intimal hyperplasia. Consequently, there has been developed a drug eluting type stent which prevents re-stenosis by coating a stent with a medicine capable of repressing migration and proliferation of a vascular smooth muscle cell, which are the direct cause of the intimal hypelplasia and by eluting the drug at the stent placement region.
The medicine used includes taxol (paclitaxel), mitomycin C, adriamycin, genistein, tylphostin, cytochalasin, sirolimus (rapamycin) or the like.
When the coating is completed, a coating liquid in which the medicine and a biocompatible polymer are dissolved into a solvent is used and applied on a portion of a stent or on the entire stent such that a predetermined quantity of medicine will exist on the surface of the stent.
Known coating methods which has been employed in the past include a dipping method and a spraying method. The dipping method is a method in which a stent is dipped into a coating liquid, pulled up, dried and solidified so as to form a coating layer on the stent.
However, a stent is formed with a groove or a through hole (hereinafter, referred to as space portion) between linear struts, and so it may happen that a web (a membrane between struts) or a bridge is generated at a space portion caused by the dipping. In the case of a stent used by being extended, there is a fear that such a web or a bridge could exert an influence on the mechanical function of the stent, and a portion of the web or the bridge may be destroyed or peeled away after applying the stent. If this portion was to flow into a peripheral vessel, there is also a fear that blood flow obstruction will occur.
The spraying method is a method in which a coating liquid is sprayed over the outer circumferential surface and/or the inner circumferential surface of a stent while rotating the stent and/or moving the spray nozzle. Drying and solidification are then applied so as to form a coating layer. However, with respect to the sprayed coating liquid, the amount actually attached on the stent as compared to the sprayed amount can be relatively small and so a large amount of coating liquid is wasted. Many of the medicines included in the coating liquid are generally extremely expensive and so wasting the coating liquid can result in a steep rise of the cost of the stent itself. Also, many of the medicines included in the coating liquid are medicines having toxicity and so it is also necessary to strictly carry out safety management during spraying so as not to scatter the medicine by the spray into the environment. The facilities cost will thus also increase.
Consequently, Japanese Unexamined Patent Publication No. 2000-51367 proposes a constitution in which a web or a bridge is not generated at the space portion by relatively moving a spindle (mandrel) holding the stent and the stent after applying a coating liquid on a stent.
In addition, Japanese Unexamined Patent Publication No. 2003-205037 discloses a method in which a principle of an electrode position coating is used and electric charge is applied between spray means and the stent so as to heighten the coating efficiency.
Further, in a method mentioned in Japanese Unexamined Publication No. 2005-514988, a shape pattern of the stent is obtained by a scanning and a coating liquid is applied along this pattern.
However, with respect to the methods disclosed in Japanese Unexamined Patent Publication No. 2000-51367 and Japanese Unexamined Patent Publication No. 2003-205037 mentioned above, nether involves a method in which the coating liquid is applied along the pattern shape of the stent and therefore, it is undeniable that coating liquid will be wasted.
Also, with the method in Japanese Unexamined Publication No. 2005-514988, the coating liquid is applied by using a solenoid and so the amount of the medicinal solution to be coated on the stent cannot be set correctly and there is a problem that the effect of reducing the re-stenosis ratio in case of the PTCA mentioned above or the like is insufficient.
SUMMARY
A coating method and coating apparatus disclosed here are able to avoid formation of a web or a bridge at the space portion of the medical device, yet accurately form a coating layer having a uniform thickness.
According to one aspect, a method of applying coating material to the struts of a medical device having plural spaces each bounded by several of the struts extending continuously involves optically scanning the outer surface of the medical device to produce position information identifying positions of the struts, using the position information to calculate a predetermined position in the width direction of the strut, setting an applying manner to apply the coating material based on the predetermined position, setting an applying path accommodating the applying manner, relatively moving the medical device and an applicator head along the applying path while dispensing the coating material from the applicator head and applying the coating material to the struts.
According to another aspect, a coating apparatus comprises a holder holding a mandrel configured to removably receive a medical device having plural spaces each bounded by struts extending continuously, rotating means connected to the mandrel for rotating the mandrel, an applicator head comprising a dispenser adapted to contain coating material and a nozzle through which coating material in the dispenser is discharged, moving means for effecting relative movement between the applicator head and the holder in two mutually orthogonal directions, first position information obtaining means for scanning an outer surface of the medical device held at the holder and for obtaining X-direction and Y-direction position information in an orthogonal coordinate system about an exterior surface of the strut, and a control unit connected to the holder, the applicator head and the moving means for controlling the holder, the applicator head and the moving means based on the position information obtained by the first position information obtaining means. The applicator head continuously discharges the coating material from the nozzle and applying the coating material on the outer surface of the strut.
The coating material is applied by being pushed out continuously along the strut of the medical device so that a web or a bridge is not susceptible to being formed in the medical device, yet it is possible to quite accurately form a coating layer having a uniform thickness on the strut of the medical device. In addition, waste of the coating material is minimized as the coating material is applied only on portions of the medical device. The method is thus economical and safety management is relatively easy.
When setting an applying route so as to apply the coating material onto all the surface of the struts, the effect of the therapeutic substance is brought out at all the regions of the struts.
When the method involves setting an applying route that includes at least one section in which repetition application is performed and/or or jumping is performed from one point to another point, the applying route can be shortened and a speedy application becomes possible. In addition, on an occasion of setting an applying manner, if the section applied overlappingly is reduced or shortened as much as possible and also if the applying route of applying the coating material onto all the surface of the struts is selected, a predetermined quantity of medicine can be applied relatively rapidly and uniformly.
When the applying path at the straight portion of the strut is set at the center line position in the width direction of the strut, the coating material is not likely to be disengaged from the strut top and the formation of a web or a bridge will be generated.
When the applying path at the curved portion of the strut is set at a position deviated by a predetermined distance in the width direction from the center line position, the coating material is inhibited from being disengaged from the strut top depending on the characteristic of the coating material discharged from the nozzle.
In particular, if the deviation position of the applying path which is located in the curved portion of the strut is set outside the center line of the curved portion of the strut, disengagement of the coating material from the strut top is more reliably inhibited.
Setting the applying path to be at an intersection point of the center axis or center lines of the plurality of struts or in the vicinity of the intersection point in the crossing portion of the strut, the coating material is inhibited from being disengaged from the strut top even if a plurality of coating layers are formed.
Setting the applying paths of the coating layer where the applying has already finished and a next coating layer to be identical allows a plurality of coating layers to be formed extremely smoothly and also rapidly.
When the applying path of a next coating layer is set so as not to overlap the applying path of the coating layer where applying has already finished for at least a portion thereof, the coating material can be applied with a generally uniform thickness without being disengaged from the strut top.
A gap can be provided between the outer circumferential surface of a mandrel adapted to hold the medical device and the inner circumferential surface of the strut of the medical device at least at a point at which coating application is initiated.
The moving speed of the applicator head can be made faster during application of the coating material in a section of the medical device in which it passes a plurality of times compared with that during the section in which it passes single time for a predetermined applying route. The coating thickness is thus more uniform and the applying time is shortened.
Plural kinds of coating materials can be applied so the medicinal effects become additive, physical and mental burdens are reduced for a patient and it becomes extremely advantageous.
The distance between the nozzle and the strut is preferably 1 μm to 100 μm, and the front edge inner diameter of the nozzle is 5 μm to 250 μm. In this way, the applying can be realized without dropping out the coating material from the strut.
The applicator head can include a plurality of nozzles and a plurality of dispensers so the application of the coating material is realized more rapidly.
The coating apparatus can include a second position information obtaining means for measuring position information of Z-direction displacement in the orthogonal coordinate system on the surface of the strut so that the application of the coating material becomes possible corresponding to various struts.
The control unit preferably controls the movement of the applicator head and the nozzle along the applying path set based on the position information obtained by the first position information obtaining means obtaining the position information of the X-direction and the Y-direction in the orthogonal coordinate system and also, such that the distance between the applicator head and the strut is based on the position information of the Z-direction displacement which the second position information obtaining means obtains. The applicator head and other parts of the apparatus can be housed in a chamber for which temperature and humidity are controlled to help facilitate forming a coating layer having a generally uniform thickness.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic front elevational view of a coating apparatus disclosed here.
FIG. 2 is a schematic front elevational view of a holder and an applicator head used in the coating method disclosed here.
FIG. 3A is an enlarged cross-sectional view of a portion of the holder shown in FIG. 2
FIG. 3B is a plan view of a portion of a stent shown in FIG. 3A .
FIG. 4 is a schematic cross-sectional view along the section line 4 - 4 line in FIG. 1 .
FIG. 5 is a cross-sectional view of a stent showing the applying state of a plurality of coating layers.
FIG. 6 is a plan view of the applying path of a curved portion.
FIG. 7 is a flowchart illustrating aspects of the coating method disclosed here.
FIG. 8 is a flowchart illustrating other aspects of the coating method disclosed here.
DETAILED DESCRIPTION
Referring the FIG. 1 , an example of the coating apparatus disclosed here includes a base 1 , a frame 2 , supported or mounted on the base 1 , and an air-tight chamber 3 inside the frame 2 .
The air-tight chamber 3 can be formed by covering the frame 2 , provided elevationally on the base 1 , from the outer surface or from the outside. This covering can be a transparent synthetic resin covering (plate). A duct 4 is interlinked to the top portion of the air-tight chamber 3 and communicates with the interior of the air-tight chamber 3 . Air whose temperature and humidity are controlled is supplied from an air conditioner 5 to the interior of the chamber 3 . The apparatus is appropriately configured so that the inside of the chamber 3 is a constant temperature and humidity, and so that drying and solidifying conditions when a coating material C mentioned later is applied on a stent W are always kept constant.
A holder 10 is provided at a lower portion of the inside of the chamber 3 . The holder 10 is configured to hold the medical device which in this disclosed embodiment is in the form of a stent W. Also positioned at the lower portion of the inside of the chamber 3 is a moving means 20 operatively connected to the holder 10 to move the holder 10 . A support frame 6 laterally bridges the frame 2 (extends between opposite upstanding sides of the frame 2 ) at an intermediate portion of the interior of the chamber 3 . An applicator head 30 which supplies the coating material C on an elongated strut S of the stent W is mounted on the support frame 6 and is positioned at an intermediate portion of the interior of the chamber 3 . Also mounted on the frame 6 and positioned at the intermediate portion of the chamber interior are: first position information obtaining means 40 which obtains position information in the X-Y-directions in an orthogonal coordinate system on the surface of the stent W, in other words, on the surface of the strut S; and second position information obtaining means 50 which obtains position information in the Z-direction in the same orthogonal coordinate system.
Positioned outside the chamber 3 is a control unit 60 operatively connected to the holder 10 , the moving means 20 , the applicator head 30 and both position information obtaining means 40 , 50 . The control unit 60 controls the holder 10 , the moving means 20 , the applicator head 30 and the first and second position information obtaining means 40 , 50 .
However, it is sufficient if there exists at least the holder 10 and the applicator head 30 in the inside of the chamber 3 . The first and second position information obtaining means 40 , 50 need not necessarily exist in the chamber in which the temperature and humidity are controlled.
The holder 10 is moved in the X-Y-directions by the moving means 20 . As shown in FIG. 2 , first moving means 20 x (X-direction moving means or first-direction moving means) can be a linear motor system in which a base plate 11 is mounted on a movable table 22 which is movable along a traveling rail 21 . The holder 10 is fixed to a slide portion 12 , and the slide portion 12 is slidably mounted on the base plate 11 . At the slide portion 12 there is provided, a second moving means 20 y (Y-direction moving means or second-direction moving mean) which is composed of a screw-transfer mechanism or the like which is rotated by a motor M 1 . The slide portion 12 is provided with a motor M 2 and a chuck portion 13 . The proximal end of a mandrel 14 on which the stent W is detachably positioned is chucked or held at the chuck portion 13 and it is constructed such that it can be rotated rotatably in forward and reverse directions by the motor M 2 .
The outside diameter of the mandrel 14 is approximately the same as or a little bit larger than the inside diameter of the stent W. The mandrel 14 is exchangeable in conformity with the inside diameter of the stent W. That is, the mandrel 14 can be exchanged for a mandrel 14 with a different diameter as the diameter of the stent changes. There can be prepared mandrels having several different outside diameters. The mandrel(s) is coated with a black coating material to absorb light and heighten a contrast ratio between the mounted strut S of the stent W and space portions O.
Also, as shown in FIG. 3A , the outer circumferential surface of the mandrel 14 is provided with concave portions 15 . These concave portions 15 can be annular in shape, meaning they each extend around the entire circumference of the mandrel 14 and are axially spaced apart from one another along the length of the mandrel. Alternatively, the concave portions 15 can be individual spaced-apart recesses or depressions in the surface of the mandrel. With the concave portions 15 formed on the outer circumferential surface of the mandrel 14 , a gap G occurs between the outer circumferential surface of the mandrel 14 and the inner circumferential surface Sa of the strut S of the stent W when the stent W is mounted on the mandrel 14 . By virtue of this gap G, when the coating material C is applied on the strut S and even if the coating material C runs out to the side surface of the strut S, the coating material C can be inhibited or prevented from turning around a portion between the surface of the mandrel 14 and the inner surface of the stent W. Also, it is possible, without generating a web or a bridge, to form a coating layer having a uniform thickness on the strut S of the stent W. Furthermore, it is possible to avoid also release difficulties that might otherwise arise when releasing the stent W from the mandrel 14 . The turning around of the coating material C occurs relatively easily at a starting point from which the coating material C is applied on the strut S, so that it is possible for the concave portion 15 to exist only at a portion corresponding to an application start point shown by “Ps” in FIG. 3B , in other words, only at the under portion of, so-called, an X shape portion (crossing portion of the strut S) which exists in one end region of the strut S. However, it is not limited solely to this as it is also possible to form them widely such that the concave portions 15 exist at the inner circumferential surface of all the struts S other than the both end portions, and it is also possible to form them partially (i.e., to provide the concave portions or recesses 15 at more then just the struts at the end portions, but not at all the struts).
Here, the stent W is a stent generally having a cylindrical shape over its entire length and is composed of bent or curved linear struts S having a predetermined width and space portions O formed between (bounded by) the struts S. Also, the stent is manufactured from a biocompatible and biostable material. For example, possible metal materials which can be used to fabricate the stent include stainless steel, Ni—Ti alloy, tantalum, titan, gold, platinum, inconel, iridium, tungsten or cobalt alloy (including cobalt-chromium-nickel alloy). Examples of high-polymer material which can be used include polytetrafluoroethylene, polyethylene, polypropylene, polyethylene terephthalate or polyamide. Examples of a biodegradable high-polymer material which can be used to fabricate the stent include polylactic acid, polyglycolic acid, polylactide, polyglycolide, polyparadioxanone, trimethylene carbonate, ε-caprolactone and the like or a mixture, a copolymer of those above.
Also, the coating material C is a material including at least a solvent, a polymer and a therapeutic substance. It is preferable for a polymer usable as the coating material C to be a material having appropriate adherence with respect to the strut S and having film formability which can follow the deformation (shape/configuration) of the stent W. The polymer can be either biodegradable or non-biodegradable, and it is preferable that the polymer have an excellent biocompatibility characteristics in order to minimize inflammation of a blood vessel wall. Also, in the case of a non-biodegradable polymer, it is preferable to select a polymer controllable such that the therapeutic substance will be eluted over time. In the case of a biodegradable polymer, it is preferable to select a polymer which will be decomposed in an appropriate time period. Examples of a biodegradable polymer which can be used include polylactic acid, polyglycolic acid, poly-butyric acid, poly-hydroxybutyric acid, polyparadioxanone, trimethylene carbonate, ε-caprolactone, poly-malic acid, poly-a-amino acid, collagen, laminin, heparan sulfate, fibronectin, vitronectin, chondroitin sulfate, hyaluronic acid and the like or a mixture, a copolymer of those above.
Examples of a non-biodegradable polymer which can be used include silicone, cellulose-based polymer, polyurethane, polyester, polymethacrylate, polyethylene-oxide, polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, poly-acrylic acid or the like.
For the therapeutic substance, examples of a medicine which suppresses migration & proliferation of vascular smooth muscle cells and which can be used in the coating include taxol (paclitaxel), actinomycin C, mitomycin C, adriamycin, genistein, tyrphostin, cytochalasin, sirolimus (rapamycin), tacrolimus, everolimus or the like.
It is preferable for the solvent to be a solvent which dissolves a polymer, a therapeutic substance and the like, but it is possible to select a solvent which can disperse those uniformly. Also, it is preferable for the stent W to be provided with wettability and an appropriate vaporization speed, and the stent is preferably selected by achieving a balance therebetween. Preferable solvents include acetone, N-methylpyrrolidone, dimethyl sulfoxide, toluene, xylen, methylene chloride, chloroform, fleon, dioxane, acetic ether, tetrahydrofuran, dimethylformamide, dimethylacetamide or a mixture of those above.
Further, it is also possible to add additive agents aiming for adjustment of the physical characteristic of the polymer film, improvement of adherence with respect to the stent W, viscosity adjustment of the coating solution, oxidation inhibition of the therapeutic substance or the like. Examples of those additives include glycerol, triacetyl glycerine, ethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, polyalkylene-oxide, sebacic acid ester, citric acid ester, phthalic acid ester or the like.
The coating material C discharged from a nozzle 38 , described in more detail below, is deployed on the strut S. The preferable viscosity of the coating material C is 0.1 cp to 10 cp, preferably 1.0 cp to 4.0 cp. When the viscosity is substantially higher than this level, there exists a possibility that a relatively large pressure will be required to discharge or the discharge of the coating material from the relatively thin nozzle 38 will not be possible. When the viscosity is substantially lower than the noted level, the discharged coating material C runs out of the strut S and there may happen a case in which a uniform coating layer cannot be formed.
The applicator head 30 includes, as shown in FIG. 4 , a dispenser 33 composed of, for example, a syringe operation mechanism and a nozzle portion 34 for discharging the coating material C. The dispenser 33 is mounted on a vertical table 32 . The vertical table 32 is mounted in the support frame 6 by a bracket 31 . The vertical table 32 is moved in the Z-direction by the screw-transfer mechanism or the like driven by a motor M 3 , and the dispenser 33 gradually discharges the coating material C retained in the inside of the nozzle. As discussed below in more detail, the syringe operation mechanism and the nozzle portion 34 are thus movable in the Z-direction to maintain a constant distance or spacing between the surface of the stent and the nozzle tip during coating application.
The dispenser 33 of this disclosed embodiment includes, as shown in FIG. 2 , a cylinder portion 35 having an interior in which the coating material C is retained, a piston portion 36 slidably positioned in the interior of the cylinder portion 35 , and a driving unit 39 which presses the piston portion 36 by a predetermined force F. The driving unit can be, for example, a motor, a liquid pressure mechanism or the like.
The nozzle portion 34 comprises a mounting member 37 at the lower end of the cylinder portion 35 , and the nozzle 38 which is directed downwardly (hangs down) from the mounting member 37 . The nozzle portion thus forms a flow route along which the coating material C flows from the cylinder portion 35 to the nozzle 38 .
The outer diameter of the tip of the nozzle 38 is 10 μm to 1000 μm, and the inner diameter of the tip of the nozzle 38 is 1 μm to 500 μm, preferably 5 μm to 250 μm, such that the coating material C having the viscosity mentioned above is able to be pushed out with a predetermined discharge speed. In the case of a nozzle tip having an inner diameter substantially less than 5 μm, the coating material C does not flow out in a sufficiently smooth manner. Also, a large pressure will be required to effect the discharge. In the case of an inner diameter substantially greater than 250 μm, there is a concern that the coating material C cannot be applied substantially smoothly on the top of the stent W which is used presently.
Also, it is preferable for the nozzle 38 (outside surface of the nozzle) to be polished to lessen surface irregularity as much as possible in order to avoid the attachment of the discharged coating material C. Consequently, it is preferable to use, for example, stainless steel, carbon steel, nickel, chromium, glass, aluminum oxide, zirconium oxide, diamond, a mixture of those above or the like, as these materials can be relatively easily processed.
As shown in FIG. 2 , the dispenser 33 in this disclosed embodiment is constructed such that it is able to deposit the coating material C on the surface of the strut S while being spaced apart from the stent such that the distance L between the nozzle 38 and the strut S is a predetermined distance and the coating material C will be pushed out continuously without a break from the nozzle 38 and directed to the surface of the strut S. If such a continuous push-out system is employed, uniform application of the coating material C becomes possible with respect to the whole surface of the stent W and also, the continuous push-out system can quantitatively discharge, so that controllability is excellent and quantitative adjustment of the therapeutic substance can be carried out relatively accurately and reliably. Furthermore, in the inside of the chamber which is adjusted for the constant-temperature & constant-humidity, the condition by which the coating material C is dried and solidified is constant, so that production of the stent W on which the coating material C is deposited can be carried out easily and also rapidly.
The distance L between the nozzle 38 and the strut S is preferably 0.1 μm to 200 μm, more preferably 1 μm to 100 μm, as measured along an imaginary continuation of an axis of the nozzle. When the distance L is substantially larger than this distance, a problem might arise in that the coating material C will be interrupted. When the distance L is substantially shorter than the noted distance (i.e., is excessively narrower), a problem can arise in which the coating material C runs out of the surface of the strut.
In the embodiment disclosed here by way of example, the applicator head 30 is a head having one nozzle 38 and one dispenser 33 , but it is also possible to employ a head having a plurality of nozzles 38 and a plurality of dispensers 33 . Providing a head having a plurality of nozzles 38 and a plurality of dispensers 33 makes it possible to carry out the application of the coating material C in shorter time, thus improving productivity and providing advantages from the standpoint of production cost.
The first position information obtaining means 40 shown in FIG. 1 includes imaging means for obtaining an image. The imaging means (e.g., a camera unit) is mounted in a position-fixed manner on a bracket 41 which is mounted on the support frame 6 . More specifically, the first position information obtaining means 40 includes a camera unit 42 and a line sensor unit arranged to extend in the axial direction of the stent W. The camera unit 42 and the line sensor scan the surface of the stent W in synchronization with the rotation of the stent W of the holder 10 , obtain an image of the surface of the stent W and communicate it to the control unit 60 . As a start position at which the line sensor unit begins to obtain the surface image of the stent W, any position is acceptable, but preferably it is set on, for example, an axial center line corresponding to the application start point Ps mentioned above. The camera unit 42 and the line sensor unit are known features and are thus not discussed in detail here.
As mentioned above, the mandrel 14 is coated with a black coating material to absorb light and to heighten the contrast ratio between the strut S of the mounted stent W and the space portion O and absorb the light. Thus, with respect to the image of the stent surface, the luminance of the strut S is relatively higher and the luminance of the space portion O is relatively lower. Consequently, it is possible for the control unit 60 to distinguish between the strut S and the space portion O, and to output the coordinates of the strut S, that is to output the X-Y-directions position information of the strut S by binarizing the obtained surface image of the stent W depending on appropriate luminance. Further, the control unit 60 calculates the coordinates of an orbit or movement path along the center line of the strut S (the center of the strut relative to the width-wise direction) based on the obtained X-Y-direction position information (X-Y coordinates of the strut S), and the obtained data of the center movement path is stored in the memory of the control unit 60 . In the case of applying the coating material C, the coating material C should be applied in a manner inhibiting or preventing the coating material from being disengaged from, or misapplied to, the strut S and also for this reason, it is important that the center of the strut S is specified.
The second position information obtaining means 50 is, as shown in FIG. 1 , comprised of a displacement measuring means of the Z-direction for measuring displacement in the Z-direction. The Z-direction displacement measuring means is mounted in a position-fixed manner on the lower end of a bracket 51 mounted on the support frame 6 . In this disclosed embodiment, the Z-direction displacement measuring means is comprised of a laser displacement sensor 52 , a so-called vertical sensor, and measures displacement or the position of the strut S in the Z-direction.
The strut S is a strut whose surface is not smooth in a precise sense and has irregularity. In order to apply the coating material C quantitatively precisely on the strut having such irregularity, the distal end of the nozzle 38 should desirably be moved so it is parallel with the surface of the strut S precisely (i.e., so the nozzle 38 follows the configuration or terrain of the strut S) and a predetermined amount of coating material C is applied. Consequently, in this embodiment disclosed by way of example, by using the laser displacement sensor 52 , the position information of the strut S that is obtained is started from a predetermined position of the stent W, for example from the application start point Ps. The laser displacement sensor 52 is scanned along the orbit or path of movement by rotating the mandrel 14 in the forward and reverse direction, and moving the holder 10 in the Y-direction because the laser sensor 52 is fixed in the support frame 6 in this embodiment. Displacement data is thus collected. The displacement data corresponds to or represents the coordinates of a movement path (orbit) along the center line of the strut(s). The obtained displacement data is communicated to the control unit 60 and stored in the memory.
In the embodiment described above, the second position information obtaining means 50 is provided as a single laser displacement sensor 52 . However, a plurality of the laser displacement sensors 52 can be provided, and in such an alternative arrangement, the position information can be realized more rapidly.
The control unit 60 includes a processor, a monitor, a keyboard and the like. Based on the position information obtained from the position information obtaining means 40 , 50 , the control unit 60 determines the setting of an applying manner by which the coating material is applied and an applying path along which the applicator head 30 applies the coating material C on the strut S of the stent W. Also, the control unit 60 controls the rotation of the mandrel 14 in the holder 10 , the movement of the moving means 20 , the discharge amount of the coating material C discharged from the applicator head 30 , the scanning of the imaging means and of the vertical sensor and the like.
Here, an applying manner refers to an applying route in a case in which the application is executed along the strut S of the stent W. It is preferable for the applying route to be a route which does not have a section in which repetitive application occurs and which can apply the coating to the surface of the strut S continuously. However, in the case of a stent W having struts S intersecting in a complicated manner, it may be difficult to set an applying route having no section in which the repetitive application occurs. In such a case, there may be provided a section in which the repetition application occurs or there may be provided a section in which jumping is done from a certain point on the strut S to another point. In this manner, the applying route can be shortened by providing for a portion with a section of repetition application or a section of jumping. Also, in a section of repetitive application (i.e., a section of a stent or strut in which the coating is applied more than once), the medicine can be applied on all the surfaces of the stent W uniformly by setting the speed to be faster in the section of repetitive application than the moving speed during the section where the coating is applied a single time, and it is possible to sufficiently exert an effect of reducing a re-stenosis ratio in the case of PTCA or the like.
Also, on an occasion of the determination of the applying path, it is preferable to implement various kinds of measures such as described below.
(1) In case of applying the coating material C on the strut S of the stent W, it is preferable, at a straight portion of the strut S, to set the applying path to be an orbit or movement path passing along the axial center-line of the strut S. However, at a curved portion of the strut S, it is preferable to set a movement path or orbit which is deviated by a predetermined distance or length from the axial center-line in the width-wise direction of the strut S as the applying path. The coating material C is a liquid and is applied on the surface of the strut S such that it is raised by surface tension. Even if this is dried and solidified, a coating layer having an arc-shaped (dome-shaped) cross-section is formed. Accordingly, when the application is executed a plurality of times (i.e., when the applying route is executed plural times), it becomes a state of being raised in an arc-shape and is not preferable. Consequently, as shown in FIG. 5 , it is preferable for a coating layer E 2 at the second time to be applied along an applying path that is deviated by a predetermined distance from the coating layer E 1 applied to the strut S the first time. It is also preferable for a coating layer E 3 at the third time to be applied along an applying path that is different from the applying paths of the first and second times. It is preferable for this amount of deviation to bet determined by taking into consideration a width B 1 of the strut S and a width B 2 of the coating layer E.
(2) In determining the applying path, it is preferable for the applying paths to be different in the linear-shaped strut portion and in the curved strut portion. At the linear shaped strut portion, it is generally adequate if the movement path is along the center of the strut S in the width direction of the strut S. However, at the curved strut portion, if the applying path coincides with the center line of the strut S in the width direction of the strut S, the application of the coating material C discharged from the applicator head 30 may be affected by the viscosity of the coating material, the falling speed from the nozzle, or the like, and so the path along which the coating material is applied may not follow the moving path of the applicator head 30 . Accordingly, in this embodiment, as shown in FIG. 6 , a curved line P (dotted line) passing outside the curved line (dashed-dotted line) passing through the center line of the curved portion of the strut S is set as the applying path.
Here, the applying path P shown by the dotted line extends outwardly to the outside portion of the strut S, and this is based on knowledge that when the coating material C applied on the strut S by being pushed out continuously, the coating material C can be prevented more reliably from being disengaged from the strut S (i.e., from being misapplied or not applied to the strut) depending on the characteristic of the coating material C.
(3) At the crossing portion of the strut S, it is preferable for an intersection point of a center line of plural struts S or the vicinity of the intersection point thereof to be the applying path. At the portion at which the struts S intersect, the applying path P will also be intersected, so that if the intersection point of a center axis line of the struts S or the vicinity of the intersection point is set to be the applying path, it is possible to inhibit or prevent running off of the coating material C which is preferable.
Next, a coating method is explained with reference to FIG. 7 and FIG. 8 which are flowcharts illustrating aspects of the coating method using the apparatus described above.
<Preparation Process>
First, upon starting the coating, the air conditioner 5 is activated and the inside of the chamber 3 is conditioned so it is a constant temperature and constant humidity. Then, at the support frame 6 , there is set the applicator head 30 , including the syringe operation mechanism 33 and the nozzle portion 34 including the nozzle 38 having an inside diameter corresponding to the width of B 1 of the strut S and the coating material C in the cylinder portion 35 .
The stent W is attached or mounted on the mandrel 14 and the mandrel 14 is mounted on the chuck portion 13 of the holder 10 which is positioned at a standby position. At that time, the application start point Ps of the strut S is set so as to positioned over the concave portion 15 of the mandrel 14 . Here, in the case of having the moving means 20 at the lower portion of the chamber 3 , as shown in FIG. 1 , the standby position is in the vicinity of an entrance portion 3 A of the chamber 3 .
<Imaging Process>
The control unit 60 accepts input in the form of imaging parameters, and the inputted imaging parameters are stored in a storage device (S 1 in FIG. 7 ). The imaging parameters are, for example, inputted from a keyboard by an operator. The imaging parameters include a rotation speed of the mandrel 14 , the number of imaging lines, an imaging line width and an operation speed when imaging.
The control unit 60 provides instructions to start imaging after storing the inputted imaging parameters. Concurrently, the X-direction moving means 20 x is activated (S 2 in FIG. 7 ). When the X-direction moving means 20 x is activated, the holder 10 moves from the standby position under the first position information obtaining means 40 by way of the traveling rail 21 . The control unit 60 confirms that the holder 10 reached the predetermined position (S 3 in FIG. 7 ) and if the holder 10 reached the predetermined position, it activates the motor M 2 of the holder 10 and starts the rotation of the stent W (S 4 in FIG. 7 ).
The line sensor of the first position information obtaining means 40 starts the imaging based on the imaging start instruction, scans the surface of the stent W relatively, because the stent W is rotating, and images the surface pattern of the stent W (S 5 in FIG. 7 ). The imaged picture is stored in the storage device (for example, memory, hard disk or the like) of the control unit 60 as a plan view development image. In addition, it is also possible to employ an arrangement in which the imaged picture is outputted to a monitor so an operator is able to view or confirm the imaged picture by watching the monitor.
With respect to the surface image of the stent W, the luminance of the strut S is relatively high and the luminance of the space portion O is relatively low. The control unit 60 converts the stent surface image to a black-and-white binarized image by setting a certain luminance as a boundary (S 6 in FIG. 7 ), and calculates the coordinates of the movement path or orbit along the center (center line) of the strut S by a thinning processing of the width of the strut S (S 7 in FIG. 7 ). This thinning processing simply refers to processing that converts the pattern image of the strut S into a linear image, for example a linear image of one pixel in width.
<Setting Process of Applying Manner>
At S 8 in FIG. 7 , judging the surface image of the stent W obtained by the process and taking into account any perceived necessities (e.g., judging whether or not it is possible to trace the applying route by a single stroke), and considering the position of any section(s) in which repetition application or jumping may be performed, the system sets the applying manner so that all surfaces of the strut S are applied or coated with the coating material during the coating application. The applying manner involves determining for example, whether or not the applying route of the nozzle will include any section(s) of repetition application and/or jumping. The applying route is preferably set such that the section(s) in which the repetition application is done and the section(s) in which the jumping is done are reduced or shortened as much as possible. In the event the applying route includes a repetitive section, the applying manner can also include the speed of the nozzle when moving along the repetitive section of the applying route.
<Displacement Measurement Process of Z-Direction>
Next, the control unit 60 accepts input of displacement measuring parameters of the second position information obtaining means 50 which is the Z-direction displacement measuring means and stores such parameters (S 9 in FIG. 7 ). These displacement measuring parameters are also inputted by an operator. The displacement measuring parameters include data (coordinates) of the measuring start position, the measuring direction, the direction at the branch point, the measuring speed and the measurement point interval. The displacement measuring parameters set the measurement method of the second position information obtaining means 50 . These parameters can be, for example, inputted at the keyboard by the operator before the Z-direction displacement measurement. The Z-direction displacement measuring means 50 works or operates according to these parameters.
The control unit 60 activates the motor M 1 of the Y-direction moving means 20 y after storing the displacement measuring parameters (S 10 in FIG. 7 ). At that time, if necessary while observing by way of a video camera and a monitor, the stent W and the measuring position of the displacement measuring means are adjusted such that the actual measurement start point of the Z-direction displacement measuring means agrees with the start point on the strut S specified by parameters on the monitor (S 11 in FIG. 7 ).
Once this adjustment results in the actual measuring position and the specified position being the same position (confirmation of coincidence of these two positions can be inputted by the operator to the control unit 60 (S 12 in FIG. 7 : Yes)), the control unit 60 instructs the second position information obtaining means 50 on the start of the measurement of the Z-direction displacement in the strut S (S 13 in FIG. 7 ). Concurrently, the control unit 60 controls the motor M 2 to repeatedly rotate in the forward and reverse rotations (clockwise and counterclockwise rotations), and controls the motor M 1 to repeatedly move in the axial direction (Y-direction). Thus, the stent W repeatedly rotates and moves in the axial direction or Y-direction (S 14 in FIG. 7 ).
Thus, the second position information obtaining means 50 moves along a movement path that follows the center line of the strut S, and the control unit 60 collects the Z-direction displacement data (S 15 in FIG. 7 ). This displacement data are stored in the storage device of the control unit 60 together with the coordinates of the movement path along the center line. This Z-direction displacement data indicates the distance between the tip of the applicator head and the surface of the strut S (stent), and this information fed to the control unit 60 allows the control unit to effect appropriate control to maintain a constant distance between the tip of the applicator head and the surface of the strut S (stent) during application of the coating material.
<Applying Process>
The control unit 60 accepts an input of application parameters, and stores this input (S 16 in FIG. 7 ). Application parameters are also input by an operator. The application parameters include data of the application start position, the application (applying) direction, the direction at the intersection, setting of the movement path adjustment section, the deviated length of the movement path, the applying speed, the discharge speed of the coating material C, the height of the applicator head, the number of applications (number of layers) and the selection of the applicator heads. Application parameters involving the direction at the intersection include parameters defining the direction in which the nozzle moves when encountering an intersection such as Ps in FIG. 3B where there are multiple direction of movement. Application parameters involving the setting of the movement adjustment section include setting the applying path to deviate from the strut center line as generally indicated by the dotted line P in FIG. 6 . Application parameters involving the deviated length of the movement path include setting the amount of deviation of the movement path from the strut center line. Since the application parameters which are inputted and stored at S 16 include, for example, data about the application start position, the application (applying) direction, the direction at the intersection, setting of the movement path adjustment section, the deviated length, of the movement path, the applying speed, the discharge speed of the coating material C, the height of the applicator head, the number of applications (number of layers), and the selection of the applicator heads, the applying path is set at S 16 . That is, S 16 constitutes the setting of the applying path which accommodates the applying manner.
The control unit 60 instructs the application start (start of coating material application) after storing the application parameters. Concurrently, the control unit 60 instructs the movement of the holder 10 by the X-direction moving means 20 x (S 17 in FIG. 7 ). Thus, the stent W is moved to the application start position under the applicator head 30 (S 18 in FIG. 7 ). Once the stent W reaches the application start position under the applicator head 30 (S 19 in FIG. 7 : Yes), the control unit provides instruction to the motor M 2 to perform the positive and reverse rotations and provides instruction to the motor M 1 to effect movement in the axial direction so that the stent W is moved in the X-axis direction and in the Y-axis direction depending on the appointed parameters according to the positive and reverse rotations by the motor M 2 and according to the axial movement by the motor M 1 (S 20 in FIG. 7 ). During this time, the coating material is applied to the stent struts.
Thus, the stent W is moved in the X-axis direction and the Y-axis direction according to the applying path previously determined (appointed parameters), the applicator head 30 is moved in the Z-direction according to displacement data (appointed parameters) received from the second position information obtaining means 50 , and the coating material C is discharged from the applicator head 2 continuously. Thus, the applicator head 2 applies the coating material C moving along the predetermined applying route and path.
During the application of the coating, the space between the distal end of the nozzle 38 and the stent W is in a state of being filled by the coating material C, so that the coating material C is discharged by a fixed amount and the amount of the therapeutic substance on the stent W is also reliably set to be a predetermined value. Furthermore, the web and the bridge are not generated between the struts S, and the coating layer E can be formed extremely accurately.
When the coating is completed, the holder 10 is moved to the standby position by the X-direction moving means 20 x , the mandrel 14 is removed from the holder 10 and is taken outside the chamber 3 , and the stent W is released or taken off the mandrel 14 .
The disclosed method and apparatus here are not limited to the embodiments disclosed by way of example above. Various modifications are possible in the technical idea of the disclosure here, depending on a person skilled in the art. For example, the embodiments described above relate to a case in which one kind of coating material C is applied, but depending on the product, the situation and the like, it is also possible to use plural kinds of coating materials. In case of applying a plurality of coating materials C, a plurality of syringes, nozzles and syringe operation mechanisms can be employed, and the coatings are applied by changing-over them sequentially. The sequential changeover of these syringes, operation mechanisms and the like is controlled by the control unit 60 . Here, the different coating material C means the polymer is different or the polymer is the same and the amount thereof is different; the therapeutic substance is different or the amount of the therapeutic substance is different; or the solvent is different. In this manner, if plural kinds of coating materials are used, the medicinal effects become additive and it becomes extremely advantageous in cases such as a case in which physical and mental burdens for a patient are reduced or the like.
Also, in the disclosed embodiments, the holder 10 is moved by the first and second moving means 20 x , 20 y and the applicator head 30 and the first and second position information obtaining means 40 , 50 are fixed. However, it may not always be necessary to employ a construction in which only the holder 10 is always moved and other parts must be fixed. It is possible for these movements to be relative and thus, it is enough if predetermined moving means is installed suitably.
Further, also with respect to the movement directions of the holder 10 , the applicator head 30 and the first and second position information obtaining means 40 , 50 , it is not necessary to always employ a construction in which the applicator head 30 and the holder 10 are relatively moved in two directions orthogonal to each other in the horizontal surface or in which the movement is executed in the vertical direction relatively. It is also possible to select the most suitable condition depending on the shape or the like of the stent W.
INVENTIVE EXAMPLE 1
For the stent W, there was used the following stent and the coating is executed.
Stent W: Inside Diameter of 1.7 mm, Thickness of 150 μm, Full Length of 30 mm
Width of Strut S (minimum): 107 μm Radius of Curvature of Strut S (minimum): R=0.1 mm
The pattern of strut S is a pattern obtained by connecting rings composed of waveforms with linear shaped links.
The material of the stent W is stainless steel.
Viscosity of Coating Material C: 2.5 cp (20° C.)
Discharge Speed of Coating Material C: 0.0067 μl/sec Adjustment Deviated Length of Orbit of Curved Portion :40 μm in Y-direction (Stent Circumferential Direction) :60 μm in X-direction (Stent Long Axis Direction) Applying Speed on Orbit Passing the Center: 2.4 mm/sec Applying Speed on Orbit Deviated from the Center: 3.3 mm/sec Applying Speed in Section of Repetition Application: 4.8 mm/sec Inner Diameter of Tip of Nozzle 38 : 43 μm Outer Diameter of Tip of Nozzle 38 : 200 μm Distance (L) between Stent W and Nozzle 38 : 40 μm Number of Applications (Number of Layers): 10 Layers
The manner of applying or the applying route was selected such that there was provided a section in which the repetition application occurred at a portion of the applying route, but there was no section in which jumping occurred.
The average thickness of the coating layer of the stent of the inventive example 1 was 40 μm, and the coating could be realized without the web, the bridge and running out to the stent side surface. Average thickness refers to the thickness determined by measuring the thickness at plural locations (e.g., three), adding together the measured thicknesses, and dividing by the number of measured locations.
INVENTIVE EXAMPLE 2
Next, with respect to the stent W, the following stent was used and the coating was carried out.
Stent W: Inside Diameter of 1.7 mm, Thickness of 150 μm, Full length of 30 mm
Width of Strut S (minimum): 104 μm Radius of Curvature of Strut S (minimum) R=0.07 mm
The pattern of the strut S is obtained by connecting rings composed of waveforms with linear shaped links.
The material of the stent W is stainless steel.
Viscosity of Coating Material C: 2.5 cp (20° C.)
Discharge Speed of Coating Material C: 0.0056 μl/sec Adjustment Deviated Length of Orbit of Curved Portion : 32 μm in Y-direction (Stent Circumferential Direction) : 52 μm in X-direction (Stent Long Axis Direction) Applying Speed on Orbit Passing the Center: 4.4 mm/sec Applying Speed on Orbit Deviated from the Center: 5.7 mm/sec Applying Speed in Section of Repetition Application: 8.8 mm/sec Inner Diameter of Tip of Nozzle 38 : 43 μm Outer Diameter of Tip of Nozzle 38 : 200 μm Distance (L) between Stent W and Nozzle 38 : 40 μm Number of Applications (Number of layers): 10 layers
The manner of applying or the applying route was selected such that there was provided a section in which the repetition application occurred at a portion of the applying route, but there was no section in which jumping occurred.
The average thickness of the coating layer of the stent of the inventive example 2 was 40 μm and the coating could be realized without the web, the bridge and running out to the stent side surface.
With the coating method and apparatus here, it is possible to reduce the re-stenosis ratio of the dilation portion drastically after the percutaneous transluminal coronary angioplasty (PTCA).
The detailed description above describes preferred embodiments of the coating method and apparatus disclosed here with reference to the accompanying drawings. However, it is to be understood that the invention is not limited to those precise embodiments described and illustrated above. Various changes, modifications and equivalents could be effected by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims. It is expressly intended that all such changes, modifications and equivalents which fall within the scope of the claims are embraced by the claims.
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A coating method and a coating apparatus are used to apply coating material to struts of a medical device (e.g., stent) which bound openings. The method involves optically scanning the medical device to produce position information identifying positions of the struts, using the position information to calculate a predetermined position, setting an applying manner to apply the coating material based on the predetermined position, setting an applying path accommodating the applying manner, and relatively moving the medical device and an applicator head along the applying route and path while dispensing the coating material from the applicator head and applying the coating material to the struts.
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FIELD OF THE INVENTION
The invention relates to a vehicle door with a cross-arm type window lift and a lock assembly connected together as a multi-function modular unit, and more particularly to a preassembled mounting panel including the multi-function modular unit.
BACKGROUND OF THE INVENTION
The prior art has long recognized the desirability of manufacturing a vehicle door with the door hardware, such as the window, the window regulator and the door handles mounted on a panel to define a module which may be preassembled away from the vehicle assembly line to speed up on-line assembly and subsequent testing and setup. For technical and economical reasons the vehicle door construction should both sufficiently absorb energy and minimize the weight of the door.
An interior door panel and an exterior door panel attached together in a spaced apart relation defining a cavity is described in U.S. Pat. No. 5,111,620. The interior door panel has a plurality of openings therein and the door components are individually mounted on the interior panel within these openings by a plurality of energy-absorbing devices which are preferably comprised of convoluted straps.
European Patent Application 0 563 742 A1 describes a preassembled operating panel which is housed inside the hollow bottom portion of a vehicle door and which represents the door lock mechanisms, a device for regulating and guiding the sliding window of the door and a central load-bearing element. The central load-bearing element consists partly of a portion of the window regulating device and comprises elements for connecting the operating panel to the door lock mechanisms being fitted to the central load bearing element.
From U.S. Pat. No. 5,251,403 it is known that a mounting panel for mounting a window and a window regulator in a vehicle door is comprised of a one-piece plastic molded member having a central planar mounting member adapted to mount the window regulator, and a plurality of spaced-apart spokes molded integrally with the center drill plate and radiating generally forward and rearward therefrom to mount the guide channel receiving the edges of the window. A plurality of snap fasteners are integrally molded with the mounting panel for snap-together fastening of such door operating hardware as the window regulator, the window regulator motor, door handle and the door latch control rods.
According to U.S. Pat. No. 5,050,350, an interior vehicle door panel is provided on its face turned toward the inside of the door with means for the fastening and preassembly on this panel of internal elements of the door, in particular a window lift, a lock, a slide for guiding and locking the window in the lowered position, and inside operating controls. These elements are provided with means for fastening to a panel forming a structure inside the door. This arrangement eliminates an internal plate supporting the elements.
Although the above described prior art vehicle doors are effective in providing preassembled window lift and door lock systems, the components are each individually mounted, and no provision is made for integrating the functions of different components. Nor do the prior art vehicle doors make provision for a dry-space between a sheet metal door panel and a trim panel. The integrity of included electrical components may, therefore, be compromised unless protected by additional and expensive weather proofing.
A simple and inexpensive vehicle door with multi-functional components mounted on a base plate and attached to the door so as to form a dry-space for electrical components is, therefore, needed for more cost-effective assembly operations.
SUMMARY OF THE INVENTION
The present invention is directed to a vehicle door which is constructed from a reduced number of individual parts and/or requires less of an assembly effort and/or permits the employment of more cost-effective structural parts or structural components.
A vehicle door in accordance with the invention suitably comprises a cross-arm type window lift which includes crossed lever arms, connected together with a hinge at the crossing point. The upper ends of the lever arms are connected to a guide rail which supports a window. One lever arm is pivotally connected to a bearing and includes a gear assembly connected to its lower end adapted to engage with a pinion drive gear for raising and lowering the window. A second lever arm is slidably connected to a second guide rail which is disposed in a fixed relationship to the vehicle door. The vehicle door also comprises a lock assembly, wherein the second guide rail of the window lift also supports the lock assembly, eliminating an otherwise customary separate support of the lock assembly. This not only results in the elimination of a structural component, but also leads to a reduction of tolerance deviations and a savings in weight and assembly cost.
In one embodiment of the invention, the lock assembly is movable along a major direction of the second guide rail by inserting more or less of an end of the second guide rail into a receiving cavity provided in a base body of the lock assembly. In an alternative embodiment of the invention, the guide rail is seated in a limitedly displaceable manner on a support plate, in which case the lock assembly is then fixed in place on the end of the guide rail. The displaceability of the lock assembly with respect to the body of the door is advantageous for compensating for manufacturing tolerances when finally assembling the door.
In a further embodiment of the invention, a vehicle door with a window which can be raised and lowered and with a lock assembly for unlocking and locking the door includes a lock assembly base body which further includes window guide means which support and guide a portion of the lateral window edge, the window guide means being integrated into the base body of the lock assembly.
In particular, the base body of the lock assembly and the guide means for the window are constructed as a one-piece component from a suitable material such as plastic. In addition, the window guide means can be constructed to extend in length beyond the outer contour of the base body of the lock assembly. The window guide means, integrated in the lock assembly, and lengthened in this way can result in the elimination of the conventional guide rails disposed in the door. The lengthened window guide means and the base body of the lock assembly are constructed in two pieces and connected together. The connection between the window guide means and the base body of the lock assembly is made to be resilient. In this way it is possible to compensate not only for manufacturing tolerances, but also unavoidable elastic stresses in the door.
In yet a further embodiment of the invention, a vehicle door is constructed with a cross-arm type window lift preassembled on a base plate which is installed inside the door body through a mounting opening in an interior sheet metal door panel. The base plate covers the mounting opening and completely seals the mounting opening by means of a circumferential seal placed around the outer edge of the base plate thereby forming a dry space between the interior sheet metal door panel and an interior door covering, as well as a wet space between the interior and the exterior sheet metal door panels. In particular, when the contour of the outer edge follows a complicated course, a profiled seal is formed directly on the outer edge of the base plate.
Preferably, when using an electrical drive element for operating the window lift, all current-carrying parts such as the electric motor, any electronic components, switches, and the plugs and cables, are mounted in the dry space. A seal is disposed between the housing of the drive element and the base plate in the area where the drive shaft passes through from the dry space to the wet space. To the extent that further openings are provided in the base plate, for example, for adjusting the window, these are sealingly closed following their use.
The base plate can also be used as a transport assistance means for transporting parts of the door lock which, for example, are connected with each other via suitable plug connections.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features, aspects and advantages of the present invention will be more fully understood when considered with respect to the following detailed description, appended claims, and accompanying drawings, wherein:
FIG. 1 is a schematic elevational view of a cross-arm window lift mounted on a base plate and connected with a lock assembly;
FIG. 1A is a semi-schematic elevational view of a two-piece lock assembly including a base body and a separate lateral window guide;
FIG. 2 is a semi-schematic cross-sectional view taken horizontally through a vehicle door body equipped with the components of FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
A schematic diagram of a cross-arm window lift is depicted in FIG. 1, in which crossed levers 4, 5 are connected together at a hinge point 45. The upper ends, 4A and 5A respectively, of each lever arm are connected at sliding hinge points 21, 22 with a guide rail 2 on which a window lift rail (not shown) is fastened. The window lift rail is a part of the lower edge 70 of a window 7. Elongated alignment holes 23, 24 are provided in the guide rail 2 for adjusting the alignment of the window in the door and for simultaneously compensating for manufacturing tolerances.
The lever 4 is rotatably supported below the hinge point 21 in a bearing 40. The bearing 40 is embedded, or otherwise mounted on a base plate 1, which is not only used as a support, but also for sealing a mounting opening 110 in an interior sheet metal door panel 100 (also see FIG. 2). The lower end 4B of the lever 4 which extends past the bearing 40 is attached to a gear assembly which comprises a toothed gear segment 41 whose tooth elements engage and mesh with the teeth of a pinion drive gear 81 for raising and lowering the window.
The lower end 5B (below the hinge point 45) of the other lever 5 i.e., the portion of the lever 5 below the hinge point 45, is slidingly supported in a guide rail 3 at a hinge point 33. The guide rail 3 is fixed or can be fixedly fastened on the base plate 1, in the same manner as the bearing 40. When the base plate is attached to the vehicle door, in a manner described further below, the guide rail 3 is, thereby, located in a fixed relationship to the vehicle door.
In operation, the pinion drive gear 81 is rotated by, for example, a hand operated crank or an electric motor, when the window is desired to be raised or lowered. The pinion gear teeth engage the teeth of gear assembly 41 which moves the gear assembly attached to the lower end of lever arm 4, thus rotating lever arm 4 about the bearing 40. As the lever arm 4 is rotated, its upper end 4A exerts an upward force on the upper guide rail 2 which transfers the force to the window 7, thus raising it.
In order to maintain an even support on the lower edge of the window, the lower end 5B of lever arm 5 is supported in the lower guide rail 3, which is maintained in fixed relationship to the vehicle door. As the window is raised, the two lever arms pivot about the hinge 45 in scissor fashion; the upper ends 5A and 5B of the lever arms sliding towards one another, along the major length direction of the upper guide rail 2, while the lower end 5B of lever arm 5 slides along the major direction of lower guide rail 3 (its length direction). Any downward force exerted by the lower end of lever arm 5 is opposed by the fixed guide rail 3. Since the lever arms 4 and 5 are both fixed at portions below the hinge 45, at least with respect to vertical movement, but are free to move at their upper portions, only the upper guide rail 2 moves, thus raising or lowering the window.
In accordance with the invention, the guide rail 3 extends in a major direction beyond its functional range needed for supporting lever arm 5, and is connected with a lock assembly 6. In this way the guide rail 3 provides a bearing function in respect to the lock assembly 6 which, in conventional vehicle doors, is provided by a separate lock support. In general, a base body 62 with a lock cylinder 63, a locking/unlocking element (not shown), and a handle 64 for operating the element are a part of the lock assembly.
Since the lock assembly 6 must, at some point, be attached to the vehicle door, and since the lock assembly attachment points of vehicle doors often have varying manufacturing tolerances, the lock assembly must be displaceable to the degree necessary to compensate for those tolerances.
Two basic variants are available to make possible the desired displaceability of the lock assembly 6. In one embodiment, a guide channel 60 is provided in the base body 62 of the lock assembly 6, into which an end 30 on the lock side of the fixed guide rail 3 can be inserted. The lock assembly 6 is moveable along the major axis of fixed guide rail 3 (displacement direction 65, shown in FIG. 1) depending on the degree of insertion of the guide rail end 30 into the guide channel 60. Guide channel 60, therefore, provides means for compensating for tolerances when the lock assembly is fastened to the door body.
In an alternative embodiment, the lock assembly 6 is fixedly seated on a moveable guide rail 3. Displaceability (displacement direction 34, shown in FIG. 1) of the assembly is accomplished by movably connecting the guide rail 3 on the base plate 1. Slots 31 and 32 are cut into the guide rail 3, which are engaged by two cap bolts 12 and 13 fastened on the base plate 1, thus allowing the assembly to move, along displacement direction 34, through a range defined by slots 31 and 32.
Guide rail 3 is preferably constructed as a one-piece structural part, having a constant, unbroken, profile. Suitable materials for fabricating such a guide rail include those produced by extrusion molding, extruding or rolling, such as aluminum, plastic or other organic or inorganic composites.
Although both displacement variations have been depicted for the sake of improved visualization, it will be understood that either one, alone, can be used for purposes of the invention. The one which best meets the practical requirements will preferably be selected.
It should also be pointed out that the guide rail. neither needs to have a continuously uniform profile nor does it need to extend in a straight line (as illustrated). A multi-section guide rail 3, with each section having a different profile, can also be employed. Such a multi-section guide rail can be advantageously employed in cases where a direct link between the window lift and the lock assembly is not possible, for example where the guide rail must be routed around a projecting piece of unrelated equipment. Such a guide rail is suitably fabricated of a stamped material such as a Low cost metal.
In accordance with the invention, the base body 62 of the lock assembly 6 is provided with guide means 61 for supporting and guiding the edge of window 7. As depicted in FIGS. 1 and 2, guide means 61 suitably comprises a channel-like cross section provided in connection with base body 62. Guide means 61 and the base body 62 are constructed as a one-piece component which is advantageously manufactured of an extruded or cast material. Alternatively as depicted in FIG. 1A, a separate guide means 61A can be provided which is then attached to the base body 62A, forming a multi-piece assembly. In this embodiment, both the base body and the guide means may be constructed of different materials. For example, if the guide means are expose to large stress forces, the guide means 61A may be constructed of metal, while the base body 62A of the lock assembly 6A may constructed of a low cost, low weight material such as plastic.
It is of course also possible to extend the window guide means 61A lengthwise, past the upper and/or lower contour of the base body 62A, thus providing a longer contact surface between the window and the guide means. This allows the elimination of the conventional window guide rails disposed in the door. In this embodiment, guide means is elastically connected to the base body by a resilient material in order to allow the guide means to flex in response to window motion, thus compensating for manufacturing tolerances and unavoidable elastic stresses in the door.
With a two-piece guide means, the guide means can be constructed of a suitable material, such as an extruded plastic, when the guide means are intended to perform mainly guide functions. When a stronger guide means is desirable, such as when it also performs supporting functions, it can be manufactured of a suitable metal or composite material. The choice of plastics, metals, a combination of materials or even composite materials to construct the guide means is, therefore, a function of the requirements and stresses of the respective use.
With the use of modular construction, it is furthermore advantageous to provide a base plane 1, supporting a window lift, with a circumferential seal 11. As depicted in FIG. 2, such a base plate preferably has a circumferential profile such that, when attached to a mounting opening 110 located in an interior sheet metal door panel 100, the base plate 1 covers the mounting opening 110 and the circumferential seal 11 provides for complete sealing of the mounting opening 110. In This manner a so-called dry space, between the interior sheet metal door panel 100 and an interior door covering 300, such as a trim panel, is created. At the same time, a so-called wet space, between the interior and exterior sheet metal door panels 100 and 200, is created without any additional manufacturing steps. Profiled rubber pieces, constructed as a single piece which can be placed on outer edge of the base plate 1, are particularly suited for use as a seal when the base plate outer edge has a simple shape, free of discontinuities. For shapes with complicated edges, the sealing material can be sprayed or adhesively affixed to the base plate edges.
Openings (10 of FIG. 1) are provided in the base plate for providing access to mounting points for fastening and adjusting mountable components, for example, the window 7. Integrity of the base plate is maintained by sealing the openings with a cover 10A constructed from a suitable deformable material, such as a rubber panel or plastic cover, which is press-fit into the opening.
Returning to FIG. 2, electrical cables 97, 98 and structural parts or structural components, such as an electric window lift motor/drive assembly 80, electronic unit 82, switches 94, 95, 96 and plugs 90, 91, 92, 93 (see FIG. 2), through which current flows, are disposed in the dry space. It is of course also necessary to provide sufficient sealing by means of a seal 14 in the area where the drive shaft with the pinion 81 passes through. The disposition in the dry space of the electric and electronic components allows the elimination of the usually very elaborate steps for protection against the entry of moisture. With a suitable disposition of the base body 62 of the lock assembly 6, a plug connection 90 for the central locking can be placed in the dry space.
An increase in the degree of integration of the module comprising the base plate 1, the window lift and possibly the lock assembly 6 can be achieved in that the base plate 1 is equipped with transport means, suitably comprising plug or clip connectors, which are connected to the base plate and which support the mechanical operating parts for the interior unlocking and locking mechanism of the vehicle door. The mechanical operating parts for the interior unlocking and locking mechanism are pre-assembled on the base plate by connection to the transport assistance means. The entire assembly can, therefore, be transported to the assembly line as a one-piece unit. Such transport assistance means can considerably reduce manipulative efforts.
The above descriptions of preferred embodiments in accordance with the present invention are for illustrative purposes. Because of variations which will be apparent to those skilled in the art, the present invention is not intended to be limited to the particular embodiments described above. The scope of the invention is defined in the following claims.
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In a vehicle door with a cross-arm type window lift and a lock assembly, which can be produced more easily and cost-effectively by employing modular construction and by using individual components for several different functions. The invention is distinguished by the guide rail of the cross-arm window lift simultaneously functioning as the support for the lock assembly, by the guide for guiding the window being integrated in the base body of the lock assembly and by the outer edge of a base plate supporting a window lift having a circumferential profiled sealing section in the interior sheet metal door panel for sealing a mounting opening, so that the protection of electrical/electronic components is provided in the dry space without additional steps.
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CROSS REFERENCE TO RELATED APPLICATION
This Application is a Continuation of U.S. Ser. No. 09/448,609, filed Nov. 24, 1999, now abandoned, which is a Continuation-in-Part of PCT/CA98/00504, filed May 22, 1998, and published Dec. 10, 1998 as International Publication No. WO98/55693, in which the United States of America was designated and elected, and which remains pending in the International phase until Dec. 4, 1999, which in turn claims priority from U.S. application Ser. No. 60/048,558, filed Jun. 4, 1997, and the benefit of 35 U.S.C. 119(e).
TECHNICAL FIELD
The present invention is in the technical field of papermaking, and, more particularly, in the technical field of wet-end additives to the papermaking stock or furnish. In particular the invention relates to a papermaking stock, a method for increasing or enhancing the retention of components of a papermaking stock during the manufacture of paper, and a method of producing paper. In an especially important embodiment the methods are carried out in relatively “closed” mill water systems while simultaneously increasing drainage and decreasing the amount of deposits from colloidal hydrophobic particles often referred to as “stickies” or “pitch” on the paper machine.
BACKGROUND ART
The manufacture of paper is a complex process which can be broken down into a series of less involved processes. One of the more important processes occurs at the paper machine. At this location, an aqueous cellulosic suspension, stock, furnish or slurry is formed into a paper sheet. The cellulosic suspension is made by providing a thick stock, diluting the thick stock to form a thin stock, draining the thin stock on a forming fabric to form a sheet, and drying the sheet.
The cellulosic slurry is generally diluted to a known consistency (based on percent dry weight of solids in the slurry) of less than 2 percent. Ideally, the consistency is between 0.8 and 1.5 percent.
The cellulosic slurry is generally, but not necessarily, a mixture of chemical, mechanical and secondary (e.g., deinked) pulps. For example, this includes all paper and board furnishes based on mechanical pulp and, in part, semi-bleached kraft pulp, unbleached kraft pulp, and/or unbleached sulfite pulp. The mechanical pulps may be stone-groundwood, pressure groundwood, thermomechanical pulp, or semi-chemical mechanical pulp. Other pulps may include deinked pulps, reslushed newsprint or any secondary fiber source.
Cellulosic slurries of high quality pulps can also be used to produce fine paper grades (e.g., photocopying paper), tissue or toweling sheets. These slurries include highly bleached mechanical or chemical pulps.
It is common to include various inorganic materials, such as bentonite and alum, and/or organic materials, such as various natural, modified natural, or synthetic polymers in the thin or thick stock for the purpose of improving the drainage and retention processes.
Such materials can be added for diverse purposes such as, for example, pitch control, increased drainage and retention, improved formation, increased wet and dry strength, defoaming, facilitation of release from drying rolls, and decolorization of effluents.
In addition, many grades of paper include substantial levels of inorganic fillers such as, for example, kaolinite, calcium carbonate, and titanium dioxide. The percentage of mineral filler added to a papermaking slurry may vary between 0 and 35% by weight of dry paper depending on the type of sheet being formed.
In the papermaking process, much of the pulp is separated from the fibers, fillers, and pigments by filtration. The filtrate, which is called the white water, contains a large amount of unretained colloidal particles which may be fibre fragments, mineral fillers, deinking plant materials, or pigment particles. The poor retention of these is a consequence of the difficulty in the filtration of material characterized by colloidal or nearly colloidal dimensions. Poor fines retention is a serious problem because it results in the loss of valuable cellulosic material and the additional loading of water treatment facilities.
The least expensive and oldest dewatering method is simple gravity drainage. More expensive methods which are also used include vacuum, pressing, and evaporation. Drainage may be accomplished either horizontally or vertically, by one side of the forming sheet only or by both sides.
In practice, a combination of such methods is employed to dewater or dry the sheet to the desired water content. Since drainage is the first dewatering method and the least expensive, improvement in the efficiency of drainage will decrease the amount of water required to be removed by other more costly methods such as drying. This will improve the overall efficiency of the process.
The papermaking fibers employed in papermaking are often of low grade and are predominantly of the mechanical type and include groundwood, thermomechanical pulp, deinked secondary fibers, semi-chemical pulps, and semi-bleached chemical kraft pulps. The cellulosic fibers thus produced are rarely very “clean” and are rarely completely separated from the residual process liquors which contain substantial levels of both organic and inorganic impurities. These impurities are derived from the pulping process and by-products which are naturally present in wood (Linhart F., Auhorn W. J., Degen H. J. and Lorz R., Tappi J. 70(10) 79-85 (1987), Sunberg K., Thornton J., Pettersson C., Holmbom B., and Ekman R., J. Pulp Paper Sci., 20(11), J317-321 (1994)). These are often referred to as detrimental substances because they interfere with the function of many additives.
Detrimental substances increase the cationic demand of the pulp slurry. The cationic demand is the number of equivalents of cationic charge that has to be added to the slurry to neutralize the excess anionic charge of the pulp slurry. The cationic demand is usually met using a low molecular weight (<500 000) highly charged synthetic cationic polyelectrolyte. These polymers are, for example, the following: polyethyleneimines, polyamines having a molecular weight of more than 50,000, polyamidoamines modified by grafting onto ethyleneimine, polyamidoamines, polyetheramines, polyvinylamines, modified polyvinylamines, polyalkylamines, polyvinylimidoazoles, polydiallydialkyl ammonium halides, in particular polydiallyldimethylammonium chloride. These polyelectrolytes are soluble in water and are used in the form of aqueous solutions.
The cationic demand of pulps used for making, for instance, newsprint is often above 1000 meq./mL of stock so that improvements only become significant with polymer weights of above 1000 grams dry polymer per tonne dry weight of paper. Such large amounts render treatment uneconomical.
Impurities in papermaking furnishes which need to be neutralized by the cationic polymer are present in solution as dispersed colloidal particles, and/or dissolved substances such as lignosulfonates and sulfites, kraft lignin, hemicelluloses, lignans, humic acids, dispersed wood resins, rosin acids and chemical by-products. These impurities impart a large negative charge on the surfaces of cellulose fibers and other materials when they are dispersed in water.
Recently, due to environmental legislation, the level of the aforementioned impurities in papermachine white-water systems has further increased. This increase is a consequence of the increased tendency for paper mill operations to “close up” the paper machine white water systems and recycle as much white water as much as possible.
A second problem often associated with the manufacture of paper is the accumulation of wood resin and synthetic hydrophobic materials on the surfaces of the process equipment. Wood resin is usually defined as the material in wood which is insoluble in water, but soluble in organic solvents (Mutton, D. B., “Wood Extractive and Their Significance to the Pulp and Paper Industries” Chap. 10, Wood Resins, Ed. W. E. Hills, Academic Press, New York (1962)). The weight of wood resin from all species of trees consists usually of 1-5% based on total weight. From the teachings of U.S. Pat. No. 5,468,396 it is seen that increased reuse of mill white water causes a build-up in the concentration of water-borne resins (Allen L. H. and Maine C. J., Pulp Paper Can., 79(4): pp. 83-90 (1978)) and exacerbates the tendency for pitch deposition (Allen L. H., Tappi J., 63(2), pp. 82-87, (1980)). Many chemicals used to combat foam in pulp and paper mills end up dispersed in the aqueous phase of a pulp suspension and co-deposit with wood resin (Dorris G. M., Douek M., and Allen L. H., J. Pulp Paper Sci., 11(5): J149-154 (1985); Dunlop-Jones N. and Allen L. H., J. Pulp Paper Sci., 15(6): J235-241 (1989)). The presence of high amounts of dissolved and dispersed resin in paper machine process liquids usually also leads to reduced paper strength and runnability (Wearing, J. T., Ouchi, M. D., Mortimer, R. D., Kovacs, T. G., and Wong, A., J. Pulp Paper Sci., 10(6): J178 (1984)). Synthetic hydrophobic materials are usually introduced via deinked pulps and have similar chemical and physical properties to wood resins.
U.S. Pat. No. 5,468,396 teaches the use of a centrifugal deresination of the pulp and paper process liquids as an economical method to remove detrimental colloidal pitch. Furthermore U.S. Pat. Nos. 5,468,396 and 4,313,790 teach further prior art for reducing the concentrations of dissolved and dispersed resin which include the use of alum, dispersants, talc (Allen L. H., Tappi J., 63(2): pp. 82-87 (1980)); Douek M. and Allen L. H., J. Pulp Paper Sci., 17(5): J171-177 (1991)), sequestrants and a number of non-chemical methods such as bleeding the system, discarding of wash water, the use of a Frotapulper, followed by caustic extraction, as described by MoDo, and saveall flotation. Most of these methods are either too expensive under most circumstances or the practice is no longer tolerated.
In light of the aforementioned discussions, there has been ongoing extensive research into the development of new retention aids which increase retention and improve drainage in closed, highly contaminated systems. Traditional retention aids have had only a limited success in accomplishing these goals.
Increased retention and drainage allow significant economic benefits for a mill. Increased retention allows for cost savings in terms of reduced fibre consumption, cleaner machine operations, and decreased cost of effluent treatment. Increased drainage allows increased savings in terms of lower steam consumption brought about by a dryer sheet at the drying section.
In U.S. Pat. No. 4,313,790, inventors Pelton, Allen and Nugent have shown that a combination of kraft lignin or modified kraft lignin and poly(ethylene oxide) effectively increases fines retention and decreases pitch deposition on a papermaking machine in a papermaking process. A possible drawback to this system is the fact that mineral filler retention is not very high.
One method extensively used in the industry to improve the retention of cellulosic fines, mineral fillers, and other furnish components on the fiber mat is the use of a coagulant/flocculant dual polymer program system. The coagulant and flocculant are added ahead of the paper machine. In such a system a low molecular weight (usually <500, 000), highly charged polyelectrolyte coagulant or cationically modified starch is added first to the furnish. This has the effect of reducing the cationic demand of the furnish and reducing the negative surface charges present on the particles in the furnish. This initial addition of the coagulant accomplishes an initial degree of agglomeration and also tends to fixate mineral fillers and colloidal pitch/stickies to the fibers. The addition of the coagulant is then followed by the addition of the flocculant. Such flocculant is generally, but not necessarily, a high molecular weight anionic, cationic, or neutral synthetic polymer which bridges the particles or agglomerates. Such a combination increases drainage and retention.
Another system employed to provide an improved combination of retention and drainage is described in Canadian Patents 1,168,404 and 1,255,856 by inventors Langeley and Litchfield. The above patents describe the addition of bentonite prior to a high shear point followed by the addition of a cationic or anionic polymer after the shear point. The initial addition of bentonite is thought to absorb the detrimental substances present in solution. The shearing generally is provided by one or more stages of the papermaking process such as the centriscreening. At these shear points the shearing breaks down the large flocs formed prior to the shear point. This system is sold under the tradename Organosorb/Organopol.
Canadian Patents 1,322, 435 and 1,259,153 call for the addition of low molecular weight synthetic polyelectrolyte and/or high molecular weight cationic flocculant prior to a shear point followed by the addition of bentonite after the shear point. This system is often referred to as the Hydrocol system.
U.S. Pat. No. 4,749,444 by Lorz, Auhom, Linhart, and Matz teaches the addition of bentonite to a thick stock followed by the addition of a coagulant to the thin stock prior to a shear point and the subsequent addition of a high molecular weight cationic or anionic flocculant after the shear point.
The system described in U.S. Pat. No. 4,388,150 teaches the combination of cationic starch followed by colloidal silica to increase the amount of material retained in the sheet. Yet another variation of the system is described in U.S. Pat. Nos. 4,643,801 and 4,795,531 which use, in addition to starch, synthetic polymers.
Additional systems to improve drainage and retention have also been proposed. South African Patent 2 389/90 corresponding to U.S. Ser. No. 397,224 teaches the use of a single, high molecular weight cationic polymer.
U.S. Pat. No. 5,089,520 suggests a drainage and retention program in which a cellulose papermaking slurry is treated with a high molecular weight cationic (meth)acrylamide polymer prior to at least one shear stage followed by the addition of a low molecular weight anionic polymer at least one shear stage subsequent to the addition of the cationic polymer.
U.S. Pat. No. 5,266,164 by Novak and Fallon provides a method for improving the retention of mineral fillers and cellulose fibers on cellulose fiber sheet. This is accomplished by the addition of an effective amount of high molecular weight cationic polymer prior to a shear point followed by the addition of a high molecular weight anionic flocculant after the shear point. The difficulty with the use of the aforementioned chemistries in “closed” mill systems is their loss of effectiveness as retention and drainage aids (Allen, L. H., Polverari, M., Levesque B., and Francis D. U., 1998 Tappi, Coating/Papermakers Conference, New Orleans, Book 1, pp. 497-513 (1998)). A further difficulty with retention aids is that some polymer chemistries work better in some mills and worse in others.
WO 95/03450 teaches the use of cationic multi armed star-like polymers (hereinafter referred to as CMA-PAM) as an effective component to improve the retention of fines fraction by structural characteristics of multi armed polymer chains connected with one starting point on the compound. The CMA-PAM were synthesized by using pentaerythritol triacrylate (PETA) as the starting point. The three acrylate bonds are then reacted with the monomers acrylamide (AM) and dimethylamino-ethylacrylate (DMAEA-MC). Ammonium persulfate (APS) was used as the initiator. The structure formed is said to be star-like because the linear DMAEA-MC-AM chains extend from the central starting point, PETA. Depending on the DMAEA-MC-AM ratios the viscosity of the CMA-PAM vary between 86 and 450 centipoise (cP) and the charge densities do not exceed 1.5 meq./g at pH=7. The star-like structure was found to be more resistant to shear than linear PAM.
WO 95/03450 is thus concerned with polyols as starting compound; linear AM and DMAEA-MC chains are “attached” to the polyol OH groups. The maximum number of branches from the center is 4; these are not dendrimers. Dendrimers, while also starting from a central point, continue to “branch out” with every subsequent reaction.
Agents are also added to some papers, during fabrication to improve the wet strength of the product paper; wet strength agents are generally required for requiring wet strength papers such as tissue and towel, but are not required for printing papers. The function of a wet strength agent is different from the function of agents for enhancing retention of papermaking stock components and of agents for increasing drainage and there is no correlation between these different agents employed for different functions in papermaking.
Thus melamine formaldehyde and urea formaldehyde are among the most commonly employed wet strength agents in paper manufacture but have no utility as retention aids.
DISCLOSURE OF THE INVENTION
It is an object of this invention to provide a method of enhancing retention of components of a papermaking stock in a cellulosic sheet formed from the stock.
It is a particular object of this invention to provide a method of producing paper employing a dendrimeric polymer to enhance retention of components of a papermaking stock in the paper formed from the stock.
It is still another object of the invention to provide a papermaking stock containing a dendrimeric polymer to enhance retention of papermaking components of the stock in a cellulosic sheet formed from the stock.
In accordance with one aspect of the invention there is provided a papermaking stock comprising: an aqueous paper-forming cellulosic dispersion of papermaking components comprising cellulosic papermaking fibers and papermaking additives in an aqueous vehicle, characterized in that said dispersion contains a dendrimeric polymer as an agent to enhance retention of said components in a cellulosic sheet formed from said dispersion in papermaking, and in an amount to effect such enhanced retention and provide a cellulosic sheet having an enhanced content of the papermaking components as compared with a cellulosic sheet from a corresponding aqueous paper-forming cellulosic dispersion of papermaking components free of said dendrimeric polymer, said dendrimeric polymer being capable of developing a positive charge at an operating pH of papermaking.
In accordance with another aspect of the invention there is provided a method of enhancing retention of components of a papermaking stock in a cellulosic sheet formed from said stock in papermaking, said stock comprising an aqueous paper-forming cellulosic dispersion of papermaking fibers and papermaking additives in an aqueous vehicle, characterized by the inclusion in said dispersion of a dendrimeric polymer being capable of developing a positive charge at an operating pH of papermaking in an amount to enhance retention of said components in the cellulosic sheet.
In accordance with still another aspect of the invention there is provided a method of producing paper comprising forming a cellulosic sheet from a papermaking stock comprising an aqueous paper-forming cellulosic dispersion of papermaking components comprising papermaking fibers and papermaking additives in an aqueous vehicle characterized by enhancing retention of said components in the cellulosic sheet by the enhancing method of the invention, recovering a cellulosic sheet from the stock having an enhanced content of the papermaking components as compared with a cellulosic sheet formed from a corresponding aqueous paper-forming cellulosic dispersion of papermaking components free of the dendrimeric polymer, and recovering an aqueous fraction of the stock having a diminished content of the papermaking components.
Still further the invention provides paper produced by the aforementioned process of the invention.
In still another aspect of the invention there is provided a cellulosic paper sheet derived from an aqueous paper-forming cellulosic dispersion of papermaking components and a dendrimeric polymer capable of developing a positive charge at an operating pH of papermaking, said paper sheet containing said dendrimeric polymer and having an elevated content of the papermaking components of the dispersion, as compared with a paper sheet derived from a corresponding dispersion free of said dendrimeric polymer.
In accordance with yet another aspect of the invention there is provided use of a dendrimeric polymer to enhance retention of components of a papermaking stock in a cellulosic sheet formed from the stock, said polymer being capable of developing a positive charge at an operating pH of papermaking.
Thus a process has been discovered for the increase or enhancement of fines and filler retention and a decrease of pitch and/or stickies deposition during the manufacture of paper or paperboard, which involves the addition to the papermaking suspension of a dendrimeric polymer typically as a polymer solution. This system has also shown itself to be effective in “closed” mill systems.
Alternatively, the dendrimeric polymer may be added to the diluted filler slurry, prior to addition of the filler slurry to the paper stock, when producing filled grades or to the undiluted thick stocks, prior to dilution.
When the present invention is practiced, the retention of fines and filler is increased which in turn results in decreased fines in the white water which, in turn, facilitates a lower head box consistency, a higher headbox freeness, and a more even distribution of fines and filler in the cellulosic sheet. In addition, practise of this invention fixes dispersed wood resin and stickies in the cellulosic sheet and results in a decrease in problems due to pitch deposition on the paper machine.
Other benefits from the practice of this invention include increased drainage, increased white water reuse, increased closure, lower energy consumption, and increased fines retention.
DESCRIPTION OF PREFERRED EMBODIMENTS
Using this invention it is possible to make any grade of paper, for example newsprint, board, and the so-called groundwood specialty grades. Tissue, toweling, and other fine papers can also be produced by practising the invention.
Papers and paperboards may be produced using, as the principle raw material groundwood (GWD), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), pressurized groundwood (PGW), bleached kraft (BK), semi-bleached kraft (SBK), unbleached kraft (UBK), sulfite or sulfate pulps. Other suitable pulps such as deinked (DIP) and refiner mechanical pulp (RMP) may also be used. Each of these pulps may contain short or long fibers.
It is also possible to produce both filler free and filler containing papers. The maximum filler content of the paper is typically 40%, by weight, based on oven dried fiber but is generally 0 to 35%, by weight, and preferably between 5 to 15%, by weight. Examples of suitable fillers are clay, kaolin, chalk, talc, precipitated calcium carbonate (PCC), ground calcium carbonate (GCC), titanium dioxide, calcium sulfate, barium sulfate, alumina, satin white, organically synthesized fillers, or mixtures thereof.
A wet strength agent, for example, a melamine formaldehyde or a urea formaldehyde may be added to the papermaking stock, in addition to the dendrimeric polymer of the invention, especially in the case of papers requiring wet strength papers such as tissue and towel.
In most cases, however, especially in printing papers, no wet strength agent is required and the dendrimeric polymer is added to the papermaking stock without the addition of a wet strength agent.
In particular, the papermaking stock may be free of wet strength agents.
The dendrimeric polymer enhances retention of papermaking components in a cellulosic sheet formed from a cellulosic dispersion of papermaking components and produces a cellulosic sheet having an enhanced content of the papermaking components as compared with a cellulosic sheet formed from a second cellulosic dispersion which differs only in that it is free of the dendrimeric polymer.
On the other hand, an aqueous fraction of the papermaking stock of the invention separated from the cellulosic sheet formed from the stock, has a diminished content of papermaking components, as compared with an aqueous fraction separated from the aforementioned second cellulosic dispersion free of the dendrimeric polymer.
The term dendrimeric macromolecules is understood as embracing very generally highly branched macromolecules that emanate from a central core and are synthesized through a stepwise, repetitive reaction sequence. Dendrimeric macromolecules are often referred to as “starburst” polymers. Dendrimers are a new class of macromolecules with a hyperbranched structure. This structure is well defined in terms of chemical composition and three-dimensional configuration. Dendrimers are synthesized in a stepwise manner, which provides unique control over chemical and physical properties. This control allows for the development of products which are tailored to specific applications. For example the end groups of the dendrimers are very well accessible for all kinds of modification reactions. Examples of modified end groups include carboxylic or fatty acid derivatives (Tomalia, D. A., Naylor, A. M., and Goddard, W. A., Angew. Chem. Intl. Ed. Engl., 29, 138-175 (1990); Frechet J. M., Science, 263, 1710-1715 (1994)).
Due to the repetitive reaction sequence in the synthetic procedure, dendrimers can be obtained with a chosen number of generations and end-groups. These structures are well defined in terms of both chemical composition and three dimensional configuration. Since dendrimers are synthesized in stages, one is afforded unique control over their chemical and physical properties such as size, shape, reactivity, solubility, and three dimensionality. This control allows the development of products which are tailored to specific applications. Reference is made to the following literature citing the synthesis of dendrimers: (Newkome G. R. et al., Macromolecules, 26(9), 2394-2396 (1993); Jansen et al., Science, 266, 1226-1229 (1994); Frechet, J. M., Science, 263, 1710-1715 (1994); Tomalia, D. A., Naylor, A. M., and Goddard, W. A., Angew. Chem. Intl. Ed. Engl., 29, 138-175 (1990); Biswas P. And Cherayil B. J., J. Chem. Phys., 100(4), 3201-3209 (1994); Kim Y. and Beckerbauer R., Macromolecules, 27, 1968-1971 (1994); Mourey T. et al., Macromolecules, 25, 2401-2406 (1992); Kremers J. A. and Meijer E. W., J. Org. Chem., 59(15), 4262-4266 (1994); van Genderen M. H. P. et al., Rec. T. Chimiques des Pays-Bas, 113(12), 573-574 (1994)).
The nomenclature of dendrimers is described in Newkome, J. Polymer Science, Part A; Polymer Chemistry, 31, (1993), pages 611-651.
For one type of dendrimer, poly(propylene imine), an efficient large scale synthesis has been described (de Brabander-van der Berg, E. M. M. and Meijer, E. W., Angew. Chem. Intl. Ed. Engl., 32-38, 1308 (1993)).
The repetitive reaction sequence involves a Michael addition of two equivalents of acrylonitrile to a primary amino group, followed by hydrogenation of the nitrile groups to primary amine groups. Diaminobutane (DAB) is used as the core molecule. Each complete reaction sequence results in a new “generation” with a larger diameter and twice the number of reactive functional end groups. For example, starting with diamino butane (DAB), double Michael addition of acrylonitrile yields a species with four cyano groups (DAB-dendr-(CN) 4 ). Catalytic hydrogenation with H 2 /Raney-Co results in a molecule with four primary amine groups (DAB-dendr-(NH 2 ) 4 ). Repeating this sequence yields dendrimers with 2 n cyano or amine end groups, where n is an integer of 2 to 1000, preferably 2 to 100 and more preferably 2 to 20, thus there may be, for example, 8, 16, 32, 64 or 128 such end groups. These end groups may be further reacted or grafted with other molecules to yield the desired surface and/or internal core chemistries.
Similarly ethylene diamine (EDA) may be used instead of diaminobutane (DAB) as the core molecule.
The hyperbranched dendrimeric structure contains primary, secondary and tertiary amines (at various ratios ranging from 0 to 100%). At lower pH values, the primary, secondary and tertiary amines become protonated thereby developing a positive charge. The charges are developed by the interior as well as the surface amine groups. For example, for one type of dendrimer, poly(propylene imine), both the interior tertiary amines as well as the surface primary amines are cationically charged at pH values below 8.
For the purpose of this invention it is necessary that the dendrimeric polymer develop a positive charge at the desired operating pH, and, in particular, this positive charge may be achieved with the end groups. The groups which yield the positive charge may be any suitable groups, for example, amino groups, as for example, primary, secondary, or tertiary amines or quarternized amine functionalities.
Suitably n is chosen such that the dendrimer is readily dispersible in water, and preferably soluble in water. A particularly advantageous subclass of dendrimer has a weight average molecular weight of less than about 50,000. Especially preferred dendrimers have a positive charge of at least 1.5 meq/gram and more preferably at least about 6 meq/gram, most preferably 14 to 19 meq/gram, measured by colloid titration at a pH of 5.
A preferred class of dendrimers are poly(propylene imines) in which the core monomer is a diamino lower alkane of 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, for example, ethylene diamine (EDA) or diaminobutane (DAB), and the core monomer is reacted with acrylonitrile.
Suitably the dendrimers employed in this invention are prepared by the repetitive reaction sequence involving a Michael addition of two equivalents of acrylonitrile to a primary amine group followed by a hydrogenation of the nitrile groups to primary amines. Diaminobutane and ethylenediamine are preferred core molecules. The end groups are preferably primary amines.
By way of example the molecular weights of the dendrimers used in this invention are 300 and 7,166 Daltons for DAB(PA) 4 which is 4-cascade:1,4-diaminobutane-[4]:propylamine and DAB(PA)64 which is 64-cascade:1,4-diaminobutane:(1-aza-butylidene) 64 propylamine, respectively and 517 and 1430 Daltons for EDA 4 and EDA 8 , respectively. The respective charge densities at pH 5 are 18.2 meq./gram net and 14.9 meq./gram net for DAB(PA) 4 and DAB(PA) 64 , respectively and 17.0 meq./gram net and 16.4 meq./gram net for EDA(PA) 4 and EDA(PA) 8 respectively. For comparative purposes, the charges of a typical poly(DADMAC) or branched polyethyleneimine at pH 5 are approximately 5.5 meq./gram net and 5.9 mEq./gram net.
In the process of this invention, the dendrimers are preferably added to the pulp slurry or stock as an aqueous solution before the papermaking stock reaches the paper machine headbox. Ideally, the point of addition is sufficiently before the headbox to enable complete mixing of the polymer into the pulp but after all points of extreme turbulence, such as fan pumps and pressure screens. However, other points of addition may be suitable, either before or after shear locations.
Additionally, the dendrimeric polymers may be added directly to a desired point of addition, such as for example the machine headbox, blend chest, mixing chest, thick stock chests, save-all, or the dilution white water silos/supply lines. Alternatively, the dendrimeric polymers may be mixed directly with the filler slurries or other chemicals prior to their addition to the pulp slurries.
The dendrimeric polymer is added to the pulp or filler slurry in an effective amount. The amount of dendrimeric polymer added can vary depending on several factors, for example, the dendrimeric molecular weight, the dendrimeric surface charge at the operating pH, the pulp used, and the type of surface chemistry. The amount can be determined by those skilled in the art for any particular product or process. However, in general terms, the dendrimeric polymer will be added at a rate between 0.1 and 20 percent by weight based on the weight of oven dried pulp; a preferred embodiment incorporates a range of between 0.1 percent and 5 percent by weight.
The dendrimeric polymers may also be used in conjunction with other papermaking additives for different purposes including improving drainage and retention performance. These additives include various inorganic materials, such as bentonite and alum, and/or organic materials, such as various natural, modified natural, or synthetic polymers which are included in the thin or thick stock for the purpose of improving the drainage and retention process. These can be added, optionally, at locations prior to or after to the addition of the dendrimeric polymer. They may also be added at the same location or variations thereof.
BRIEF DESCRIPTION OF DRAWING
FIG. 1 illustrates schematically a modified drainage jar (MDDJ) employed in the experiments illustrating the invention.
FIG. 2 illustrates a dendrimeric polymer formulation.
MODE FOR CARRYING OUT THE INVENTION
With further reference to FIG. 1, a modified dynamic drainage jar 10 has a drainage tank 12 , a stirrer 14 and level sensing electrodes 16 and 18 .
Tank 12 has a papermachine wire 20 disposed in a lower region above an outlet 22 . Outlet 22 communicates with a vacuum flask 24 which is operatively connected to a vacuum pump and gauge 26 . A ball valve 28 functions to open and close outlet 22 .
Stirrer 14 is operatively controlled by a stirrer control 30 , and electrodes 16 and 18 are operatively connected to a timer 32 .
In order to disclose more clearly the nature of the present invention the following examples illustrating the invention are given:
A. i) The Approach
The performances of different dendrimer polymers, used alone or with a polyacrylamide, were measured in the laboratory in TMP newsprint pulps at three levels of system closure. In this specification the degree of system closure is defined in terms of fresh water makeup to the machine. Accordingly, the levels of system closure used were: 55, 20, and 2 m 3 /t. Additionally the dendrimers were tested on two board stocks, a filled stone groundwood-DIP-ultra high yield sulfite newsprint furnish, a peroxide bleached TMP furnish, and a hydrosulfide bleached TMP furnish.
ii) Pulps and White Waters
Headbox pulp and wire pit white water samples were taken from two integrated TMP newsprint mills. Mill A was modem and the fresh water usage, 20 m 3 /t, was typical of TMP newsprint mills built in the last ten years. Mill B had a fresh water usage of 55 m 3 /t, typical of an older facility. Retention aids were not employed in either mill. Mill A produces 100% TMP from 40% spruce and 60% fir. Mill B produces 100% TMP from 75% spruce and 25% fir.
Simulated white water for an advanced closure level was prepared in the laboratory by washing pulp collected from the secondary refiner discharge in Mill B. The apparatus for white water preparation consisted of a stock tank, screw press, white water tank and pumps (Francis D. W. and Ouchi M. D. (to be published)). It was operated in batch mode. The unwashed pulp at 30% consistency was diluted to 2% consistency with fresh water and agitated for 30 minutes at 60° C. The pulp suspension was then dewatered to approximately 44% consistency with the screw press and the pressate was recycled to dilute the next batch of pulp. This cycle was repeated for 13 more batches until the desired contaminant level was attained. A small volume of fresh water was added after batch 10 to produce the desired volume of white water. Gravity clarification was used to remove the suspended solids.
The contaminant level in the paper machine white water depends on a number of factors in addition to the fresh water usage, including the white water management strategy and the choice of dewatering equipment. Therefore, it is not possible to directly relate the contaminant level of the simulated white water to a mill closure level. The simulated white water corresponded to the white water expected in a fully integrated white water system with a process fresh water addition of about 2 m 3 /t.
Headbox stock was also obtained from a third newsprint mill producing newsprint using groundwood (GWD), deinked (DIP), and ultra high yield sulfite (UHYS) pulps. Clay content in the sheet is nominally 5-7%.
Two board stocks were obtained from a corrugated medium producer. The first stock was 100% old corrugated container (OCC) and the second stock was 50% OCC/50% NSSC (neutral sulfite semi-chemical). The NSSC was produced using spruce chips.
Lastly, three other newsprint furnishes were obtained:
(i) A supercalendered newsprint furnish composed of 69% peroxide bleached TMP, 6% kraft, and 25% broke with a normal clay content of 22%.
ii) A standard newsprint furnish composed of 75% hydrosulfite TMP and 25% broke with no clay.
iii) A standard newsprint furnish composed of 50% hydrosulfite bleached TMP, 25% deinked fibre and 25% broke.
iii) Polymer Preparation
The polymer solutions were prepared with twice-distilled water produced in a glass distillation apparatus. Solutions were freshly prepared every day at a concentration of 1% active ingredients. DAB(PA) 4 and DAB(PA) 64 were obtained as 100% and 97.5% active solutions, and the EDA polymers were obtained as 100% active solutions, based on total weight. The cationic polyacrylamide (CPAM) was prepared by mixing 1 gram of the solid polymer and adding 99 grams of twice-distilled water. The polymer solution was then diluted to 0.25% actives prior to use.
iv) Charge Densities of the Polymers by Colloid Titration
The cationic demands were determined using a modified polyelectrolyte titration technique outlined by Horn (Horn D., Progr. Coll. Poly. Sci., 65, 255-264 (1978)) at pH 5. 10 mL of a 0.01% active ingredients wt/wt polymer solution was diluted to 100 mL and titrated with PVSAK to a pink end-point.
v) Retention and Drainage Measurements
Retention and drainage measurements were done in three ways: (1) using the Dynamic Drainage Jar (DDJ), using the modified Dynamic Drainage Jar (MDDJ), and using a modified DDJ for gravity drainage measurements (FDDJ) as described in the following three sections. All measurements were done at 60° C. and at a pH of 5.2.
vi) 1) Modified Dynamic Drainage Jar (MDDJ)
First pass- retention (FPR) with mat formation (nominal basis weight 80-120 g/m 2 ), drainage rate, and consistency after vacuum were obtained using our modified dynamic drainage jar (MDDJ) method (Yaraskavitch I. M., Allen L. H. and Heitner C., Pulp Pap. Sci. , 16(3), J87-93 (1990)). All polymer concentrations are expressed as net active ingredients in the results. The modified drainage jar is illustrated in FIG. 1 . The MDDJ is fitted with a nylon machine wire with an 86:60 mesh.
The headbox stocks were diluted with white water to ˜0.15% consistency. To do so, the white water was previously filtered once through a Reeve Angel 202 (Trade-mark) filter paper to remove all the suspended solids. Headbox stock from mill A was diluted with filtered white water from mill A and headbox stock from mill B was diluted with filtered white water from mill B or filtered simulated white water at 2 m 3 /t. These were the 20 m 3 /t, 55 m 3 /t, and 2 m 3 /t furnishes, respectively.
With the propeller rotating at 500 rpm, air was bubbled under the screen in order to keep the sample from draining into the part of the MDDJ below the screen where it would not be properly mixed. 15 seconds after pouring the furnish into the MDDJ, the dendrimer being tested was added. At 30 seconds, the CPAM was added (if required). 50 seconds after pouring the stock into the MDDJ, the polymer being tested was added to the MDDJ. After 50 seconds, the airflow was stopped and the vacuum was applied to the vacuum flask at 20 cm Hg. At exactly one minute, the drainage valve was opened allowing the sample to drain. The level sensing electrodes measured the drainage time and when the timer had stopped, full vacuum (64 cm Hg) was applied for 40 seconds.
The mat was peeled off the screen and weighed. The sample was placed in a centrifuge tube equipped with a screen and centrifuged at 5000 RPM (4500 g) for 30 minutes using a Sorvall RC-3B (Trade-mark) centrifuge with an HG-4L rotor. The mat was reweighed, dried overnight in an oven at 105° C. and the dry weight was recorded. The response of the wet web to vacuum was evaluated by calculating the consistency of the mat after exposure to vacuum (i.e., dryness), and the water retention values (WRV) are reported as the consistency after centrifugation (Tappi Useful Method UM256; Scallan A. M. and Charles J. E., Svensk Papperstidn. 75, 699-703 (1977)).
The consistency of a 100 mL sample of the total filtrate collected during vacuum was used to calculate the first-pass retention (FPR) with mat formation. A minimum of three runs was performed for each experimental point from which an average was calculated. An additional 25 mL of filtrate were collected for turbidity measurements.
vii) Dynamic Drainage Jar (DDJ)
The Dynamic Drainage Jar (DDJ) is fully described in Pulp Paper Can., 80(12):T425 (1979). The DDJ was fitted with a 40 mesh stainless steel wire screen and a nozzle consisting of the tip of 25 mL pipette. For all experiments the stock in the DDJ was stirred at 500 RPM. 15 seconds after the stock is added into the DDJ, the dendrimer is added. If required the CPAM was added at 30 seconds. After 45 seconds the nozzle was opened allowing the white water to flow out.. The first 25 mL portion was discarded. The next 100 mL portion was collected. The consistency (solids content) of the white water was determined gravimetrically after filtration and drying of the Whatman 40 (Trade-mark) filter pad at 105° C. The first pass retention was calculated. If needed, the filter pads were washed and the ash content was determined according to TAPPI test procedure T-211.
viii) Free Dynamic Drainage Jar
Drainage measurements were carried out using a standard D.D.J. which was slightly modified to allow unrestricted drainage. The modification consisted of a 2 cm opening at the bottom of a standard D.D.J. and a further 0.5 cm opening on the side of the standard D.D.J. located below the screen. This allowed any white water flowing through the screen to be freely evacuated. The FDDJ was equipped with a 40 mesh screen and a glass funnel deposited on the top of the DDJ. The glass funnel is stoppered with a rubber plug. Essentially the experiment is carried out by adding the polymers in the same manner as they are added in the DDJ experiments: a standard DDJ is fitted with a plexiglass bottom, the polymers are added, and after 45 seconds, the stirrer is stopped. The furnish is added into the glass funnel and the rubber stopper is quickly removed. The furnish drops into the FDDJ and the time required to drain 100 mL is measured.
B. i) Pilot Machine Trial
The pilot machine had a trim of 330 mm and consisted of a twin-former, a three roll inclined press followed by an extended nip press, a forth press, and a reel for collection of pressed wet paper. The operating speed of the pilot machine was 600 m/min. The first two press nips were loaded to 45 to 90 kN/m while the third and fourth press nips were operated at 300 and 100 kN/m, respectively. The paper machine had no dryers: the wet paper samples were cut from the reel and were either used to determine the web-web properties or dried between blotters on a rotary photographic dryer for subsequent evaluation of dry paper.
The headbox opening was 0.00369 m 2 . The fibre flux through the machine was 748 kg/hour. The targeted sheet basis weight was 45 g/m 2 . The machine wire used was an MT Series Monoflex 2000 (Trade-mark) by JWI.
The stock ash was 11.71%. The reslushed stock consistency was 2.8%. At the beginning of the trial one ton of SCC newsprint paper was reslushed and diluted to about 1% consistency. Paper was produced on the pilot machine and subsequently discarded in order to produce white water with a steady-state consistency. The white water produced was stored in a white water tank. Following production of the white water, another ton of newsprint was reslushed and stored in the thick stock tank. Headbox stock for the pilot trial was produced by diluting the thick stock with the produced white water in the white water tank.
The reslushed peroxide bleached newsprint used to produce the pilot machine headbox stock was composed of 75% virgin fibre (80% peroxide bleached TMP, 10% hydrosulfite TMP, 9% kraft) and 25% broke. The stock produced had a freeness of 55 mL CSF, an ash content of 11.71% and a pH of 5.1. The headbox consistency for the pilot trial was approximately 0.85%.
ii) Polymers Preparation
The flocculant used was a 10% mole ratio cationic polyacrylamide. 200 liters of 0.05% flocculant solution were prepared by dispersing the polymer in water at room temperature and agitating the polymer until full dilution had been accomplished. The DAB(PA) 4 dendrimer retention aid was prepared by diluting, with agitation, the 100% actives liquid to a concentration of 0.5% actives. 750 liters of solution were prepared at room temperature.
The 0.5% solution of dendrimer retention aid was metered to the pulp suspension at an inlet at the fan pump to ensure good mixing. The polyacrylamide solution was metered after the fan pump. The temperature of the headbox stock was maintained at 50° C. The time for the pulp to travel from the injection points to the headbox for the polyacrylamide and dendrimer retention aid was estimated to be 5 seconds and 7 seconds, respectively. The pH was monitored at 4 minute intervals and was kept constant at 5.1 by slow addition of 10% sulfuric acid into the returning white water flow.
iii) Experimental Procedure
The pilot plant trial was run by dividing the total trial into 11 time periods. Each time period had a duration of 30 minutes. Sampling of the machine headbox and white water was done at every 4 minute interval in conjunction to pH monitoring.
Headbox and white water samples were used to measure the change of FPR, FPAR, turbidity and cationic demand as a function of polymer dosage.
EXAMPLES
Example 1
For this experiment the gravity drainage rate was measured using the FDDJ. Stocks at 2 m 3 /t and 55 m 3 /t were prepared from the headbox stock obtained from Mill B. The headbox stock was 100% TMP and contained no additives or fillers. The headbox stock were diluted to a consistency of 0.48% and 0.47% for the 55 m 3 /t and 2 m 3 /t furnishes, respectively. Dilution for the 55 m 3 /t stock was done using filtered machine white water. The dilution for the 2 m 3 /t stock was accomplished using filtered recirculated white water from our laboratory screw press. Branched modified PEI (BM-PEI) a highly charged polyethyleneimine coagulant was also tested for comparative purposes. (BM-PEI) was prepared at 1% net actives. All polymer dosages are based on net actives. The diluted furnish was heated to 60° C. and mixed at 500 R.P.M prior to each experiment. As can be seen from the data in Table I, the increased addition of both dendrimer polymers increases the drainage rate of the furnish. The effect of dendrimer addition is most pronounced in the 55 m 3 /t stock. A four-fold improvement in drainage was obtained with the first generation dendrimer. The improvement in drainage for the 2 m 3 /t was not as pronounced. In either case both dendrimer polymers outperformed BM-PEI at an equivalent net dosage.
Example 2
For this experiment the first-pass retention (FPR) was measured using the D.D.J.. Stocks at 2 m 3 /t and 55 m 3 /t were prepared from the headbox stock obtained from Mill B. The headbox stock was 100% TMP and contained no additives or fillers. The headbox stocks were diluted to consistencies of 0.52% and 0.54% for the 55 m 3 /t and 2 m 3 /t furnishes, respectively. Dilution for the 55 m 3 /t stock was done using filtered machine white water. The dilution for the 2 m 3 /t stock was accomplished using filtered recirculated white water from our laboratory screw press. BM-PEI, a highly charged polyethyleneimine coagulant was also tested for comparative purposes. BM-PEI was prepared at 1% net actives. All polymer dosages are based on net actives. The furnish was heated to 60° C. and mixed at 500 R.P.M. As can be seen from the data, the increased addition of the dendrimer polymer increases the first-pass retention of the furnish (Table II). The first-pass retention is again most improved in the 55 m 3 /t furnish. A gain of over 15% is noted at the highest polymer concentration. In both cases, the dendrimer polymers outperform Polymin SKA.
Example 3
For this experiment the first-pass retention (FPR), dryness, WRV, drainage rate using the electrodes (E), drainage rate using the dry spot (DS), and turbidity were measured using the modified D.D.J.. (MBDJ) Stocks at 2 m 3 /t and 55 m 3 /t were prepared from the headbox of Mill B. The headbox stock was 100% TMP and contained no additives or fillers. The headbox stocks were diluted to a consistency of 0.16% and 0.18% for the 55 m 3 /t and 2 m 3 /t furnishes, respectively. Dilution for the 55 m 3 /t stock was done using filtered machine white water. The dilution for the 2 m 3 /t stock was accomplished using filtered recirculated white water from a laboratory screw press. BM-PEI, a highly charged polyethyleneimine coagulant was also tested for comparative purposes. BM-PEI was prepared at 1% net actives. All polymer dosages are based on net actives. For these experiments CPAM was also used. The dendrimer was added to the stock prior to the addition of the CPAM. The furnish was heated to 60° C. and mixed at 500 R.P.M. As can be seen from the results in Table III ((a) and (b)), the addition of the dendrimers, with or without the further addition of CPAM, improves the measured properties: the FPR is seen to increase, the measured turbidity decreases, the drainage rates (E) and (DS) increase, and the dryness and WRV values increase. However, the results are less pronounced for 2 m 3 /t.
Example 4
For this experiment the first-pass retention (FPR), first-pass ash retention (FPAR), dryness, drainage rate using the electrodes (E), drainage rate using the dry spot (DS), and turbidity were measured using the modified D.J.. A stock at 20 m 3 /t was prepared from the headbox of Mill A. The headbox stock was 100% TMP and contained no additives. The filler content in the stock was 20%. The headbox stock was diluted to a consistency of 0.16% using filtered white water from the papermachine. BM-PEI, a highly charged polyethyleneimine coagulant was also tested for comparative purposes. BM-PEI was prepared at 1% net actives. All polymer dosages are based on net actives. The furnish was heated to 60° C. and mixed at 500 R.P.M. As seen from the results in Table IV, the use of the dendrimer polymers increases dryness, drainage rates, FPR, and FPAR. Both dendrimers outperform BM-PEI at equivalent actives dosages.
Example 5
Headbox stock was obtained from a third newsprint mill producing newsprint using a furnish composed of groundwood (GWD), deinked (DIP), and ultra high yield sulfite (UHYS) pulps. The clay content in the sheet is nominally 5-7%. The first-pass ash retention (FPAR) was measured using the DDJ. The furnish was loaded with additional clay. The final clay content was 30.5%. The clay was treated with dendrimer prior to addition to the stock. The headbox stock consistency was 0.84% after dilution with filtered white water. The Furnish was heated to 60° C. and mixed at 500 R.P.M. Results in Table V indicate that the addition of either of the dendrimers increases FPR.
Example 6
Two board stocks were obtained from a corrugated medium producer. The first stock was 100% old corrugated container (OCC) and the second stock was 50% OCC/50% NSSC (neutral sulfite semi-chemical). The NSSC was produced using spruce chips. For this experiment the first-pass retention (FPR), WRV, and drainage rate using the electrodes (E) were measured using the modified D.J.. The stock consistencies were 1.15% for the OCC and 1.20% for the 50% OCC/50% NSSC as received from the mill. These stocks were used as is and the consistency was not adjusted. The Furnish was heated to 60° C. and mixed at 500 R.P.M. Results in Table VI indicate a marked improvement in drainage rate for the 100% OCC furnish and a slight improvement in WRV and FPR. On the other hand the dendrimer only slightly improved the WRV and FPR for the 50% NSSC/50% OCC stock and was detrimental to the drainage rate.
Example 7
The same stocks as in Example 6 were used. For this experiment the gravity drainage rate was measured using the FDDJ. The stock consistencies were 1.15% for the OCC and 1.20% for the 50% OCC/50% NSSC. The Furnish was heated to 60° C. and mixed at 500 R.P.M. The drainage rate is seen in Table VII to increase substantially for the 100% OCC stock. The improvement in drainage for the 50% OCC/50% NSSC stock was only slight.
Example 8
Illustrated in this example is the effect of the dendrimers on dispersed resin particle concentration. The same headbox stock as used in example I (55 m 3 /t headbox stock) was used for this example. The concentration of colloidally dispersed wood resin in the D.J. was determined (Allen L. H., Trans. Tech. Sect. CPPA, 3, 32, 1977). In this procedure the resin particle concentrations were determined with a hemacytometer and microscope which was fitted with a 40× objective lens and gave an overall magnification of 800×. The results are shown in Table VIII as a function of the concentrations of the two dendrimers. At the highest polymer concentrations the dispersed resin in the white-water was reduced by 97% by the DAB(PA) 64 and 63% by the DAB(PA) 4 . The furnish was heated to 60° C. and mixed at 500 R.P.M.
Example 9
Headbox stock was obtained from a newsprint mill producing supercalendered newsprint using a furnish composed of 69% peroxide bleached TMP, 6% Kraft and 25% broke. The clay content in the sheet was nominally 22.17%. The first-pass retention (FPR) was measured using the standard D.D.J. The headbox stock consistency was 0.89%. The furnish was heated to 50° C. and mixed at 1200 R.P.M. The dendrimer was added first followed by the addition of 500 g/ton of a 10% mole ratio cationic polyacrylamide. Results in Table IX indicate that the addition of dendrimers increases FPR.
Example 10
Headbox stock was obtained from a newsprint mill producing standard newsprint using a furnish composed of 75% hydrosulfite bleached TMP and 25% broke. The furnish contained no clay. The first-pass retention (FPR) and first pass ash retention (FPAR) were measured using the standard D.D.J. The headbox stock consistency was 0.85%. The furnish was heated to 50° C. and mixed at 1200 R.P.M. The dendrimer was added first followed by the addition of 500 g/ton of a 10% mole ratio cationic polyacrylamide. Results in Table X indicate that the addition of dendrimers increases FPR and FPAR.
Example 11
Headbox stock was obtained from a newsprint mill producing standard newsprint using a furnish composed of 50% hydrosulfite bleached TMP, 25% deinked pulp and 25% broke. The furnish contained no clay. The first-pass retention (FPR) and pitch counts were measured using the standard D.D.J.. The headbox stock consistency was 1.01%. The furnish was heated to 50° C. and mixed at 1200 R.P.M. The dendrimer was added first followed by the addition of 500 g/ton of a 10% mole ratio cationic polyacrylamide. Results in Table XI indicate that the addition of dendrimers increases FPR and decreases pitch counts.
Example 12
The results of the pilot machine trial are presented in Table XII. The procedures and polymer preparation are described in the preceding section. Results indicate that the dendrimer polymer increases FPR and FPAR while decreasing turbidity and cationic demand.
TABLE I
Polymer Dosage
Drainage Rate (mL/s)
Polymer
(kg/t)
2 m 3 /t
55 m 3 /t
DAB(PA) 4
0
5.4
11.6
5
9.3
17.4
10
10.4
36.9
15
10.9
48.1
20
11.3
48.8
DAB(PA) 64
0
5.4
11.6
5
7.5
43.3
10
7.7
39.4
15
8.6
35.3
20
9.2
35.0
BM-PEI
0
5.4
11.6
5
5.7
14.8
10
6.6
15.7
15
7.4
16.9
20
8.0
21.6
TABLE II
Polymer Dosage
FPR (%)
Polymer
(kg/t)
2 m 3 /t
55 m 3 /t
DAB(PA) 4
0
53.2
61.2
0
5
52.2
64.6
10
53.5
74.5
15
53.9
75.6
20
54.1
77.2
DAB(PA) 64
0
53.2
61.2
5
53.1
69.2
10
53.8
72.0
15
57.2
77.2
20
58.4
80.2
BM-PEI
0
53.2
61.2
5
53.0
61.6
10
53.8
63.0
15
53.5
68.0
20
53.3
72.8
TABLE III(a)
MODIFIED DYNAMIC DRAINAGE JAR
(closure: 2 cubic meters/tonne)
Drain-
age
Drain-
Polymer
Dry-
Rate
age
First-Pass
Dosage
Turbidity
ness
WRV
(E)
Rate(DS)
Retention
Polymer
(kg/t)
(NTU)
(%)
(%)
(mL/s)
(mL/s)
(%)
DAB(PA) 64
0
427
21.3
41.8
10.8
10.1
81.0
5
424
24.9
42.2
9.3
8.9
82.8
10
422
24.2
43.9
8.6
7.4
81.5
15
416
23.9
43.5
8.0
6.3
77.8
20
355
20.9
42.6
6.5
4.9
78.3
DAB(PA) 4
0
427
21.3
41.8
10.8
10.1
81.0
5
404
21.4
42.3
11.7
11.2
81.1
10
382
22.9
43.0
11.8
11.4
81.6
15
316
24.4
43.6
13.7
13.8
82.0
20
218
25.3
44.2
23.9
21.2
82.8
BM-PEI
0
427
21.3
41.8
10.8
10.1
81.0
5
422
23.3
41.6
11.5
14.6
81.8
10
69
23.5
43.0
10.0
12.9
81.4
15
365
24.3
43.3
10.3
11.9
82.1
20
282
24.3
43.6
10.8
10.0
82.3
DAB(PA) 64 /
0/0
482
21.3
43.8
10.8
10.1
81.0
CPAM
0/2
460
23.6
43.1
12.5
10.2
84.2
5/2
440
22.3
43.1
9.5
10.2
84.9
10/2
418
22.4
43.0
10.8
10.5
86.3
15/2
355
22.5
43.0
13.2
12.0
86.5
20/2
308
23.2
43.2
14.0
14.1
86.8
DAB(PA) 4 /
0/0
482
21.3
43.8
10.8
10.1
81.0
CPAM
0/2
460
22.6
43.1
12.5
10.2
84.2
5/2
389
23.0
43.5
12.5
10.2
83.2
10/2
309
23.4
44.1
11.8
10.2
82.5
15/2
236
24.4
44.8
9.7
10.7
82.4
20/2
172
25.8
45.2
7.7
12.8
82.2
TABLE III(b)
MODIFIED DYNAMIC DRAINAGE JAR
(closure: 55 cubic meters/tonne)
Drain-
age
Drain-
Polymer
Dry-
Rate
age
First-Pass
Dosage
Turbidity
ness
WRV
(E)
Rate(DS)
Retention
Polymer
(kg/t)
(NTU)
(%)
(%)
(mL/s)
(mL/s)
(%)
DAB(PA) 64
0
195
15.2
40.8
29.4
23.9
77.4
5
191
20.0
41.7
31.8
24.4
77.5
10
144
23.2
43.0
32.6
25.0
78.9
15
112
23.9
43.1
33.4
25.7
80.4
0
111
27.6
43.7
33.5
26.1
81.9
DAB(PA) 4
0
191
15.2
40.8
29.4
23.9
77.4
5
119
21.8
42.2
33.3
27.5
78.3
10
47
23.3
45.1
36.6
28.8
82.0
15
29
24.5
45.4
38.4
32.3
83.3
20
28
26.1
45.5
42.2
32.6
84.7
BM-PEI
0
195
15.2
40.8
29.6
24.0
77.4
5
190
21.3
39.2
25.3
19.1
84.0
10
180
21.5
38.6
25.4
17.8
85.6
15
176
22.1
38.8
25.4
17.6
85.5
20
174
22.1
38.8
25.5
16.9
86.3
DAB(PA) 64 /
0/0
250
21.0
40.2
35.2
26.6
82.4
CPAM
0/2
148
21.8
40.3
21.5
19.1
83.6
5/2
143
23.1
43.9
12.4
10.7
87.0
10/2
136
22.8
43.6
18.2
15.8
86.7
15/2
134
21.4
42.2
19.8
18.9
86.0
20/2
126
21.3
41.5
22.0
21.3
86.9
DAB(PA) 4 /
0/0
250
21.0
40.2
35.2
26.6
82.4
CPAM
0/2
148
1.8
40.3
21.5
19.1
83.6
5/2
123
22.2
40.3
23.6
21.3
84.0
10/2
93
22.4
40.0
28.1
26.9
85.0
15/2
79
22.8
40.0
28.8
27.5
86.0
20/2
62
23.2
40.0
29.6
28.6
86.8
TABLE IV
Drain-
Drain-
First-
age
age
pass
First-
Polymer
Dry-
Rate
Rate
Ash
pass
Dosage
ness
(E)
(DS)
Retention
Retention
Polymer
(kg/t)
(%)
(mL/s)
(mL/s)
(%)
(%)
DAB(PA) 4
0
21.9
11
12
38.1
72.8
1.13
21.4
9.59
10.2
75.5
79.8
2.26
21.2
8.34
8.98
76.7
77.9
3.39
23.6
8.29
8.77
78.0
75.8
4.51
20.5
8.17
8.66
79.1
73.7
DAB(PA) 64
0
21.9
11.0
12.0
38.1
72.8
1.02
25.1
11.0
13.5
74.8
84.8
2.05
25.2
10.8
11.7
73.1
79.7
3.07
26.4
10.9
11.7
74.6
75.9
4.09
27.7
10.9
12.1
74.9
72.3
BM-PEI
0
21.9
11.0
12.0
38.1
72.8
1.09
22.4
12.5
13.7
46.1
77.7
2.17
21.4
11.7
13.5
53.8
78.2
3.26
22.4
10.9
13.3
59.4
75.3
4.34
20.1
10.4
13.4
61.9
72.4
TABLE V
Polymer Dosage
FPAR
Polymer
(kg/t)
(%)
DAB(PA) 4
0
6
5
14.6
10
16.5
15
17.8
20
17.7
DAB(PA) 64
0
6
5
14.2
10
18.5
15
18.1
20
23.1
TABLE VI
DAB(PA) 64
Drainage
First-pass
Polymer Dosage
WRV
Rate (E)
Retention
Stock
(kg/t)
(%)
(mL/s)
(%)
100% OCC
0
2.08
88.7
94.5
0.5
2.11
127
95.4
1
2.11
124
95.7
2
2.14
122
100.0
4
2.17
106
96.8
8
2.19
102
97.8
50% OCC/
0
2.08
88.6
94.5
50% NSSC
0.5
2.13
86.2
99.3
1
2.31
78.5
99.1
2
2.21
72.1
99.2
4
2.14
58.3
99.5
8
2.13
52.4
99.6
TABLE VII
DAB(PA) 64
Polymer Dosage
Drainage Rate
Stock
(kg/t)
(mL/s)
100% OCC
0
8.9
0.5
16.9
1
18.6
2
19.7
4
29.9
8
33.2
50% OCC/
0
2.3
50% NSSC
0.5
2.8
1
2.8
2
2.8
4
3.5
8
3.6
TABLE VIII
Polymer
Particle
Percent
Dosage
Count
Reduction
Polymer
(kg/t)
(millions/ml)
(%)
DAB(PA) 64
0
149
—
5
137
8.05
10
123
17.44
15
82
44.97
20
54
63.76
DAB(PA) 4
0
116
—
5
63
45.69
10
27
76.73
15
6.2
94.66
20
3.5
96.98
TABLE IX
Polymer Dosage
FPR
Polymer
(kg/t)
(%)
DAB(PA) 4
0
44.34
2
46.89
4
47.55
8
47.65
DAB(PA) 64
0
44.34
2
50.12
4
51.41
8
50.18
EDA(PA) 4
0
44.34
2
47.82
4
47.12
8
47.43
EDA(PA) 8
0
44.34
2
46.75
4
47.25
8
47.21
Linear polyethylene imine
0
44.34
2
48.95
4
48.76
8
50.31
TABLE X
Polymer Dosage
FPR
FPAR
Polymer
(kg/t)
(%)
(%)
DAB(PA) 4
0
32.4
30.5
2
34.7
30.6
4
34.9
30.3
8
35.3
30.1
DAB(PA) 64
0
32.4
30.5
2
35.9
30.2
4
35.7
30.3
8
39.7
30.6
EDA(PA) 4
0
32.4
30.5
2
36.4
30.5
4
37.8
30.4
8
37.8
30.3
EDA(PA) 8
0
32.4
30.5
2
36.1
30.7
4
36.8
30.3
8
39.7
29.8
Linear polyethylene imine
0
32.4
30.5
2
34.7
30.3
4
36.0
30.3
8
38.8
30.4
TABLE XI
Polymer Dosage
FPR
Pitch Particles
Polymer
(kg/t)
(%)
(millions/ml)
DAB(PA) 4
0
27.5
227
2
29.0
153
4
30.5
109
8
30.4
93
DAB(PA) 64
0
27.5
227
2
31.6
116
4
30.5
54
8
30.8
23
EDA(PA) 4
0
27.5
227
2
33.0
131
4
34.1
82
8
33.2
73
EDA(PA) 8
0
27.5
227
2
30.9
169
4
29.2
158
8
29.8
116
Linear Polyethylene imine
0
27.5
227
2
32.1
81
4
33.1
30
8
33.2
12
TABLE XII
Polymer Dosage
Cationic
Time
(kg/t)
FPR
FPAR
Demand
Period
DAB(PA) 4
CPAM
(%)
(%)
Turbidity
(mEq./L)
1
0
0
64.8
0.5
132
1.28
2
0
0.05
73.2
5.5
80
0.84
3
0
0
65.0
2.7
70
0.78
4
0.5
0
70.9
23.8
4
0.67
5
1.0
0
73.8
18.7
2
0.62
6
2.0
0
76.2
20.4
1
0.41
7
0
0
64.8
2.8
1
0.38
8
1.0
0
73.1
25.6
1
0.22
9
0
0
66.4
10.1
1
0.12
10
1.0
0.05
78.2
33.8
1
0.14
11
0
0
78.6
32.4
1
0.04
|
A papermaking stock and a method for improving the retention of pulp fines, mineral fillers, dispersed wood resin, and/or synthetic hydrophobic stickies and cellulose fibers in a cellulosic fiber sheet, employs dendrimeric polymers for increasing the retention of fines, fillers, dispersed hydrophobic particles, and cellulosic fibers. The application in the paper industry provides a means of (1) increasing the retention of fillers in paper and decreasing the loss of filler materials in white water waste from papermaking; (2) increasing the retention of cellulosic fines and fibers in the paper-making process; increasing drainage on the paper machine; and (3) removing a significant fraction of the wood resin, plastics, and stickies from the process stream thus enabling a greater extent of reuse of filtrates and, hence, less effluents from mills, fewer problems from wood resins such as deposit formation, loss of strength of product, and contamination of product with dirt particles.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a fuse for protecting components connected to an electric circuit against burning that may occur when abnormal overcurrent flows through the electric circuit.
Recently, there have been strong demands for the miniaturization of electronic apparatus. In order to meet these demands, the length of wiring of a circuit on a printed board tends to be rather small with charging sections having opposite polarities tending to be placed in close proximity to each other as well. Due to this, when compared with a case in which a conventional printed circuit board is used, a greater magnitude of abnormal current tends to flow once a short-circuit occurs.
In order to cope with this, smaller circuit protecting components also have been demanded, and the distance between terminals of such smaller circuit protecting components has been decreased. In cutting off abnormal current, there is a close relationship between the occurrence of arc discharge and the magnitude of abnormal current and/or the distance between the terminals. The greater the magnitude of abnormal current becomes, or the smaller the distance between the terminals becomes, the more easily longer arc discharge occurs. Arc discharge generates heat having a high temperature of several thousand degrees centigrade, and due to this there is a risk of the circuit protecting components themselves being burnt. Thus, cutting off the current becomes more and more difficult when trying to satisfy the demands for the miniaturization of circuit protecting components.
2. Prior Art
Conventionally, in a well known fuse of this type is well known an arc-extinguishing material is packed around a fusible element so as to extinguish a high-temperature arc that is generated after the fusible element has been fused by abnormal current.
In the fuse described above, since the arc-extinguishing material is brought into direct contact with the fusible element, the arc-extinguishing material abrades or cuts into the surface of the fusible element, whereby the fusible element is damaged. Thus, the fuse of this type has a drawback in that it mechanically breaks down due to the damage so caused. In addition, when the fusible element is fused by a great magnitude of current, the complete dispersion of metal vapors rising from the fused fusible element is prevented by the arc-extinguishing material surrounding the fusible element, preventing the creation of wide spaces between metal particles, and resulting in poor insulation. Thus, there is the risk of an arc discharge being caused again. Moreover, it is a very difficult operation to pack a particulate arc-extinguishing material into a small fuse's main body. Therefore, the productivity associated with the manufacturing process is low.
SUMMARY OF THE INVENTION
The present invention was made in view of the above drawback inherent in the prior art. So, the object thereof is to provide a reliable high breaking capacity micro-fuse capable of ensuredly breaking a great magnitude of current, as well as of maintaining a fusible element, used therein, free from damage when in proper operation.
In order to achieve this object, a high breaking capacity micro-fuse according to the present invention comprises an insulating body having a wall and a cavity defined by said wall in said body; a pair of conductive terminals extending outwardly from said cavity through said wall and being opposed to each other; a fusible element having opposite ends, one of said ends being mechanically and electrically connected to one of said pair of terminals within the cavity, said fusible element extending from said one of said pair of terminals to the other of said pair of terminals, the other of said ends of said fusible element being mechanically and electrically connected to said other of said pair of terminals within the cavity; and an insulating member having a hole which passes through said insulating member and through which said fusible extends, said insulating member having a shape by which a space is provided between the inner surface of said wall of said body and said insulating member with said insulating member being disposed in said cavity of said body.
The insulating member disposed in the cavity of the body functions to allow metal vapor, generated when the fusible element extending through the hole of the insulating member has been fused by an abnormal overcurrent flowing through the fusible element, to be released from the hole to the outer surface of the insulating member, and then to the inner surface of the wall of the body for dispersion, whereby the deposition density of metal vapors on the respective surfaces of the body and the insulating member is low, thereby making it possible to achieve a high insulation resistance.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a fuse of the present invention before assembly;
FIG. 2 is a perspective view of the same fuse in which components have been incorporated;
FIG. 3 is a perspective view of the fuse of the present invention which has been completely assembled;
FIG. 4 is a longitudinal sectional view of the fuse of the present invention; and
FIG. 5 is a cross-sectional view taken along the line A-A' of FIG. 4.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, a preferred embodiment of the present invention will be described.
In FIGS. 1 to 5, a fuse's main body 1 is formed from a heat-resistant insulating material, such as ceramic, by embossing and baking the same material into a rectangular parallelepiped-shaped box which is 2 to 3 mm wide, 7 to 8 mm long, and 2 to 3 mm high with the thickness of the materiel ranging from 0.5 to 1 mm.
Particularly speaking, slots are formed in longitudinal ends of the box 1 so as to allow terminals 3, 4 to extend outwardly from the box 1. A fusible element 6 is fixed between these terminals 3, 4 inside the box 1, and the terminals 3, 4 are electrically connected to electric circuits outside the box 1, respectively.
Partition walls 10, 11 are provided internally at the longitudinal ends of the box so as to prevent the inward movement of the terminals 3, 4, as well as movement of a cylindrical tube 2 provided in the box.
Solder-plated copper is used for the terminals 3, 4 and is press-formed into a T-shaped lead wire, so as to prevent the withdrawal of the lead wire longitudinally of the main body 1 once a T-shaped end thereof is placed in the box-shaped main body 1. A heat-resistant insulating material such as ceramic is used for the cylindrical tube 2, and this material is embossed and baked, so as to be formed into a cylindrical tube having an outside diameter of 1 mm and an inside diameter of 0.5 mm, and as shown in FIG. 2, this cylindrical tube 2 has a length allowing itself to just fit inside 5 of the box-shaped main body 1 after the fusible element 6 has been put therethrough.
The fusible element 6 is fixed to the terminals 3, 4 at the ends thereof, respectively, by solder 8, 9. Afterwards, a lid 7, made from the same material as that of the box-shaped main body 1, is placed on the top of the box-shaped main body 1 so as to seal the upper opening thereof, whereby a micro-fuse having an external appearance as shown in FIG. 3 is completed.
Thus, as can be seen in FIG. 5, the cross-sectional shape of a cavity formed by the box-shaped main body 1 and the lid 7 placed thereon is rectangular, and spaces 12, 13, 14 and 15 are formed between the inner wall surface of the box-shaped main body 1, including the lid 7, and the outer surface of the cylindrical tube 2.
Even in the high breaking capacity micro-fuse as mentioned above, which has a simple construction in which the cylindrical tube with the fusible element extending therethrough is inserted in the box-shaped main body, it is possible to attain superior insulation resistance by allowing metal vapors to be dispersed into spaces 12, 13, 14 and 15 and to be absorbed by the inner wall surfaces of the box-shaped main body 1 and the lid 7, and the outer and inner surfaces of the cylindrical tube 2. It is also possible to obtain a performance good enough to securely break a great magnitude of current by means of an additional simple component such as a cylindrical tube 2 and simple assembling thereof. Moreover, there is no material surrounding the fusible element 6 in the cylindrical tube such as an arc-extinguishing material, and therefore the fusible element 6 is made free from restraint that would be imposed when an arc-extinguishing material is used. In addition, the surface of the fusible element 6 is also prevented from being abraded and damaged whereby any mechanical breakage is prevented, thereby making it possible to obtain a highly reliable fuse.
A comparison test, between the high breaking capacity micro-fuse according to the present invention and a conventional fuse using an arc-extinguishing material, was carried out. With the high breaking capacity micro-fuse of the present invention, a proper current breaking operation was performed without any difficulty under the short-circuit breaking test condition voltage of 125 V, short-circuit current 50 A and power factor of 0.7 which are stipulated under the overcurrent protection fuse standards UL198G. The micro-fuse exhibited a short-circuit breaking capacity performance similar to that of the fuse in which an arc-extinguishing material is used. Moreover, in a repeated overcurrent test, in which an exciting current equal to the rated current is repeatedly switched on and off for one second intervals in an alternate fashion, the conventional fuse in which an arc-extinguishing material is used was fused after it had been switched on and off eight hundred and fifty-two times, while the high breaking capacity fuse of the present invention managed to endure the repeated energizations of ten thousands times, without fusing.
As is clear from the above description, the high breaking capacity fuse according to the present invention has a superior performance.
It should be noted that in order to form a space or spaces between the inner wall surface of the main body 1 and the lid 7, and the outer surface of the tube 2, various cross-sectional shapes of the cavity formed by the main body 1 and the lid 7 placed on the top of various main body 1, and the cross-sectional shapes of the outer surface of the tube 2 may be employed, respectively. Moreover, it should be noted that the cylindrical tube 2 may consist of a plurality of cylindrical tubes which are disposed in series inside of the main body 1.
The present invention has been described in detail with reference to a certain embodiment thereof, but it will be understood that various modifications can be effected within the spirit and scope of the invention.
|
A high breaking capacity micro-fuse includes a body having a wall which forms a cavity in a body, pair of conductive terminals extending through the wall, and a fusible element extending between the pair of conductive terminals and connected thereto in the cavity. An insulating member with a hole through which the fusible element extends has a shape by which a space is provided between the inner surface of the wall of the body and the insulating member when the insulating member is disposed in the cavity of the body.
| 7
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This application is a continuation of application Ser. No. 07/018,569, filed Feb. 25, 1987, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is related to a rotary combustor, or incinerator, for waste material and, more particularly, to an improvement in windboxes which supply combustion air to a rotary combustor, for preventing clogging of the windboxes by low-melting temperature metals, such as aluminum.
2. Description of the Related Art
Proper disposal of solid waste has become an increasingly serious problem as existing sites for land disposal near capacity and new sites become increasingly difficult to locate while the amount of toxic chemicals, particularly in municipal waste, appears to be increasing. Incineration of combustible solid waste has long been used to reduce the quantity of solid matter needing disposal. One device used for this purpose is a water-cooled rotary combustor which has been used in an increasing number of applications over the last one to two decades. While a rotary combustor is capable of burning most types of combustible waste, ranging from eight-foot long logs to typical kitchen waste, certain problems arise when the waste includes low-melting temperature metals, particularly those used in beverage containers, foil, disposable trays, etc. Thus, municipal solid waste, which includes kitchen waste as well as waste from other sources, contains aluminum in a relatively pure state. The combustion temperature in a rotary combustor reaches well in excess of 660° C., at which pure aluminum melts. Therefore, molten aluminum is formed in the rotary combustor and flows downward, solidifying shortly after leaving the combustor and eventually clogging passageways that provide the air required for combustion.
SUMMARY OF THE INVENTION
An object of the present invention is to provide means for preventing clogging, by resolidified metal, of combustion air passageways in a rotary combustor.
Another object of the present invention is to provide means for removing molten metal from a rotary combustor to prevent clogging problems.
A further object of the present invention is to provide means for separating recyclable aluminum from municipal waste undergoing incineration.
The above-mentioned objects are attained by providing an apparatus for preventing accumulation of molten metal dropping from a combustion barrel and solidifying in a windbox of a rotary combustor. The apparatus comprises a heatable contact surface disposed in the path of the molten metal dropping from the combustion barrel, heating means for heating the contact surface, and heat insulation which separates the heatable contact surface from the windbox. In one embodiment of the present invention, the heatable contact surface has a funnel shape with a downwardly extending tube and is generally disposed in the horizontal center of the windbox. In this embodiment, the apparatus also includes means, such as a pipe coupled and sealed to the downwardly extending tube, for discharging the molten metal from the windbox. The pipe is also heated by the heating means.
In a second embodiment of the present invention, the heat insulation covers a significant portion of the interior surface of the windbox and the heatable contact surface is disposed on the insulation, conforming to the interior surface of the windbox. In this embodiment, the apparatus includes airlock doors, disposed at the lower end of the windbox, having a heated portion abutting the heatable contact surface lining the interior surface of the windbox. The metal is discharged from the windbox by opening the airlock doors one at a time.
These objects, together with other objects and advantages which will be subsequently apparent, reside in the details of construction and operation as more fully hereinafter described and claimed, reference being had to the accompanying drawings forming a part hereof, wherein like reference numerals refer to like parts throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a cross-sectional, side elevational schematic view of a rotary combustor in which the present invention can be utilized.
FIG. 1B is a schematic top plan view of the rotary combustor illustrated in FIG. 1A;
FIG. 2 is a cross-sectional and elevational schematic view of the rotary combustor illustrated in FIG. 1A;
FIG. 3A is a schematic, cross-sectional and elevational view in a plane transverse to the axis of an associated rotary combustor, of windboxes and a segment of a combustion barrel in the associated rotary combustor, in accordance with a first embodiment of the present invention;
FIG. 3B is a cross-sectional, side elevational schematic view, taken in a plane transverse to that of FIG. 3A, of one of the windboxes shown in FIG. 3A; and
FIG. 4 is a schematic, cross-sectional and elevational view in a plane transverse to the axis of an associated rotary combustor, of windboxes and a segment of a combustion barrel in the associated rotary combustor in accordance with a second embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A conventional water-cooled rotary combustor is illustrated schematically in a cross-sectional, side elevational view in FIG. 1A; the rotary combustor generally includes a combustion barrel 10 having a generally cylindrical side wall 23 formed of longitudinally extending cooling pipes 24 arranged in spaced axial relationship. The cooling pipes 24 are encircled by, and secured to, bands 13 which in turn are supported by rollers 12. The combustion barrel 10 receives solid waste 14 at an input end 16 and discharges heat 20 and solid combustion products 22, e.g., ash, at an exit end 18. The combustion barrel 10 may be rotated by driving the rollers 12 or by a separate ring gear (not shown) affixed to the barrel and driven by a pinion, as disclosed in U.S. Pat. No. 3,822,651 to Harris et al., incorporated herein by reference.
The combustion barrel 10 has a central axis of rotation which is inclined slightly from the horizontal, proceeding downwardly from the input end 16 to the exit end 18. Combustion air is forced into the barrel 10 through gas-porous interconnections 51 between adjacent cooling pipes 24 by windboxes, including windboxes 32, 34 and 36 illustrated in FIG. 1A. The gas-porous interconnections 51 are preferably formed of bar steel perforated by openings 52. The interconnections 51 extend from the input end 16 and along the generally straight axial portions of the pipes 24 to an angled section, or truncated conical section, 24a which is received within a flue 28. No interconnections 51 are included in the angled section 24a, in which the cooling pipes 24 extend in a somewhat converging relationship to the exit end 18 of the barrel 10. The lack of interconnections 51 in the angled section 24a permits flue gas 20 and ash 22 to escape more easily from the barrel 10.
The temperature of cooling pipes 24 is maintained at approximately 275° C. by circulating coolant therethrough. The resulting high-energy coolant is discharged from the barrel 10 via a ring header 17 and supply pipes 26. The high-energy coolant discharged by the supply pipes 26 is circulated by a pump 25 through a rotary joint 35, such as the joint disclosed in Harris et al. '651, to heat exchanging equipment 27 which returns low-energy coolant to the ring header 17 via the pump 25, joint 35 and supply pipes 26. The supply pipes 26 preferably include a double-walled, or coaxial, pipe 37 for connection to the joint 35. The ring header 17 distributes the low-energy coolant received from the heat exchanging equipment 27 to a first set of the cooling pipes 24 which transport the coolant the length of the barrel 10 to return means, such as U-tubes 39, at the input end 16 of the barrel 10. The U-tubes 39 couple the first set of the cooling pipes 24 to a second set of the cooling pipes 24 which return the coolant to the ring header 17 to be discharged to the heat exchanging equipment 27. The heat exchanging equipment 27 may include a boiler, a condenser, connection to a steam driven electrical power generating system, etc. (all not shown), as known in the art.
Referring to FIGS. 1A, 1B and 2, the combustion air is supplied to the combustion barrel 10 by an air duct 30 and windboxes 32, 34, 36 and 38. The windboxes 32-38 are disposed underneath the combustion barrel 10 and generally perpendicular to the axis of the generally cylindrical barrel 10. Air is transferred from the duct 30 to the windboxes 32-38 via control ducts 40, 42, . . . , 50, best seen in FIG. 1B. As illustrated in FIG. 2, control duct 46 supplies combustion air from the air duct 30 to the middle "overfire" windbox 34, while control duct 44 supplies combustion air to the middle "underfire" windbox 38. The air supplied by air duct 30 may be preheated by the exhaust from the flue 28 and may be blown by a conventional forced draft fan (not shown). Preferably, the combustion air is drawn from a waste input area 15 to provide a source of ventilation for the waste material 14 being loaded into the combustion barrel 10.
FIG. 2 is a schematic cross-sectional, end elevational view of the conventional rotary combustor illustrated in FIG. 1A. As illustrated in FIG. 2, the combustion barrel 10 is housed within an enclosure 57, not illustrated in FIG. 1A for simplicity, which ensures that the flue gas 20 exits via the flue 28. The enclosure 57 is supported on an appropriate surface by supports 58. A cut-away 59 is provided in FIG. 2 to illustrate a control duct 44 which supplies combustion air to "underfire" windbox 38. As further illustrated in FIG. 1B, control duct 44 lies behind control duct 46 in the plane in which FIG. 2 has been taken.
As viewed in FIG. 2 from the exit end 18 (FIG. 1A), the combustion barrel 10 rotates in a clockwise direction. As a result, the waste material 14 is shifted to the left side of the combustion barrel 10, as seen in FIG. 2. Therefore, above the "overfire" windboxes, e.g., windbox 34, there are usually at least a few openings 52 which are not covered by waste material 14 and thus are able to supply large quantities of air to the top of the pile of waste material 14 to support combustion. On the other hand, the "underfire" windboxes, e.g., windbox 38, direct air to the base of the waste material 14 to aid in combustion. Ordinarily, the waste material 14 is sufficiently large and irregularly shaped so that a sufficient number of the openings 52 are unblocked above the underfire windboxes, permitting air to penetrate into the waste material 14 in the barrel 10.
Typically, the air pressure differential between the windboxes and the barrel 10 is a couple of inches of water, i.e., slightly less than one-tenth (0.1) psi. As illustrated in FIG. 2, seal strips 54 cooperate with windbox edges 56 to afford a pressure seal between the windboxes and the combustion barrel 10. The seal strips 54 extend longitudinally, i.e., in a parallel-axial direction, along and secured to the exterior of the combustion barrel 10, and have a dogleg-shaped cross section as illustrated in FIG. 2. Each of the seal strips 54 is continuous for at least the axial length of one windbox.
Small particulate matter, such as ashes, and liquids, such as molten aluminum, drop through the openings 52 in the interconnections 51. This occurs most often in the windboxes closest to the exit end 18 of the combustion barrel 10. In a combustor with six windboxes, such as the combustor illustrated in the drawings, the greatest accumulation of material occurs in overfire windboxes 34 and 36 (FIG. 1A), underfire windbox 38 (FIG. 2) and the underfire windbox (not shown) closest to the exit end 18. To avoid an excess accumulation of the materials dropping through the openings 52, airlock doors 60 (FIG. 3A) enable the accumulated solid matter to be discharged through the lower end 65 of the windboxes. However, the temperature of the air in the windboxes, even if the air is preheated as described above, is typically 250° C. As a result, the molten aluminum quickly solidifies after dropping through the openings 52 into the windboxes. In a conventional rotary combustor used for incinerating municipal waste, the resolidified aluminum accumulates in the windboxes, particularly at the angled portions 61 (FIG. 2) where the horizontal cross section of the windboxes is reduced. As the resolidified aluminum builds up in this region, the accumulated aluminum constricts the flow of combustion air, eventually preventing the flow of air into the combustion barrel 10.
According to the present invention, such results are avoided by including a heatable contact surface on which the aluminum accumulates as it drops from the combustion barrel 10. The contact surface is maintained at a temperature of at least 660° C. so that the aluminum remains in a molten state. Heat insulation separates the heatable contact surface from the walls of the windbox.
A first embodiment of the present invention is illustrated in FIGS. 3A and 3B in which the heatable contact surface forms a funnel 62 with a downwardly extending tube 64 that discharges the molten aluminum captured by the funnel 62. An electrical source for heating 80 maintains the heatable contact surface 62, 64 and pipes 66 above 660° C. The pipes 66 are coupled and sealed to the tube 64, pass through the walls of windboxes 34 and 38 at apertures 69 and are separated from the side walls 63 of the windboxes 34, 38 by insulation 68.
A second embodiment is illustrated in FIG. 4, in which heatable contact surfaces 70 line the interior surface 63a of the side walls 63 of each of the windboxes 34 and 38 and are separated therefrom by insulation 72. The contact surfaces 70 may have a beveled portion 74 near the opening 76 connected to the control duct 44 or 46 to ensure that the molten aluminum does not accumulate excessively in the opening 76. The airlock doors 60a and 60b include heatable portions 78a and 78b, respectively, in their central areas spanning the open area between the insulated and heatable contact surfaces 70 to maintain the molten aluminum which accumulates on the upper surfaces 79a and 79b, respectively, in a molten state until it is removed. Removal preferably is performed by first opening airlock door 60a while door 60b remains closed, and then opening airlock door 60b after door 60a is closed. The airlock doors 60a and 60b may be of any conventional type, and thus may be mounted for sliding movement as schematically indicated in FIG. 4, to permit the described selective opening thereof, or may be hinged at one end so that the molten aluminum slides off.
In FIG. 4, the heated portion 78b is in the center of airlock door 60b, separated from the walls of the windbox 72 by heat insulation 72b. Thus, airlock doors 60a and 60b are constructed identically. This is preferable both for convenience of manufacturing and because aluminum is present in the region between the airlock doors 60a and 60b, only during the time period between alternate and successive openings of the airlock door 60a and the airlock door 60b, typically a few minutes or less. It is, of course, possible to extend the heated surface 70 and insulation 72 into this region, and even below airlock door 60b, if desired.
The simplest means of heating the contact surfaces 62, 64 and 70 is to use electrical resistance. For this purpose, an electrical source 80 for heating is connected to the heatable contact surfaces 62, 64 and 70 by heating elements which may be similar to the heating elements on electric ranges. In other words, the heating elements may include a core having a high electrical resistance, surrounded by cladding formed of a material which is a relatively poor conductor of electricity and a relatively good conductor of heat. The heatable contact surfaces form an outer layer on at least one side of the heating elements and may be formed from inexpensive stainless steel.
The many features and advantages of the present invention are apparent from the detailed specification and thus, it is intended by the appended claims to cover all such features and advantages of the device which fall within the true spirit and scope of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation illustrated and described. Accordingly, all suitable modifications and equivalents may be resorted to falling within the scope and spirit of the invention.
|
A rotary combustor for incinerating solid waste material, such as municipal trash, includes a combustion barrel supplied by air through windboxes underneath the barrel. Molten metal, such as aluminum, which is commonly present in the waste material, drops through perforations in the side wall of the combustion barrel and collects on a heated contact surface in each of the windboxes. The heated contact surface may have a funnel shape and be connected to a heated pipe for transferring the molten metal out of each windbox. Alternatively, the heated element may be attached to the interior surface of each windbox and separated therefrom by heat insulation. In this case, heated airlock doors at the lower end of the windboxes are used to discharge the molten metal from the windboxes.
| 5
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FIELD OF THE INVENTION
The invention concerns a ram boring apparatus with a generally cylindrical body, a head having formed in it at least one jet opening for the ejection of a stream of high pressure fluid and a hammering mechanism arranged in the body and driven by a pressure medium for driving the apparatus forwardly.
BACKGROUND OF THE INVENTION
A ram boring apparatus of the aforementioned character is known, for example, from U.S. Pat. No. 4,858,703. In the apparatus described by that patent the hammering mechanism is driven by air pressure. The fluid required for the high pressure stream is delivered by a line to an expansion chamber in the housing and is driven out of the expansion chamber by means of air pressure.
In the prior art, approaches are also known in which the hammering mechanism is driven by air pressure, while separate therefrom high pressure fluid is delivered to the jet.
Common to all known approaches is the disadvantage that two kinds of pressure medium have to be supplied. Therefore, at least two pressure fluid sources are required and the construction of the ram boring apparatus is correspondingly complicated. Moreover, several pressure fluid lines have to be provided which in practice represent a large source of operational problems. With high pressure, these conductors have to be made with strong walls and they are, therefore, inflexible, heavy and a hindrance to practical operation.
The invention has as its object the provision of a ram boring apparatus of the aforementioned kind which is simple and economical in construction and easy to handle.
This object is solved in accordance with the invention in that the hammering mechanism is formed as an hydraulic hammering mechanism and it and the jet opening are connectable with the same pressure fluid source.
Therefore, only one pressure fluid source is required for the ram boring apparatus of the invention, which source can, for example, be water, a water-polymer-mixture or Bentonite under high pressure delivered to the ram boring apparatus. Thereby a single pressure fluid conductor to the ram boring apparatus is sufficient. The ram boring apparatus can accordingly be simply constructed and is easy to handle, since it need be connected by only a single pressure fluid conductor with the stationary station.
If the body is connected with a forward drive rod, a control valve can be arranged in the pressure fluid line in the body upstream of the hammering mechanism and/or the jet opening for selectively delivering the pressure fluid to the hammering mechanism and/or to the jet opening. This offers the possibility that, in accordance with the workability of the earth encountered by the ram boring apparatus, the ram boring apparatus can be driven forwardly with or without the use of the hammering mechanism. For example, the control valve can be so made that it is controllable in dependence on the pressure of the pressure fluid. For example, the arrangement can be that with fluid pressures up to 80-100 bar the hammering mechanism does not operate, with the pressure fluid only being ejected in known way forwardly out of the one or more flushing jets of the boring head to break up the earth. If the operator adjusts the pressure of the pressure fluid to a value above 80-100 bar, the control valve opens to deliver the fluid to the hammering mechanism, so that this mechanism begins to operate. In this way the ram boring apparatus is actively driven through gravelly earth. While the hammering mechanism operates, at the same time flushing fluid is ejected in known way forwardly from the boring head for loosening the earth.
Preferably the head, along with the body, is rotatable about its longitudinal axis by means of the forward drive rod and has a control surface oriented at an angle other than 90° to the body longitudinal axis. For improving the boring efficiency, at least the control surface can be studded with hard metal bodies. For straight bores, the ram boring apparatus is rotated at, for example, 100-200 revolutions per minute. For the control of the ram boring apparatus and a change in the direction of the boring, the ram boring apparatus is held in a given position of the head and the apparatus is then moved forwardly, percussively or statically, without rotation, so that through the control surface on the head it is deflected in the desired direction. This process is assisted by the fluid which is ejected from the one or more jet openings.
The head can also be symmetrical with respect to the longitudinal axis of the body. Such a head can better destroy obstacles than the asymmetrical head with control surface. Its control characteristics are, however, not as good as those of the asymmetrical head since the control effect in its case can only be achieved by asymmetrical arrangement of the jet openings.
The head can be axially rigidly or movably connected with the body. Practically, the head is exchangeable with the body, so that in accordance with the type of earth at hand different forms of heads can be put into use.
For locating the ram boring apparatus in the earth, the apparatus can also contain in a known way a sender for transmitting electromagnetic radiation by the help of which the position of the apparatus can be determined and from which also the measurement of the ram boring apparatus to the upper earth surface can be determined. Practically the sender is impact dampeningly arranged in a sender housing positioned behind--with respect to the forward drive direction--the hammering mechanism in order to better protect it against damage.
For manufacturing and maintenance reasons, the body can be divided into a hammering mechanism containing portion and a sender receiving portion.
In a preferred embodiment of the invention, the outer diameter of the ram boring apparatus decreases from front to rear. This on one hand eases the control of the apparatus and on the other hand eases the carrying away toward the rear of the bored out or washed out material by the flushing fluid. Practically, the outer diameter of the body portion containing the hammering mechanism is smaller than the outer diameter of the head and the outer diameter of the body portion receiving the sender is smaller than the outer diameter of the body portion receiving the hammering mechanism.
In order to be able to use water as the pressure fluid without danger of corrosion, it is practical if at least the portions of the ram boring device which come into contact with the pressure fluid are made of a corrosion resistant material, especially stainless steel.
Further features and advantages of the invention will be apparent from the following description, which in connection with the accompanying drawings explain the invention by way of exemplary embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawings are:
FIG. 1--A schematic illustration of a boring system using a ram boring apparatus embodying the invention.
FIG. 2--A schematic longitudinal section through a ram boring apparatus embodying the invention and having a symmetrical head.
FIG. 3--A schematic longitudinal section through a ram boring apparatus comprising a second embodiment of the invention and having asymmetrical head.
FIG. 4--A fragmentary sectional view corresponding to FIG. 3 taken through the ram boring apparatus with a partially schematic illustration of the hammering mechanism with its hammering piston in its forward position.
FIG. 5--A view corresponding to FIG. 4 but with the hammering piston in its rearward position.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a boring wagon 2 with a ramp 4 for driving forwardly, rotating and controlling a ram boring apparatus 6, by means of a boring rod 8. The boring wagon includes a non-illustrated source of pressure fluid.
The ram boring apparatus 6 illustrated in FIG. 2 includes a cylindrical body 10 on the forward end of which is arranged a boring head 12 symmetrical with respect to the longitudinal axis of the body. The boring head 12 has at least one jet opening 14 which through a canal 16 and a control valve 24 stands in connection with a pressure fluid connector 18 at the rear end of the body or housing 10.
Inside of the body 10 is a hammering mechanism, indicated only schematically at 20, which can drive the body 10 together with the head 12 automatically through ground of given composition. The hammering mechanism 20 is connected with the pressure fluid connector 18 through a conductor 22 and the control valve 24. The control valve 24 is controllable in such a way in dependence on the pressure that selectively either the jet opening 14 only is, or the jet opening 14 and the hammering mechanism 20 are, connected with the pressure fluid source.
At its rear end, the housing 10 is connected with the hollow forward drive or boring rod 8, through which the ram boring apparatus can be driven statically forwardly and rotated by the boring wagon 2.
Through the pressure fluid connector 18 and a pressure fluid conductor 26, connected with the pressure fluid connector 18 and carried inside the hollow boring rod 8, a pressure fluid, for example water, a water-polymer mixture or another known boring fluid is delivered. If the pressure of this fluid lies below a pre-given threshold value, for example 80-100 bar, the control valve 24 closes the conductor 22, and the pressure fluid discharges from the jet opening 14 in order to break up or wash away the region of earth lying in front of the head 12.
If the composition of the earth is such that static forward drive of the ram boring device by means of the forward drive rod 8 is no longer possible, the pressure of the pressure fluid is increased to a value above the threshold value so that the control valve 24 opens and the pressure fluid drives the hammering mechanism 20. In this way, the ram boring apparatus can also, for example, be forwardly driven through gritty or stony earth or individual hindrances can be disintegrated.
The threshold value at which the control valve 24 again closes the conductor 22 and thereby interrupts the drive of the hammering mechanism 20 should lie distinctly below the threshold value for the switching on of the hammering mechanism 20 in order to avoid a fluttering of the control valve. At the moment the hammering mechanism is turned on, the pressure fluid pressure decreases suddenly because of the increased requirement for pressure fluid. If the two threshold values for the turning on and turning off of the hammering mechanism are not different from one another or are only slightly different from one another, a constant turning on and turning off of the hammering mechanism would be unavoidable.
The directional control of the ram boring apparatus according to FIG. 2 takes place in the way, that the ram boring apparatus is held in a definite rotational position so that the unsymmetrically arranged jet softens the earth to the side of the ram boring apparatus, toward which the ram boring apparatus is to be deflected. If the ram boring apparatus is thereafter driven forwardly with the help of the boring rod or the hammering mechanism, it will be deflected into the softened region of the earth. Then for a straight run the ram boring apparatus can again be rotated by means of the boring rod.
In the embodiment illustrated in FIG. 3, the body 10 includes a first section 30, in which the hammering mechanism 20 and the control valve 24 are located. An asymmetrical control head 32 is exchangeably arranged on the forward end of the body section 30. The control head 32 has a control surface 36, oriented at an inclination to the axis 34 of the housing and studded with hard metal bodies 38. The control head 32 and body 10 can, by means of the boring rod 8, be rotated about the body axis 34 or can be held in a desired position relative to the body axis. The control head 32 further has a jet opening 14, which so opens away from the side, that the ejected jet stream is directed forwardly at an inclination to the body axis 34.
At the connection point between the body section 30 and the control head 32 a coupling 28 is provided for the connection of the fluid conductor 16 of the section 30, which coupling 28 permits an axial movement of the control head 32 relative to the body 10, as explained further in connection with FIGS. 4 and 5.
Connected to the rear end of the body section 30 is a sender housing 40 in which a sender 42 is supported so as to be damped against impact. The sender 42 sends electromagnetic radiation outwardly through slits 44 provided in the sender housing 40 so that with the help of that radiation the position of the ram boring apparatus can be determined by a suitable receiver on the upper surface of the earth. The sender 42 also serves to indicate the position of the control surface 36 in space so that a control of the ram boring apparatus can be practically effected.
At the rear end of the housing section formed by the sender housing 40 is a connecting part 46 for the hollow pushing rod 8, through which the pressure fluid delivery occurs.
As can be seen, the outer diameter of the cylindrical body section 30 is somewhat smaller than the outer diameter of the control head 32. The outer diameter of the sender housing 40 is in turn somewhat smaller than the outer diameter of the body section 30.
The hammering mechanism will now be explained in more detail in connection with FIGS. 4 and 5. These figures show the control head 32 and the body section 30 of the embodiment illustrated in FIG. 3. Similar parts are given the same reference numbers. The body section 30 consists of three body portions 48, 50, 52. The body portions 50 and 52 are threadably connected with one another at 54. The two portions 50 and 48 are plugged together and secured by bolts 56. The control head 32 has a pin 58 inserted into the forward end of the body portion 48. The pin 58 has a groove 60 in its circumferential surface which receives a bolt 62 extending through the body portion 48. As will be seen from FIGS. 4 and 5, the control head 32 is thereby held to the body portion 48 so as to be non-rotatable but axially movable relative to the body portion 48.
A percussive piston 66 is axially slideably supported in an axial bore, indicated generally at 64, in the housing section 30. It includes a larger diameter forward shaft 68 and a smaller diameter rear shaft 70. A first forward piston portion 72 and forward seals 74 limit in the axial direction a forward chamber 76 of the bore 64. A second rear piston portion 78, axially spaced from the first piston portion 72, together with the first piston portion 72, limits in the axial direction a middle chamber 80 of the bore 64. The rear piston portion 78, together with rear seals 82, limit in the axial direction a rear chamber 84 of the bore 64.
The pressure line 22 for the delivery of pressure fluid to the hammering mechanism 20 connects the control valve 24 with an inlet opening 86 in the forward chamber and an inlet opening 88 in the rear chamber. The rear chamber and the middle chamber are connected to one another by a control line 90. The middle chamber 80 is further connected with an outlet 94 for the pressure fluid by a discharge opening 92. The outlet 94 is further connected with a discharge opening 98 for the rear chamber 84 by a line 96.
The rear shaft 70 is surrounded with radial spacing by a control sleeve 100 having a plurality of radial bores 102.
FIG. 4 shows the percussive piston in its forwardmost position, at which it impacts on the pin 58 of the control head 32, the axial movement of the control head having not been taken into consideration in the illustration. The axial movability of the control head 32 makes possible a better utilization of the kinetic energy of the percussive piston 66. In this position the control sleeve 100 is also in its forward end position. The middle chamber 80 is connected with the outlet 94. The delivery of pressure fluid through the inlet opening 88 is blocked by the control sleeve 100. The inlet opening 86 in the first chamber is, on the other hand, only partially blocked by the forward piston portion 72, so that pressure fluid can work on the annular forwardly facing surface 104 of the piston portion 72. Since the middle chamber 80 and the rear chamber 84 are connected with the non-pressurized outlet 94, and the inlet opening for the pressure fluid in the rear chamber 84 is blocked by the control sleeve 100, the percussive piston 66 will be moved rightwardly from the position illustrated in the figure, that is toward the rear. As soon as the piston portion 72 is driven past the outlet opening 92 of the middle chamber 80, pressure fluid can no longer escape from the middle chamber. The dimensioning of the surfaces of the control sleeve 100 on which the pressure fluid is effective is so chosen that lastly under the conditions of FIG. 4 it is likewise moved to the right or rearwardly, until it abuts a shoulder 106 of the housing section 52. In this position, the inlet opening 88 for the entry of pressure fluid to the rear chamber 84 is unblocked. This position of the hammering mechanism is illustrated in FIG. 5. The pressure of the entering pressure fluid works on the rearwardly facing annular surface 108 of the piston portion 78, which is larger than the annular surface 104 of the piston portion 72. Thereby the percussive piston 66 is not only braked but is also again driven toward the left from the end position illustrated in FIG. 5, that is, moved forwardly until the piston impacts onto the pin 58 of the control head 32. Thereby the piston portion 72 frees the outlet opening 92 of the middle chamber 80 so that the pressure in this chamber can fall off. The reduction of pressure in the middle chamber 80 has the effect, through the control line 90, that now the pressure in the rear chamber 84 moves the control sleeve 100 toward the left, that is forwardly, until it reaches the position illustrated in FIG. 4, in which the inlet opening 88 for pressure fluid to the rear chamber 84 is again closed. The described cycle then begins anew.
The apparatus of FIGS. 3 and 5 as so far described operates in the following ways:
The pressure of the flushing liquid can be adjusted from the boring wagon 2 arranged on the surface of the earth or in a starting excavation. With a flushing liquid pressure up to about 100 bar the control valve 24 remains closed so that the hammering mechanism is not operated. In this case the apparatus works only as a boring apparatus. To bore straight ahead, the ram boring apparatus, that is the head 32 and body 10, is rotated at about 100 to 200 revolutions per minute and at the same time is pushed forwardly by the non-illustrated rod 8. The flushing liquid which is discharged by the jet directed forwardly or toward the side breaks up the earth and thereby makes easier the boring operation. In special soils, such as sandy soils, it is necessary that the earth be carried away rearwardly along the rod. This is accomplished by the escaping flushing fluid. Practically for this fluid a polymer-water-mixture or Bentonite is, for example, used. In order to control the boring direction and thereby change the direction of the bore, the boring head is brought to a suitable rotational position, with information as to the actual rotational position being supplied by the sender 42. Thereafter the boring apparatus is pushed forwardly with the boring head 32 non-rotating. The control surface 36 inclined to the body axis 34 effects a deflection of the boring apparatus in the desired direction. This procedure is also supported by the flushing liquid which is discharged by the jet 14. This is especially the case when the jet is directed sidewise, since then the earth is broken up in the direction in which the boring apparatus is to be deflected.
In the case of densely compacted gravel or stony sub-soil, the previously described way of operating is no longer possible. In such ground, the boring apparatus can be driven forwardly only by means of the hammering mechanism 20. To switch on the hammering mechanism, the flushing liquid pressure is adjusted to 150 to 200 bar. Since the control valve 24 opens at a flushing liquid pressure of about 100 bar, the hammering mechanism 20 begins to hammer. The flushing liquid now flows through the channel 16 to the one or more jets 14 as well as through the line 22 to the hammering mechanism 20 so as to drive the hammering mechanism. The flushing fluid flows from the hammering mechanism 20 at close to zero pressure laterally through the bore 64 in the body section 30. This flow is eased by the somewhat smaller outside diameter of the body section 30. The discharged boring fluid thereby takes with it the bored out material. By the smaller diameter of the body sections 30 and 40 with respect to the head 32, the control capability of the ram boring apparatus is increased. The hammering mechanism 20 supports also the forward drive of the ram boring apparatus during straight runs and during curved runs in gravelly and stony earths in which purely static forward drive supported by flushing fluid is no longer sufficient.
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A ram boring apparatus has a generally cylindrical body with an attached head, the apparatus being connected to a drive rod which pushes the apparatus forwardly through the earth. The drive rod can also rotate the body and the attached head about the longitudinal axis of the apparatus, and operation of the apparatus can also be supported by the ejection of pressure fluid from one or more jets arranged on the head and by a hammering mechanism carried by a portion of the body. The hammering mechanism is activatable by pressure fluid from the same source as the pressure fluid supplied to the one or more jets. The pressure fluid is delivered through the hollow drive rod and a control valve in a fluid supply line in the body, in dependence on the pressure of the pressure fluid supplied to the apparatus, selectively directs the pressure fluid to the one or more jets in the head or simultaneously to both the one or more jets and to the hammering mechanism. A sender may be included in a portion of the body for the transmission of electromagnetic radiation by means of which the location and angular orientation of the apparatus can be determined from the surface of the earth or other remote location.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to reception of asynchronous tone signals as used in telecommunication systems and more particularly to a synchronizer circuit for use with tone reception equipment.
2. Description of the Prior Art
Most state of the art tone receivers employ as detectors peak detectors or rectifiers with filters, to drive two separate devices. Usually one of these devices is a parity checking circuit which in turn drives a parity timer, the second being an output circuit driven by both the detector outputs and the output of the parity timer. Such circuitry is taught in U.S. Pat. Nos. 2,719,959, 3,288,940 and U.S. Pat. No. 3,582,565.
In such tone receivers, the intended or usual operation requires that when a prescribed number of tone detectors (usually two) are activated, a parity checking circuit activates a parity timer. When the parity timer reaches its true or high state after a predetermined delay, the output circuitry is enabled so that it can latch up those output circuits being fed by detectors which have been turned on. The output circuits are then placed under the control of some other device such as a timer or handshake circuit, so that the output duration and/or identity is no longer controlled by the tone detectors.
The above-outlined arrangement creates problems in that the parity checking circuit and timer all have a finite out-of-time delay in their operation. As a result of this, a delay occurs in the activation of the output circuitry for some time after the parity timer should have enabled the outputs. If in the mean time an output has gone low or an extra one has gone high, the output circuits will latch into a state which represents a transient condition and not the condition which existed during the majority of the time that the parity timer was timing.
Because the parity timer is a long duration timer, its delay will be fairly large. In most applications, this has been on the order of several tens of microseconds for a timer with a timing period of around 25 milliseconds. In order to solve the resulting problem, one approach that has been attempted is to try to shorten the delay of the parity checking circuit and parity timer. This delay however can never be reduced to zero and will always leave some finite probability of the problem occurring. A more reasonable approach is to try to introduce a delay signal equal to the parity checking circuit delay plus the parity timer delay into the path between each detector and output circuit. The disadvantage of this approach is that delays could never be balanced exactly allowing a finite chance of error. Accordingly neither of these solutions is fully satisfactory and accordingly it is the object of the present invention to provide a new and improved approach to synchronization that overcomes such problems.
SUMMARY OF THE INVENTION
In the present invention the problem of time delay is overcome by synchronizing the output of the detectors with a clock signal, so that changes in the detector stage from "on" to "off" or "off" to "on" can only occur at the beginning of a clock cycle. If the chosen clock period is short compared to the fastest expected changes of the unsynchronized detector outputs, very little information is lost due to the quantization of timing. The synchronization of detector outputs is accomplished by a first or input latch stage consisting of ordinary master-slave "D" type flip-flops with the "D" input tied to the unsynchronized detector output and the clock input tied to a clock source. The "Q" or "true" output of the flip-flop then becomes the synchronized output.
In the arrangement of the present invention, the parity checking circuit is fed from the sychronized detector outputs and incorporates a short (compared to the clock period) delay at the output to make sure that the flip-flops and the checking circuitry have settled before an output occurs from the parity checker. Alternatively a "D" flip-flop running from the opposite half of the clock could be used. A second or intermediate latch stage of "D" flip-flops utilizes the delayed output of the parity checker as a clock to sample the synchronized detector outputs. Thus any valid combination of inputs is locked into the second stage when it first is recognized and is left there until there is an interval of no parity, followed by another interval of parity. The parity timer, times the delayed output of the parity checking circuit by charging a capacitor when parity exists and discharging it when parity is no longer present. When the capacitor is changed to a high enough voltage, an output occurs to the parity timer. Such an arrangement is well known and does not necessarily form a portion of the present invention. When an output does occur it passes through another "D" flip-flop which is triggered from the clock. This guarantees that the second stage of flip-flops has settled before the output of the flip-flop connected to the parity timer and gated from the clock source, triggers a third or output latch stage.
It should also be noted that while the present invention has been drawn primarily to a synchronizer circuit for use with a multi-channel tone receiver it would also be possible to employ similar technique for single channel tone detection wherein synchronization is also required. In such an arrangement the obvious change required would be, to eliminate the parity checking circuit since no parity checking would be performed. The remaining circuitry would be similar to that suggested.
BRIEF DESCRIPTION OF THE DRAWING
The attached single sheet of drawings is a functional and logic diagram of a tone synchronizer circuit in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawing of the present invention a tone synchronizer for use with a multi-channel tone receiver in accordance with the present invention is shown. The circuitry includes a plurality of "D" type flip-flop circuits, which function as latching circuits. Each flip-flop has two inputs (D and C) which is response to true signals on both, to cause a true output to appear on the flip-flop output (Q) and remain in that state until the next clock pulse or input signal on the C input, at which time the output will remain true if a signal is still present on the "D" input or alternately the output will become false if no signal is present on the "D" input. This type of flip-flops is well known in the electronics art and is available as integrated circuits from a number of commercial suppliers.
In the present circuit, the "D" inputs of flip-flops numbered 1 through 6 inclusive are connected to the outputs of the tone detectors, and their respective "C" inputs connected to a source of clock pulses. The outputs (Q) of flip-flops 1-6 provide the initial synchronized detector outputs. These outputs are connected to the "D" inputs of a second group of flip-flops (8 through 13 inclusive) and also to a parity checking circuit 7. The output of the parity checking circuit is connected to an R/C delay network consisting of resistor 22 and capacitor 23 and buffer gate 24. This circuit produces a fractional clock pulse delay of the rise or fall of the parity checking circuit output. The buffered output from the delay circuit connects to the "C" input of flip-flops 8 through 13 inclusive. The delay circuit consisting of resistor 22, capacitor 23 and buffer 24 could be replaced by another "D" type flip-flop with its "D" input connected to the output of the parity checking circuit 7 and its clock input connected to the compliment of the provided clock signal. The timer circuit 14 receives its input from the output of buffer 24 and feeds its output to the input of another "D" flip-flop 15.
The parity timer disclosed is a well known type of capacitor charge-discharge timer in which a capacitor is charged when the input of the timer is high and discharged when the input is low. In the arrangement there are two limit values V H and V L and the capacitor cannot charge above V H or below V L . When the capacitor charges to V H , the timer output will go high and remain high until the input of the timer goes low for a long enough period for the capacitor to discharge to V L , at which time the output will go low. The output of this timer will then stay low until the input has been high long enough to charge the capacitor again above V H , causing the output to go high. The described timer circuitry is well known in the art and commercially available. Flip-flop 15 allows the output stage consisting of flip-flops 16 through 21 inclusive, to be triggered by timer 14 only in synchronism with pulses from the clock source.
The tone synchronizer of the present invention as disclosed functions as follows: normally two of the connected detectors are turned on, and at the next occurring clock pulse two flip-flops (for example, flip-flops 1 and 2) in the first group (1-6) would go high at their output (Q). The parity checking circuit 7 would then function in any well known manner to detect parity and output a signal which after a fractional portion of a clock pulse, will emerge from buffer 24, triggering flip-flop 8 and 9 into their true state. In this manner the varified combination will be locked into the second stage (flip-flops 8 through 13 inclusive) turning on flip-flops 8 and 9. This signal provides an output from flip-flops 8 and 9 to the "D" inputs of flip-flops 16 and 17 included in the last or output state (flip-flop 16 through 21). After the delay additionally inserted by timer 14 which is applied to the "D" input of flip-flop 15 and on the occasion of the next clock pulse applied to the "C" input of flip-flop 15, flip-flop 16 and 17 will be gated "on" to produce at their output (Q) true or high signals properly synchronized and indicative of the originally detected signals.
It will be obvious from the above that for single channel operation the circuit arrangement would be similar with the exception of elimination of the parity checking circuit 7 in which case assuming that a single channel employed flip-flops 1, 8 and 16 the output from flip-flop 1 as well as being connected to the input (D) of flip-flop 8 will also be connected to resistor 22 of the delay network that also includes capacitor 23 and buffer 24. With the exception of the elimination of parity checking the operation would be exactly as outlined above for the multi-channel device.
While but selected embodiments of the present invention have been shown and/or described, it would be obvious to those skilled in the art that numerous modifications may be made without departing from the spirit of the present invention which shall be limited only by the scope of the claims appended hereto.
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A synchronizer circuit for use with tone receivers employed in the reception of asynchronous tones. A plurality of latch stages controlled by an external clock pulse source and internal timing circuitry provides synchronized outputs of a series of signals which represent the input tone on-off sequences.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a model of a living body, and more particularly to a model of a living body suitable for teaching medical students or interns.
2. Description of the Prior Art
Feature components (ear, tongue etc.) are made of hard resin in a conventional model of the human body which is used for teaching medical students or interns. Compared with the real human body, the conventional model does not give the user a feeling of reality at all.
In an actual medical examination of a patient, for example, the tongue is put out from the mouth in order to observe the inside of the throat, or the concha is so deformed by fingers as to be able to observe the middle ear or operate on the middle ear. However, since the feature components are made of hard resin in the conventional model, for example, the tongue cannot be so put out from the mouth as to observe the inside of the throat, or the concha cannot be so deformed by fingers as to be able to observe the middle ear or operate on the middle ear. Accordingly, for the teaching of the inside of the throat and the middle ear, text books exclusively had to be relied on.
SUMMARY OF THE INVENTION
Accordingly, it is an object of this invention to provide a model of a living body which overcomes the above described defects of the conventional model of the living body.
Another object of this invention is to provide a model of a living body which gives a user a feeling of reality.
A further object of this invention is to provide a model of a living body in which the insides of the organ or feature components can be easily observed.
In accordance with one aspect of this invention, a model of a living body includes a main body; and organ components made of yieldable material, arranged on said main body, wherein an external force is applied to one of the organ components from the external of the main body to deform the organ component, and thereby the inside of the organ component can be observed from the external of the main body.
Various other objects, advantages and features of the present invention will become readily apparent from the ensuing detailed description, and the novel features will be particularly pointed out in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a model of the head and neck of the human body according to one embodiment of this invention in which a nose portion and an ear portion are disassembled;
FIG. 2 is a perspective view of the model in which a front integument is removed from the model of FIG. 1;
FIG. 3 is a longtudinally sectional view of the model of FIG. 1 particularly for explaining a tongue portion;
FIG. 4 is a perspective view of the tongue portion of the model of FIG. 1;
FIG. 5 is an enlarged longitudinally sectional view of a part of the model of FIG. 1 particularly for explaining the ear portion;
FIG. 6 is an enlarged perspective view of the ear portion in which a holding member with an eardrum is disassembled; and
FIG. 7 is an enlarged longitudinally sectional view showing one modification of the ear portion similar to FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
One embodiment of this invention which will be applied to a model of the head and neck of the human body, will be described with reference to FIG. 1 to FIG. 7.
A model 1 of the head and neck of the human body includes mainly a cranium portion 2 as a main body (FIG. 2 and FIG. 3), a front integument portion 3a and a back integument portion 3b. The cranium portion 2 is made of polyester resin. The front and back integument portions 3a and 3b are made of silicone rubber. The cranium portion 2 is covered with the front and back integument portions 3a and 3b.
A front opening 9 is made in the main body 2. At the front opening 9, a nasal fossa portion 4, an upper jaw portion 5, a lower jaw portion 6 and a tongue portion 7 are combined with the main body 2. Side openings 10 are further made in the main body 2. At the side openings 10, ear portions 8 are combined with the main body 2. A pair of pins 23 are formed in the upper jaw portion 5 which may be made of polyester resin and covered with an integument of silicone rubber. The upper jaw portion 5 is fixed at the pins 23 to cut-out portions of the main body 2. A pair of studs 11 are formed on the lower jaw portion 6 which may be made of polyester resin and covered with an integument of silicone rubber. The lower jaw portion 6 is rotatably supported at the studs 11 on cut-out portions of the main body 2. The upper jaw portion 5 and the lower jaw portion 6 cannot be demounted from the main body 2 after combined with the main body 2.
The nasal fossa portion 4, the upper jaw portion 5 and the tongue portion 7, as clearly shown in FIG. 1, are exposed at an opening 12 made in the front integument portion 3a. A nose integument 3c having a nose portion 13, which may be made of silicone rubber, is fitted to the opening 12 of the front integument 3a to cover the nasal fossa portion 4 and the upper jaw portion 5. Thus, a mouth portion 14 is formed in the model 1. The tongue portion 7 is viewed through the mouth portion 14 from the external.
Openings 15 to be aligned with the side openings 10 of the main body 2 are made in the combined front and back integument portions 3a and 3b. The ear portions 8 are inserted through the aligned openings 10 and 15 to be combined with the main body 2. A pipe 26 is embedded in the lower end of the main body 2. A support rod of a stand (not shown) is tightly inserted into the pipe 26 to support the model 1. Characteristic portions of the model 1 according to this embodiment are particularly the tongue portion 7 and the ear portion 8.
First, there will be described the tongue portion 7. As shown in FIG. 3, the tongue portion 7 consists of a yieldable outer layer 17 of silicone rubber and a yieldable inner layer 16 of silicone gel, covered with the outer layer 17. As shown in FIG. 2, a guide rod 18, for example, made of metal, is fixed to the opposite sides of the lower jaw portion 6. The tongue portion 7 is directed toward the mouth portion 14 in contact with the guide rod 18. The rear part of the tongue portion 7 is directed downwardly in a hole 19 made in the main body 2. A trachea portion 21 provided with a thyroid gland portion 20 is disposed adjacent to the rear part of the tongue portion 7. And a throat rear wall portion 22 is so arranged as to surround the trachea portion 21. The tongue portion 7, the trachea portion 21 and the throat rear wall portion 22 may be fixed in the model 1, in different manners. For example, the tongue portion 7 is fixed at one end of the outer layer 17 to the lower jaw portion 6. The trachea portion 21 is fixed to the other end of the outer layer 17 of the tongue portion 7. The throat rear wall portion 22 is integrally formed with the nasal fossa portion 4 which is fixed to the main body 2.
For example, in operation, the top end of the tongue portion 7 is seized by a suitable device, and drawn forward from the mouth 14. As shown by the dot-dash line in FIG. 3, the tongue portion 7 is yieldably deformed to reduce its cross section. As the result, a uvula portion 25 and the neighborhood of the uvula portion 25 in the inside of the mouth 14 can be clearly observed from the external.
When the tongue portion 7 is drawn forward from the mouth portion 14 in the above described manner, the tongue portion 7 is smoothly guided by the guide rod 18. Accordingly, the tongue portion 7 can be easily deformed as shown by the dot-dash line in FIG. 3, merely by pulling the top end of the tongue portion 7. The operation is simple. The drawn tongue portion 7 can be stably held on the guide rod 18. When the tongue portion 7 is released from the device, the tongue portion 7 is restored to its original shape as shown by the solid line in FIG. 3.
The above-described elastic deformation and restoration of the tongue portion 7 gives the user a feeling of reality, and allows the user to clearly observe the interior of the throat portion from the exterior. A conventional model of the head and neck of the human body did not allow a user to observe the interior of the throat portion from the exterior. Accordingly, the model according to this embodiment is superior as a teaching material.
The tongue portion 7 and the trachea portion 21 may be so designed as to be demountable from the main body 2. In such a case, the interior of the throat portion or neck portion can be more widely observed from the exterior by demounting the tongue portion 7 and trachea portion 21.
Next, there will be described the ear portion 8.
As shown in FIG. 5 and FIG. 6, the ear portion 8 includes mainly a concha portion 8a made of soft silicone rubber and an ear holding portion 8b made of hard silicone rubber. The concha portion 8a and the ear holding portion 8b are so covered with an integument 27 of soft silicone rubber as to be combined with each other and to leave a slight space 28 between them. A piercing hole is made as an external auditory miatus or middle ear portion 29 in the center of the ear holding portion 8b. A tubular portion 8c extending from the center of the concha portion 8a is fixed to the piercing hole of the ear holding portion 8b to form the middle ear portion 29. A holding member 31 provided with an eardrum 30 is inserted into the middle ear portion 29 of the ear holding portion 8b from the inside of the main body 2. In the assembling step of the model 1, the ear holding portion 8b of the ear portion 8, to which the holding member 31 with the eardrum 30 is fitted, is inserted into the opening 15 of the combined front and back integuments 3a and 3b and the side opening 10 of the main body 2 aligned with each other, as shown in FIG. 1 and FIG. 5. The diameter of the ear holding portion 8b is nearly equal to the diameter of the side opening 10 of the main body 2. Accordingly, the ear holding portion 8b is tightly fitted to the side opening 10 of the main body 2. Since a flange 32 of the concha portion 8a contacts with the integuments 3a and 3b, the ear holding portion 8b is restrained from being further inserted.
In operation, for example, the yieldable concha portion 8a is pulled backward by fingers substantially in the direction normal to the plane of the drawing. Accordingly, the concha portion 8a is so deformed as shown by the dot-dash line in FIG. 5. In such a condition, an applicator can be easily inserted into the middle ear portion 29 without hindrance of the concha portion 8a. Further, the inside of the middle ear portion 29 can be easily observed from the exterior. When the concha portion 8a is released from the fingers of the user, it is restored to its original shape as shown by the solid line in FIG. 5.
The above-described elastic deformation and restoration of the concha portion 8a of the ear portion 8 gives the user a feeling of reality. Further, the holding member 31 with the eardrum 30 can be demounted from the ear holding portion 8b of the ear portion 8. Accordingly, in the lesson of the surgical operation of the eardrum, the incised eardrum 30 of the holding member 31 is demounted from the ear holding portion 8b, after the surgical operation, and the incised condition of the eardrum 30 can be observed in detail outside of the model 1. That is very convenient.
FIG. 7 shows one modification of the ear portion 8 of the above-described embodiment. Parts in this modification which correspond to the parts in FIG. 1 to FIG. 6, are denoted by the same reference numerals. In this modification, the ear holding portion 8b and the holding member 31 are omitted. The tubular portion 8c of the ear portion 8 is attached directly to the main body 2. The flange 32 of the concha portion 8a is fixed to the integuments 3a and 3b, for example, with adhesive. The eardrum 30 is fitted to the top end of the tubular portion 8c. It may be fixed to the top end of the tubular portion 8c. A small space is formed at the opening 15 between the tubular portion 8c and the integuments 3a and 3b. In operation, the concha portion 8a is deformed in the manner shown in FIG. 5. Further, the tubular portion 8c can be spread at the opening 15 by the inserted applicator, since the small space is formed at the opening 15.
While there has been described a preferred embodiment of this invention, obviously further modifications and variations 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 practised otherwise than as specifically described.
For example, although the nose portion 13 is fitted to the opening 12 of the front integument portion 3a in the above embodiment, it may be formed integrally with the front integument 3a or the main body 2. The front and back integuments 3a and 3b may be fixed to the main body 2 with adhesive, and further may be formed integrally with each other. In any case, the nose portion can be deformed in the similar manner to the tongue portion and ear portion.
In the above embodiment, the top end of the tongue portion 7 is pulled out from the mouth 14 by the suitable device in order to observe the inside of the throat. However, the tongue portion 7 may be pushed downward at the upper surface by a suitable device in order to observe the inside of the throat, in the same manner as in the actual examination of a patient.
Further, although the above embodiment is applied to the model of the head and neck of the human body, this invention may be applied to a model of any other organs of the human body, or to a model of any other living body than the human body.
Further, although the organ components such as the tongue portion and the ear portion are individually manufactured in the above embodiment, they may be formed integrally with the main body. In such a case, they may be thinner formed than the main body.
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A model of a living body includes a cranium as a main body; and organ components (tongue portion and ear portion) made of yieldable material, arranged on the main body, wherein an external force is applied to one of the organ components from the external of the main body to deform the organ component, and thereby the inside of the organ component can be observed from the external of the main body.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a fuel pump adapted to suck in and pressurize a fuel such as gasoline and discharge the pressurized fuel.
2. Discussion of Related Art
A fuel pump has an impeller and a pump casing, as disclosed in Japanese Patent Application Unexamined Publication (KOKAI) No. Hei 7-279881. The impeller has an approximately disk-shaped configuration with a plurality of blade grooves formed serially in a region extending along the outer peripheries of the obverse and reverse sides of the disk-shaped impeller. The impeller is rotated by a driving device such as a motor. The pump casing surrounds the impeller and has a circumferentially extending recess for forming a circumferentially extending flow passage groove between the same and the blade grooves of the impeller. The pump casing further has a suction opening communicating with the upstream end of the recess and a discharge opening communicating with the downstream end of the recess. Further, the pump casing has a circumferential wall forming an inner peripheral surface extending along the outer peripheral surface of the impeller. When the impeller rotates, fuel is sucked into the flow passage groove from the suction opening and pressurized while flowing circumferentially in the flow passage groove. The pressurized fuel is discharged from the discharge opening.
In this case, the size of the clearance between the impeller outer peripheral surface and the pump casing inner peripheral surface has a significant effect on the pump efficiency. The smaller the clearance, the smaller the amount of fuel leakage, and the higher the pump efficiency.
However, the fuel pump is usually used for a long period of time. During use, the bearings supporting the shaft for rotating the impeller unavoidably wear out, causing the center of rotation of the impeller to be displaced gradually by small amounts. For this reason, if the above-described clearance is set excessively small, the impeller outer peripheral surface and the pump casing inner peripheral surface may contact each other when the rotation center of the impeller is displaced, resulting in a failure of the pump operation.
Therefore, the conventional practice is to allow some margin for the clearance between the impeller outer peripheral surface and the pump casing inner peripheral surface so that these peripheral surfaces will not contact each other even if the rotation center of the impeller is displaced as a result of wear of the bearings.
SUMMARY OF THE INVENTION
Consequently, the conventional fuel pump has a pump efficiency lower than that exhibited when the fuel pump is designed without considering the wear of the bearings. The reason for this is as follows. If the wear is taken into consideration, it becomes necessary to allow some margin for the clearance between the impeller outer peripheral surface and the pump casing inner peripheral surface, and if a margin is allowed for the clearance, the pump efficiency reduces unfavorably.
Under these circumstances, it has been demanded to improve the pump efficiency while ensuring a clearance sufficient to prevent the impeller outer peripheral surface and the pump casing inner peripheral surface from contacting each other even if the rotation center of the impeller is displaced as a result of wear of the bearings.
The present inventors examined in detail the phenomenon that the rotation center of the impeller is displaced as a result of wear of the bearings, and as a result, found that the wear progresses intensively in a specific direction. The reason for this may be understood as follows. The fuel is pressurized while flowing circumferentially along the flow passage groove, as stated above. The pressure in the circumferentially extending flow passage groove is not uniform. The pressure is low in a portion adjacent to the suction opening and high in a portion adjacent to the discharge opening. Accordingly, the impeller outer peripheral surface is subjected to a non-uniform pressure. That is, a relatively low pressure acts on the impeller outer peripheral surface at the portion adjacent to the suction opening, and a relatively high pressure acts on the impeller outer peripheral surface at the portion adjacent to the discharge opening. The non-uniform pressure distribution causes a force to act on the impeller in the direction from a region where the flow passage groove pressure is high toward a region where the flow passage groove pressure is low. The bearings keep the rotation center of the impeller against the force acting on the impeller as stated above. If the fuel pump continues to be used under the above-described conditions, the bearings supporting the rotating shaft of the impeller wear out intensively in the region where the flow passage groove pressure is low.
The conventional fuel pump does not make use of the knowledge that the wear progresses intensively in a specific direction. Even if the rotation center of the impeller has been displaced as a result of wear of the bearings, the clearance sufficient to avoid contact between the impeller outer peripheral surface and the pump casing inner peripheral surface is ensured in all directions.
The studies conducted by the present inventors have revealed that the wear progresses intensively in a specific direction, and hence proved that it is necessary to allow for the expected amount of wear only in the direction of progress of wear to ensure the required clearance, and it is unnecessary to allow for the wear in a direction in which wear will not progress. It has been found that the clearance can be reduced in the direction in which no wear will progress, and a reduction in the clearance causes an improvement in the pump efficiency.
A first structure of the fuel pump created by the present invention has an impeller and a pump casing. The impeller has an approximately disk-shaped configuration with a plurality of blade grooves formed serially in a region extending along the outer peripheries of the obverse and reverse sides of the disk-shaped impeller. The outer peripheral surface of the impeller is a circumferential surface. The impeller is rotated by a driving device. The pump casing has a circumferentially extending recess for forming a circumferentially extending flow passage groove between the same and the blade grooves of the impeller. The pump casing further has a suction opening communicating with the upstream end of the recess and a discharge opening communicating with the downstream end of the recess. Further, the pump casing has a circumferential wall forming an inner peripheral surface facing the outer peripheral surface of the impeller. The clearance between the inner surface of the circumferential wall, i.e. the pump casing inner peripheral surface, and the impeller outer peripheral surface is relatively small in a region where the flow passage groove pressure is high, and the clearance is relatively large in a region where the flow passage groove pressure is low.
The impeller accommodated in the pump casing is subjected to a force derived from the flow passage groove pressure varying in the circumferential direction. An example of the force acting on the impeller will be described below with reference to FIG. 8 . The impeller 90 has an approximately disk-shaped configuration with a plurality of blade grooves 91 formed serially in a region extending along the outer peripheries of the obverse and reverse sides of the disk-shaped impeller 90 . The outer peripheral surface 90 a of the impeller 90 is a circumferential surface. The impeller 90 is rotated by a driving device (not shown). The pump casing has a circumferentially extending recess 94 for forming a circumferentially extending flow passage groove between the same and the blade grooves 91 of the impeller 90 . The pump casing further has a suction opening communicating with the upstream end 92 of the recess 94 (the impeller 90 rotates in the direction of the arrow R) and a discharge opening 98 communicating with the downstream end of the recess 94 . Further, the pump casing has a circumferential wall 99 forming an inner peripheral surface 99 a extending opposite the outer peripheral surface 90 a of the impeller 90 .
The pressure in the flow passage groove 94 varies as shown schematically by the arrows 96 - 1 to 96 - 10 . The pressure is low in a portion adjacent to the suction opening and high in a portion adjacent to the discharge opening 98 . As a result, the impeller 90 is subjected to a force, indicated by F in the figure, by the fuel pressure. Because the force F acts on the bearings supporting the impeller rotating shaft, the bearings wear out intensively in the direction of the arrow F. Consequently, the impeller 90 also shifts in the arrow F direction as the bearings wear out.
In the present invention, a relatively large clearance allowing for the expected amount of wear is ensured in a region where the flow passage groove pressure is low (i.e. a region on the side indicated by the arrow F). Therefore, even if the center of rotation of the impeller is displaced as a result of wear of the bearings, the impeller outer peripheral surface and the pump casing inner peripheral surface will not contact each other. The useful service life of the fuel pump is long as in the case of the conventional fuel pump. It should be noted that the term “relatively large clearance” as used herein means a clearance substantially equal to that in the conventional fuel pump but does not mean a clearance larger than the conventional one. In a region where the flow passage groove pressure is high (i.e. a region remote from the side indicated by the arrow F), it is unnecessary to allow for the wear. Therefore, the clearance is set smaller than the conventional clearance. Consequently, it is possible to minimize the amount of fuel leaking from the flow passage groove 94 in the region where the pressure is high, and hence possible to increase the pump efficiency.
The fuel pump according to the present invention enables the pump efficiency to be improved without reducing the useful service life of the fuel pump.
In the region where the flow passage groove pressure is high (i.e. the region remote from the side indicated by the arrow F), the clearance can be minimized without reducing the useful service life of the fuel pump. In this case, it is not always necessary to reduce the clearance in the whole region where the clearance can be reduced. The present invention may be applied intensively only to a portion where the advantages of the present invention can be offered particularly effectively.
A second structure of the fuel pump realized as stated above is as follows. A portion of the pump casing inner peripheral surface that extends from the discharge opening to the suction opening along the rotation direction of the impeller projects toward the impeller more than a portion of the pump casing inner peripheral surface that extends from the suction opening to the discharge opening along the impeller rotation direction. Consequently, the clearance between the pump casing inner peripheral surface and the impeller outer peripheral surface is relatively small in a region extending from the discharge opening to the suction opening along the rotation direction of the impeller. The clearance is relatively large in a region extending from the suction opening to the discharge opening in the impeller rotation direction.
The region extending from the discharge opening to the suction opening along the impeller rotation direction is basically where the flow passage groove pressure is high. Accordingly, even if the clearance in this region is reduced, the pump lifetime will not decrease. The region extending from the discharge opening to the suction opening along the impeller rotation direction includes a portion belonging to the region where the flow passage groove pressure is low. However, the direction of shift of the impeller position caused by the wear in this portion of the region is substantially parallel to the pump casing inner peripheral surface. Therefore, the clearance can be reduced uniformly in the region extending from the discharge opening to the suction opening along the impeller rotation direction. It is a matter of course that the clearance can be reduced only in a region extending from the discharge opening to the suction opening along the impeller rotation direction and belonging to the region where the flow passage groove pressure is high.
During use of the impeller for a long period of time, the center of rotation thereof shifts, as shown in FIGS. 9A to 9 D, owing to the fact that the above-described resultant force F acts on the impeller. As shown in FIG. 9A , in a case where the center of the rotating impeller shifts from X to Y, it is preferable that the pump casing inner peripheral surface should project to extend along a line segment connecting A and B. The clearance at the projecting inner surface AB can be reduced to a minimum distance at which the impeller will not lock. The wear of the bearings need not be taken into consideration in this region.
A third structure of the fuel pump according to the present invention is as follows. Of the inner peripheral surface of the pump casing, a discharge opening-side half-circumferential surface portion (i.e. a discharge opening-side approximately half-circumferential surface portion) including the discharge opening but excluding the suction opening projects toward the impeller more than a suction opening-side half-circumferential surface portion (i.e. a suction opening-side approximately half-circumferential surface portion excluding the discharge opening) opposite the discharge opening-side half-circumferential surface portion with respect to the center line of the pump casing. The clearance is small at the discharge opening-side half-circumferential surface portion. The clearance is large at the suction opening-side half-circumferential surface portion.
As shown in FIG. 9B , in a case where the center of the impeller shifts from X to Y during use for a long period of time, the clearance can be reduced to a minimum distance at which the impeller will not lock at the discharge opening-side half-circumferential surface portion (i.e. an approximately half-circumferential surface portion indicated by hatching from C to D). The pump lifetime will not be reduced if the clearance is minimized to such an extent. Accordingly, it is possible to increase the pump efficiency while preventing the pump lifetime from being reduced.
FIG. 9C shows a maximum range within which the clearance can be reduced without the pump casing inner peripheral surface contacting the impeller while the center of the impeller is being displaced from X to Y during use for a long period of time. It will be understood from the figure that the clearance can be reduced not only at a half-circumferential region C 1 where the flow passage groove pressure is high, but also at regions C 2 and C 3 where the impeller displacement direction is approximately parallel to the pump casing inner peripheral surface. The non-hatched region of the pump casing inner peripheral surface will hereinafter be referred to as “the expected surface portion of contact” that is expected to be contacted by the impeller outer peripheral surface when the impeller rotating shaft shifts in a predetermined direction as a result of wear of the bearings supporting the impeller rotating shaft. The pump efficiency can be further increased in a fuel pump in which a portion of the pump casing inner peripheral surface other than the expected surface portion of contact projects toward the impeller more than the expected surface portion of contact.
It is possible to set the clearance relatively small in a region where the flow passage groove pressure is high and relatively large in a region where the flow passage groove pressure is low, while maintaining basically the pump casing inner peripheral surface in the form of a circumferential surface.
In this case, the center of rotation of the impeller is offset from the center of the circumference of the pump casing inner peripheral surface.
Let us assume, as shown in FIG. 9D , that the impeller center is displaced from X to Y (distance therebetween is denoted by L) during the useful service life of the fuel pump because of the force acting on the impeller in the direction F. In this case, if the pump casing inner peripheral surface is a circumferential surface 100 centered at a position offset from X in the direction of Y by a distance L/2 (i.e. the middle point between X and Y) and having a radius equal to the sum of the impeller's radius r and L/2, there will be no interference between the impeller outer peripheral surface and the pump casing inner peripheral surface during the useful service line of the fuel pump. Reference numeral 101 denotes a circumferential surface (i.e. a circle centered at X and having a radius r+L) required in the conventional pump. Thus, the radius of the pump casing inner peripheral surface can be reduced by offsetting the center of rotation of the impeller.
In this case, the impeller rotation center may be offset with respect to the pump casing inner peripheral surface that has been finished to a circumferential surface. Alternatively, the pump casing inner peripheral surface may be finished to a circumferential surface centered at a point offset from the impeller rotation center.
The pump casing is preferably formed by combining together a pump body and a pump cover. In this case, a circumferential wall forming the pump casing inner peripheral surface may be formed on the pump body having a suction opening. Alternatively, the circumferential wall may be formed on the pump cover having a discharge opening.
In the fuel pump according to the present invention, a relatively large clearance allowing for the expected amount of wear is ensured in a region where the flow passage groove pressure is low. Therefore, even if the center of rotation of the impeller is displaced as a result of wear of the bearings, the impeller outer peripheral surface and the pump casing inner peripheral surface will not contact each other. The useful service life of the fuel pump is long as in the case of the conventional fuel pump. In a region where the flow passage groove pressure is high, it is unnecessary to allow for the wear. Therefore, the clearance is set smaller than the conventional clearance. Consequently, it is possible to minimize the amount of fuel leaking from the flow passage groove in the region where the pressure is high, and hence possible to increase the pump efficiency.
The fuel pump according to the present invention enables the pump efficiency to be improved without reducing the useful service life of the fuel pump.
Still other objects and advantages of the invention will in part be obvious and will in part be apparent from the specification.
The invention accordingly comprises the features of construction, combinations of elements, and arrangement of parts which will be exemplified in the construction hereinafter set forth, and the scope of the invention will be indicated in the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a fuel pump according to a first embodiment of the present invention.
FIG. 2 is an end view of a pump cover in the first embodiment.
FIG. 3 is a sectional view of the pump cover.
FIG. 4 is an end view of an impeller of the fuel pump according to the present invention.
FIG. 5 is an end view showing the impeller accommodated in the pump cover according to the first embodiment.
FIG. 6 is an end view of a pump cover according to a second embodiment of the present invention.
FIG. 7 is an end view of a pump cover according to a third embodiment of the present invention.
FIG. 8 is a schematic view showing the distribution of fluid pressure applied between the impeller and the peripheral inner wall of a recess in the pump cover.
FIGS. 9A to 9 D are schematic views showing the relationship between the shift of the impeller during operation and the configuration of the peripheral inner wall of the recess in the pump cover according to each embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A first embodiment of the present invention will be described below with reference to the accompanying drawings. The first embodiment shows a fuel pump for use in an automobile, which is used to supply fuel to the engine of the automobile.
FIG. 1 is a sectional view of the fuel pump. In the figure, the fuel pump has a pump part 1 and a motor part 2 for driving the pump part 1 . The motor part 2 comprises a brush DC motor. The motor part 2 has an approximately circular cylinder-shaped pump housing 4 . A magnet 5 is disposed in the pump housing 4 . A rotor 6 is disposed in the pump housing 4 in concentric relation to the magnet 5 .
The rotor 6 has a shaft 7 . The lower end portion of the shaft 7 is rotatably supported through a bearing 10 by a pump cover 9 secured to the lower end portion of the pump housing 4 . The upper end portion of the shaft 7 is rotatably supported through a bearing 13 by a motor cover 12 secured to the upper end portion of the pump housing 4 .
In the motor part 2 , the rotor 6 is rotated by supplying electric power to the coil (not shown) of the rotor 6 through a terminal (not shown) provided on the motor cover 12 . It should be noted that the arrangement of the motor part 2 is well known. Therefore, a detailed description thereof is omitted. It should also be noted that the motor part 2 can use a motor structure other than the illustrated one.
The arrangement of the pump part 1 driven by the motor part 2 will be described below. The pump part 1 comprises a pump cover 9 , a pump body 15 , and an impeller 16 . The pump cover 9 and the pump body 15 are formed by die casting of aluminum, for example. When combined together, the pump cover 9 and the pump body 15 constitute a pump casing 17 for accommodating the impeller 16 .
The impeller 16 is formed by molding of a resin material. As shown in FIG. 4 , the impeller 16 has an approximately disk-shaped configuration. A plurality of blade grooves 16 a are formed serially in a region extending along the outer peripheries of the obverse and reverse sides of the disk-shaped impeller 16 . The center of the impeller 16 is formed with an approximately D-shaped engagement hole 16 b . The engagement hole 16 b is engaged with an engagement shaft portion 7 a with a D-shaped sectional configuration at the lower end of the shaft 7 . Thus, the impeller 16 is connected to the shaft 7 so as to be rotatable simultaneously with the shaft 7 and slightly movable in the axial direction. The outer peripheral surface 16 c of the impeller 16 is a circumferential surface.
FIG. 2 is an end view of the pump cover 9 as seen from the direction of the line II—II in FIG. 1 . That is, FIG. 2 shows an end of the pump cover 9 closer to the impeller 16 . FIG. 3 is a sectional view of the pump cover 9 . The pump cover 9 has a circumferentially extending recess 21 for forming a circumferentially extending flow passage groove between the same and the blade grooves 16 a of the impeller 16 . The pump cover 9 further has a discharge opening 24 communicating with the downstream end of the recess 21 (the impeller 16 rotates in the direction of the arrow R). Further, the pump cover 9 has a circumferential wall 9 b . As shown in FIG. 1 , the discharge opening 24 extends through the pump cover 9 to communicate with a space 2 a inside the motor part 2 . The inner peripheral surface 9 c of the circumferential wall 9 b faces the outer peripheral surface 16 c of the impeller 16 across a clearance. The inner peripheral surface 9 c comprises a first circumferential surface portion 9 c 1 and a second circumferential surface portion 9 c 2 . The first circumferential surface portion 9 c 1 extends over from the upstream end 22 of the recess 21 to the discharge opening 24 at the downstream end of the recess 21 along the rotation direction R of the impeller 16 . The second circumferential surface portion 9 c 2 extends over from the discharge opening 24 to the upstream end 22 of the recess 21 along the rotation direction R of the impeller 16 . The radius of the first circumferential surface portion 9 c 1 is larger than the radius of the second circumferential surface portion 9 c 2 . The second circumferential surface portion 9 c 2 projects toward the impeller 16 more than the first circumferential surface portion 9 c 1 .
As shown in FIG. 1 , the pump body 15 is laid on the pump cover 9 . In this state, the pump body 15 is secured to the lower end portion of the pump housing 4 by caulking or the like. A thrust bearing 18 is secured to the impeller-side surface of a central portion of the pump body 15 . The thrust bearing 18 bears the thrust load of the shaft 7 . The pump cover 9 and the pump body 15 constitute a pump casing 17 . The impeller 16 is accommodated in the pump casing 17 so as to be rotatable and slightly movable in the axial direction. The inner surface of the pump body 15 is formed with a circumferentially extending recess 20 for forming a circumferentially extending flow passage groove between the same and the blade grooves 16 a of the impeller 16 . The pump body 15 further has a suction opening 22 a communicating with the upstream end of the recess 20 .
The circumferentially extending recess 21 of the pump cover 9 and the circumferentially extending recess 20 of the pump body 15 extend along the rotation direction R of the impeller 16 from a position corresponding to the suction opening 22 a on the pump body 15 to a position corresponding to the discharge opening 24 on the pump cover 9 to form a flow passage groove extending circumferentially from the suction opening 22 a to the discharge opening 24 . When the impeller 16 rotates in the direction R, fuel is sucked into the flow passage groove from the suction opening 22 a . While flowing through the flow passage groove from the suction opening 22 a to the discharge opening 24 , the fuel is pressurized, and the pressurized fuel is delivered to the motor part 2 from the discharge opening 24 . Neither of the recesses 21 and 20 are formed in an area extending in the rotation direction R of the impeller 16 from a position corresponding to the discharge opening 24 on the pump cover 9 to a position corresponding to the suction opening 22 a on the pump body 15 , thereby preventing the pressurized fuel from returning to the suction opening 22 a side as much as possible. It should be noted that the high-pressure fuel delivered to the motor part 2 is delivered to the outside of the pump from a delivery opening 28 .
FIG. 5 is an end view of the impeller 16 accommodated in the pump cover 9 . As has been stated above, the second circumferential surface portion 9 c 2 , which extends over from the discharge opening 24 to the suction opening 22 a along the rotation direction R of the impeller 16 , projects toward the impeller 16 more than the first circumferential surface portion 9 c 1 , which extends over from the suction opening 22 a to the discharge opening 24 along the rotation direction R of the impeller 16 . Therefore, the clearance between the impeller outer peripheral surface 16 c and the pump casing inner peripheral surface 9 c is relatively large in a region extending from the suction opening 22 a to the discharge opening 24 along the rotation direction R of the impeller 16 and relatively small in a region extending from the discharge opening 24 to the suction opening 22 a along the rotation direction R of the impeller 16 . The latter clearance is set to a minimum distance at which the impeller 16 will not lock. When the fuel pump is used for a long period of time, the center of the impeller 16 may be displaced owing to the wear of the bearings, as has been stated above. However, it has been confirmed by the studies conducted by the present inventors that the direction in which the wear of the bearings progresses is limited, and the wear of the bearings will not progress toward the circumferential wall in a region extending from the discharge opening 24 to the suction opening 22 a along the rotation direction R of the impeller 16 . Even if the clearance in this region is set at such a small distance that the impeller 16 would lock if the impeller center is displaced toward the circumferential wall in this region, there is no possibility that the outer peripheral surface 16 c of the impeller 16 will contact the inner peripheral surface portion 9 c 2 projecting toward the impeller 16 .
In this case, the clearance between the outer peripheral surface 16 c of the impeller 16 and the inner peripheral surface 9 c of the pump casing is reduced in the region extending from the discharge opening 24 to the suction opening 22 a along the rotation direction R of the impeller 16 . Consequently, the amount of pressurized fuel leaking out toward the suction opening 22 a is minimized. Thus, the pump efficiency is improved.
A second embodiment of the present invention will be described below with reference to FIG. 6 . The second embodiment is a modification of the first embodiment. Therefore, only the modified part of the fuel pump will be described below in detail. The other features of the second embodiment are the same as those of the first embodiment.
FIG. 6 is an end view showing the inner peripheral surface configuration of the pump cover 9 according to this embodiment. In the second embodiment, as shown in FIG. 6 , a discharge opening-side approximately half-circumferential surface portion (indicated by the arrow 61 , by way of example) of the pump casing inner peripheral surface that includes the discharge opening but excludes the suction opening projects toward the impeller 16 more than a suction opening-side approximately half-circumferential surface portion of the pump casing inner peripheral surface, which is opposite the discharge opening-side approximately half-circumferential surface portion with respect to the center line of the pump casing. In the discharge opening-side approximately half-circumferential region, the fuel pressure acting on the impeller 16 is high. Accordingly, there is no possibility of the impeller 16 being displaced toward the discharge opening-side approximately half-circumferential region. Therefore, the clearance is reduced in this region to a minimum distance at which the impeller 16 will not lock. In the approximately half-circumferential region on the opposite side, a margin is allowed for the clearance in anticipation of the possibility that the impeller 16 may be displaced toward the inner peripheral surface of the pump cover 9 , thereby preventing the impeller 16 from contacting the inner peripheral surface of the pump cover 9 even if the impeller 16 is displaced during long-term use of the fuel pump.
A third embodiment of the present invention will be described below with reference to FIG. 7 . The third embodiment is also a modification of the first embodiment. Therefore, only the modified part of the fuel pump will be described below in detail. The other features of the third embodiment are the same as those of the first embodiment.
FIG. 7 is an end view showing the inner peripheral surface configuration of the pump cover 9 according to the third embodiment. In this embodiment, the inner peripheral surface 9 f of the pump cover 9 is a circumferential surface centered at point 9 g.
Reference symbol F in the figure denotes the direction of force acting on the impeller 16 owing to the imbalance of pressure. Reference symbol L in the figure denotes the distance through which the rotation center of the impeller 16 may be displaced as a result of wear of the bearings during the lifetime of the fuel pump guaranteed by the manufacturer.
In this case, the bearing center is provided at a position 16 h offset in the opposite direction from the center 9 g of the inner peripheral surface 9 f of the pump cover 9 by L/2 at the time of manufacture.
During use for a long period of time, the bearings wear out. Consequently, the rotation center of the impeller 16 shifts from 16 h through 9 g to 16 k . During this period of time, there is no possibility of the impeller outer peripheral surface contacting the inner peripheral surface 9 f of the pump cover 9 .
In this embodiment, a hole for setting bearings is formed by die casting at a position offset from the center 9 g of the inner peripheral surface 9 f of the pump cover 9 by L/2 in a direction opposite to the direction in which the impeller 16 may shift, i.e. toward the discharge opening 24 . However, the present invention is not necessarily limited to this arrangement. Conversely, the inner peripheral surface 9 f of the pump cover 9 may be formed by die casting so as to coincide with a circumferential surface centered at a point offset from the bearing center of the impeller 16 by L/2 in the direction in which the impeller 16 may shift. These two arrangements are equivalent to each other.
With the conventional technique, the radius of the inner peripheral surface 9 f of the pump cover 9 needs to be set equal to the sum of the impeller radius and the distance L. The third embodiment allows the radius of the inner peripheral surface 9 f of the pump cover 9 to be reduced by L/2 in comparison to the prior art. Accordingly, the clearance between the impeller outer peripheral surface and the pump casing inner peripheral surface can be reduced correspondingly, and the pump efficiency improves favorably.
It should be noted that advantageous effects similar to those described above can be obtained by an arrangement other than those of the embodiments exemplarily shown above. That is, the arrangement may be such that the peripheral inner wall of the recess in the pump cover 9 projects at a portion between the suction opening 22 a communicated with the flow passage groove 21 and the discharge opening 24 where no flow passage groove is provided, and also projects at an approximately half-circumferential portion on a side of the pump cover 9 closer to the discharge opening 24 communicated with the flow passage groove 21 . In other words, the inner peripheral surface of the pump cover 9 may be shaped so as to have the features of both the first and second embodiments.
It should be noted that the present invention is not necessarily limited to the above-described embodiments, and that various changes and modifications may be imparted thereto without departing from the gist of the present invention. For example, the present invention is not necessarily limited to automotive fuel pumps but may be widely used as pumps for delivering various fluids such as water under pressure. Further, the technical elements described in this specification or in the drawings exhibit technical utility singly or in various combinations and are not limited to the combinations recited in the claims as filed. The techniques illustrated in this specification or in the drawings attain a plurality of purposes simultaneously, and attaining one of the purposes per se offers technical utility.
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A fuel pump capable of using the pump efficiency most efficiently without reducing the useful service life is provided. A relatively large clearance allowing for the expected amount of wear is ensured in a region where the flow passage groove pressure is low. In a region where the flow passage groove pressure is high, it is unnecessary to allow for the wear. Therefore, the clearance is set relatively small.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national stage application, according to Chapter II of the Patent Cooperation Treaty.
This is a filing of a national phase PCT application in the United States originating from PCT Application No. PCT/GB99/03977 filed Nov. 30, 1999 which claimed priority from United Kingdom Patent Application No. 9828291.6 filed Dec. 23, 1998.
BACKGROUND OF THE INVENTION
The present invention concerns improvements in or relating to apparatus and methods for winding a cover yarn or yams around a core yarn. The method and apparatus especially, but not exclusively, is concerned with yarns ultimately to be knitted into hosiery, for example ladies stockings and tights.
U.S. Pat. No. 3,834,143 discloses a method and apparatus for covering a core yarn, in which a cover yarn is wound around the core yarn.
The relatively small diameter of the core and covering yarns and the relative fragility of the yams gives rise to certain difficulties. Prior apparatus and methods have overcome some of these difficulties but certain disadvantages remain.
In one presently accepted apparatus, cover yarn is pre-wound on to a specially shaped, doubled flanged bobbin which is mounted on a hollow spindle positioned between a core yarn supply and a core yarn take-up with the core yarn passing through the hollow spindle. Cover yarn is wound around the core yarn after it has passed through the hollow spindle by rotating the flanged bobbin. The maximum rotational speed of the bobbin is restricted by virtue of its mass and dimensions and this means that only a limited amount of cover yarn can be wound on to the core yarn if it is to achieve an acceptable rotational speed. The relatively small amount of cover yarn on the bobbin means that the apparatus has to be stopped frequently to change bobbins. The length of covered yarn taken up on the core yarn take-up is relatively short and, in practical terms, perhaps a quarter of the length of yarn normally carried by the yarn spools utilised on commercial knitting machines. To provide a spool of yarn for a commercial knitting machine it is therefore preferable to rewind the covered core yarn from several yarn take-up spools. Normally the contents of at least four take-up spools are wound onto the knitting machine package and this means that, in addition to the inconvenience of providing re-spooling machinery, providing man power to operate this re-spooling machinery and the replacement of bobbins in the covering machinery, the yarn supplied to the knitting machine includes knots at the joints between lengths.
SUMMARY OF THE INVENTION
According to one aspect of the present invention there is provided a method of covering a core yarn with a cover yarn comprising supplying a package of core yarn on a member which is fixed against rotation, supplying a package of cover yarn, guiding the cover yarn to form a loop which on rotation about an axis defines an envelope which surrounds the core yarn package, drawing off core yarn along the auras of rotation of the envelope in the direction away from the cover package so that when the core yarn intercepts the envelope it is covered by cover yarn.
Preferably a plurality of cover yarns are provided to form a multiple covering on the core, yarn, each cover yarn being taken from an independent supply of cover yarn, all of which are arranged in sequence on one side of the core yarn supply, the cover yarn from each supply being guided to form a loop which on rotation about an axis defines an envelope which surrounds the core yarn supply and all cover yarn supplies which are closer to the core yarn supply than the said cover yarn supply.
The loops are spaced from each other and rotated at the same speed and in the same direction.
Preferably all cover yarn envelopes are intercepted by the core yarn at the same point or closely spaced points. Preferably the loops which define all the envelopes are equally spaced angularly at the interception point.
According to a second aspect of the present invention there is provided apparatus for covering a core yarn comprising a mounting for a package of core yarn fixed against rotation, a first rotatable member located on one side of the core yarn package and a second rotatable member located on the other side of the core yarn package, the rotatable members being axially spaced from the core yarn package, means for rotating the first and second rotatable members at the same speed and direction, a mounting for a package of cover yarn, take-off means for leading cover yarn from said cover yarn package to the centre of said first rotatable member, first guide means in or on the first rotatable member for guiding cover yarn from the centre to or near to the periphery of said first rotatable member, second guide means in the first rotatable member for leading cover yarn from the first rotatable member to or near to the periphery of the second rotatable member, guide means in or on the second rotatable member for guiding cover yarn from or near to the periphery of the second rotatable member to the centre of the said rotatable member, core yarn take-off means for leading core yarn through the second rotatable member along its axis of rotation whereby cover yarn exiting from the second rotatable member at its centre is wound around the core yarn, and means for drawing off covered yarn.
Preferably the rotatable members are discs.
Preferably the mounting for the cover yarn package is fixed against rotation.
Preferably the guide means for the cover yarn in or on the second disc includes a guide closely adjacent to the aids of rotation of the disc such that cover yarn is wound around the core yarn from a direction generally perpendicular thereto.
Preferably the means for holding the core yarn packaging against rotation includes a magnet in the core yarn mounting and a magnet on a fixed member located on the side of the second disc opposite to said core yarn mounting.
Preferably a hollow member passes through the core yarn package through which core yarn from the package is guided to the centre of the second disc.
Preferably a yarn tensioner is provided for the core yarn.
Preferably the tensioner comprises first and second annular discs mounted for axial movement over the surface of the hollow member, a spring for biasing discs towards the end of the hollow member and an annular member resting on the disc closest to the end of the member, the weight of said annual member being variable to vary tension on yarn passing between the discs prior to it passing through the spindle.
Preferably the axes of the cover yarn package, the first and second disc and the core yarn package are coincident.
Preferably a cylindrical enclosure is provided around a pair of co-operating discs and the core yarn package, extending between members located on the sides of the discs remote from the core yarn package.
Preferably one or more additional cover yarn packages are interposed between the said cover yarn package and the core yarn package, each of said interposed packages having a pair of discs on each side thereof, with each disc being provided with cover yarn guide means for directing cover yarn from preceding package(s) from the centre to the periphery of the upper disc of the pair, from the periphery of the upper disc to the periphery of the lower disc, from the peripheral of the lower disc to the centre thereof and thereafter to the centre of the next succeeding discs with all the discs being rotated at the same speed and in the same direction.
Preferably each disc has guide paths for each cover yarn passing across the disc.
Preferably said paths are angularly equispaced.
Alternatively the apparatus includes a further mounting for a package of second cover yarn, means for holding the further mounting against rotation, third and fourth discs located on each side of the said mounting and package, means to rotate the third and fourth discs at the same speed and in the same direction, means for leading covered yarn from an earlier covering apparatus to the centre of the third disc, guide means in or on the third disc for guiding covered yarn from the centre to or near to the periphery of the third disc, means at or near the periphery of the third disc for guiding covered yarn to a point at or near the periphery of the fourth disc, guide means in or on the fourth disc for guiding covered yarn from its periphery to its centre, and further guide means for guiding covered yarn through the centre of the fourth disc whereby the second cover yarn and the covered yarn are wound together and means for drawing off covered yarn.
Preferably the guide passages are formed through each disc. Alternatively, they may be formed over a surface of the disc.
Preferably yarn guides are located at the ends of each passage, the yarn guides being formed from a hard wearing material, for example a ceramic material. Preferably yarn guides are mounted at a position spaced internally from the periphery of the disc.
According to a further aspect of the present invention there is provided a method of covering a core yarn with a cover yarn comprising removing core yarn from a package of core yarn fixed against rotation, drawing the core yarn through a hollow member, rotating first and second discs at the same speed, about the axis of said spindle with the discs spaced on either side of the core yarn package, supplying a cover yarn to the centre of the first disc, leading the cover yarn from the centre of the first disc to its periphery, then to the periphery of the second disc, then from the periphery of the second disc to the centre of the second disc, guiding core yarn through the centre of the second disc along the axis if rotation thereof, winding cover yarn around the core yarn and drawing off the covered core yarn.
A further aspect of the present invention provides a method for producing covered yarn in which a cover yarn is tensioned and guided radically away from the axis of a core yarn package, axially alongside the core yarn package and thereafter radially towards the axis of the core yarn package while being rotated about the said axis, core yarn being drawn off its package and along said axis whereby the cover yarn is wound around the care yarn after being guided towards it.
According to a still further aspect of the present invention there is provided a yarn tensioner comprising generally vertical hollow member, first and second discs mounted for axial movement along the member and adapted to receive the yarn to be tensioned therebetween, biasing means for urging the discs towards the top of the hollow member and an adjustable weight located on the upper disc.
Preferably the yarn is guided radially from the outside to the inside of the discs and thereafter along the hallow member to and over its top.
Another aspect of the present invention provides an enclosure for a yarn covering apparatus comprising a cylindrical member adapted to be arranged in an apparatus in which a loop of covering yarn is caused to rotate about a core yarn to be covered coaxial with and around the rotating loop of cover yarn and means for causing a rotational movement of the air within the enclosure in the same direction as the rotation of the loop and at a speed no greater than the loop speed.
Preferably the same means rotate the loop and the air.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the present invention will now be described by way of example only with reference to the accompanying drawings in which:
FIG. 1 shows an apparatus for providing a single yarn covering on a core yarn;
FIG. 1 a shows a detail of the apparatus of FIG. 1,
FIG. 2 shows diagrammatically an apparatus for providing a double yarn covering on a core yarn;
FIG. 2 a shows a detail of the apparatus of FIG. 2;
FIG. 3 shows diagrammatically an apparatus for providing a multi yarn covering on a core yarn; and
FIG. 4 shows a detail of the mounting of a yarn package of the apparatus of FIGS. 1, 2 and 3 .
DETAILED DESCRIPTION OF THE INVENTION
A package 10 of cover yarn comprises a standard cylindrical spool 12 which has no end flanges and on which is wound, in a helical path, a cover yarn 14 , the yarn removal point 16 being at the outer periphery of the package. The cover yarn package 10 is mounted by any convenient means about a central yarn tensioner assembly 18 which is coaxial with the axis of the package 10 and has a yarn tensioner 20 at its end. A mounting means 22 supports the cover package 10 against rotation and is in turn fixed to a mounting member 30 of the framework of the apparatus. A bearing 32 is mounted by the member 30 and rotatably supports a spindle 26 which is coaxial with the yarn tensioner assembly 18 , is hollow and communicates with a hollow member 17 of the yarn tensioner assembly 18 . The spindle 26 has a toothed drive wheel 28 fixed thereto and around which a toothed drive belt (not shown) is passed, the drive belt being driven by an electric motor (not shown) mounted to the framework member 30 .
A first disc 38 manufactured from a suitable plastics material is mounted to the lower end of the rotatable spindle 26 . A yarn passage (not shown) is formed in a radial direction from the periphery of the first disc 38 to its centre, communicating with the hollow centre of the spindle 26 . Ceramic yarn guides are provided at each of the yarn passage to guide cover yarn taken from the package removal point 16 , by way of the tensioner 20 and through the coaxial, hollow member 17 and spindle 26 , to the yarn guide adjacent the centre of the first disc 38 , and through the radial passageway to the yarn guide 40 mounted at or near the periphery of the disc.
A mounting arrangement is provided for a package 42 of core yarn. Core yarn package 42 is more clearly illustrated in FIG. 4 and comprises a non-flanged cylindrical bobbin 44 having core yarn 43 , which is normally an elastic yarn, for example LYCRA (Registered Trade Mark), wound thereon in a normal helical arrangement. The bobbin 44 is mounted on a mounting plate 46 by a bobbin mounting assembly 48 . The assembly includes a plurality of angularly spaced resilient members 45 having a serrated upper surface, the members 45 preventing any tendency for the bobbin to move over the mounting plate as yarn is drawn off the bobbin. The assembly 48 includes also a hollow member 50 carrying a yarn tensioner 52 at its upper end. The yarn tensioner 52 comprises a first ceramic disc mounted for axial movement over the outer surface of the member 50 and spring biased towards the upper end of the member by a coil spring 56 . A second ceramic disc 55 is also mounted for axial movement along the end of the member 50 . Core yarn taken from a take-up point 60 on the periphery of yarn package 42 is led between the discs 54 and 55 up the outer wall of the member 50 , over an annular ceramic guide 62 fixed at the top of the member 50 and down through the member 50 to a guide 64 . It will be realised that the coil spring 56 provides a shock absorbing effect to the yarn tensioner and tension in the yarn is determined by the weight on an annular member 58 resting on the top disc 55 .
A rotatable hollow spindle 70 , which is coaxial with the member 50 , supports through a bearing 72 , the mounting plate 46 and carries a toothed drive wheel 74 (FIG. 1) driven by a toothed belt (not shown) which in turn is driven by an electric motor mounted on the framework 30 of the machine. The motor drives the wheel 74 at exactly the same speed as the toothed wheel 28 , this being most readily achieved by using a single output shaft from the electric motor to drive both toothed belts.
Magnets 76 on the mounting plate 46 are located by corresponding magnets 78 fixed to the machine frame work 30 to hold the core package and its mounting plate 46 against rotation. This enables a second plastics material disc 80 fixed to the hollow spindle 70 to rotate in the magnetic field between the magnets 76 and 78 . The second disc 80 is of similar construction to the first disc 38 and includes a radial passageway (not shown) extending therethrough from a peripheral yarn guide 82 to a yarn guide 84 (FIG. 1 a ) at the centre of the disc 80 . FIG. 1 a shows that core yarn 42 is guided through the rotating spindle 70 and past the rotating yarn guide 84 as cover yarn 14 is wound therearound due to the rotation of the second disc 80 .
FIG. 1 further shows that the cover yarn 14 is led from the yarn guide 40 at the periphery of the first disc to the yarn guide 82 at the periphery of the second disc which is rotating at exactly the same speed and in the same direction as the first disc. The cover yarn is therefore guided by the rotating discs around the fixed package of core yarn without any noticeable ballooning effect in the length of yarn between the guides 40 and 82 .
Covered core yarn is removed by draw rollers 86 to a take-up package 88 driven in a known manner by a take-up drive roller 90 . It will be realised that by adjusting the tension at the core yarn tensioner assembly 52 the degree of stretch in the core yarn is adjusted, that is the core yarn is stretched as it is covered with cover yarn.
It will be realised that as the discs 38 and 80 rotate at high speed the length of cover yarn 14 extending between them moves through the ambient air at high speed and is subject to undesirable drag. To obviate this problem a cylindrical enclosure 150 is constructed between the framework members 30 to provide a totally enclosed volume of air around the path of the cover yarn 14 . This volume of air, on rotation of the discs 38 , 80 will be induced to rotate thus reducing the drag effect. Additionally, the enclosure acts as a safety cage around the rotating components of the apparatus.
FIG. 2 shows an apparatus for applying two cover yarns to a core yarn. That part of the apparatus labelled “A” in FIG. 2 takes the form of the apparatus illustrated in FIG. 1 and will not be described in further detail. In this embodiment, the covered core yarn at the draw rollers 86 , rather than being wound on a package, is passed through another covering apparatus section labelled “B” in FIG. 2 . The section of the apparatus labelled “B” comprises a second package 92 of cover yarn which is mounted in a manner similar to that described with reference to FIG. 1 on a mounting place 94 which is held against rotation by magnets 96 on the mounting plate 94 which are located by magnets 98 on the framework 30 of the machine. A third disc 100 is mounted on a hollow rotatable spindle 104 through which the covered yarn 101 is passed and which is rotatably mounted by a bearing 102 on the machine framework 30 . The disc 100 and spindle 104 are rotated, as before, by a toothed drive wheel and belt arrangement. The third disc 100 resembles the first and second discs 38 , 80 . The passageway in disc 100 guides the covered yarn 101 from the centre of the disc 100 to the yarn guide at its periphery. The second cover yarn is guided from the periphery of the package 92 to a yarn tensioner assembly 108 on the upper end of a member 107 of the mounting assembly for the second cover yarn. Thereafter it is guided down through the member 107 to the centre of a fourth disc 109 .
The fourth disc rotates in the space between the lower frame member 30 and the mounting plate 94 for the second cover yarn package 92 and is driven at the same speed and in the same direction as the third disc 100 by a tooth drive wheel and belt assembly. FIG. 2 a shows that the guide passage for the covered yarn 101 leads the covered yarn to the centre of the disc where it is wrapped together with the second cover yarn 106 as it is drawn off by draw rollers 87 to a take-up package 88 driven by a drive roller 90 in the manner described above.
The third and fourth discs 100 , 109 can be rotated in the same direction as the first and second discs 38 , 80 such that the direction of the helical winding of the first and second cover yarns is the same. However it is preferable that the third and fourth discs 100 , 109 are rotated in the opposite direction to the first and second discs 38 , 80 such that the second cover yarn is wrapped in the opposite direction of the first cover yarn.
FIG. 3 illustrates an apparatus for providing three cover yarns on a core yarn.
In general, its form and method of operation is similar to the form and method of operation described with reference to FIG. 1 and, as a result, a detailed description will not now be given, rather a general description will be given and reference can be made to FIG. 1 for detail.
In this embodiment, three cover yarn packages 110 , 112 and 114 are arranged vertically one above the other and all vertically above the core yarn package 116 . A first cover yarn 118 is taken, by way of first and second discs 121 , 122 past the second cover package 112 which is fixed against rotation, in the manner described above, by magnetic means. The second cover yarn 124 is led through the centre of its package to a third disc 126 having two, diametrically opposed, radial passages and rotating at the same speed and direction as the second disc 122 .
The first and second cover yarns 118 and 124 are guided past the third cover yarn package 114 to a fourth disc 128 having two, diametrically opposed radial passages therethrough. The third cove yarn 130 from the third cover yarn package 114 is led through the spindle at the middle of this package to a radially extending passage in the fifth disc 132 which is driven in the same direction and at the same speed as the fourth disc 128 and has three radial passages mutually arranged at 120° spacing. The three cover yarns (only two of which are shown in FIG. 3) are then supplied to three radial passages spaced at 120° in a fifth disc 134 , passing the core yarn package 116 which is held against rotation in the normal manner on a mounting plate 136 by magnets 76 and 78 . The core yarn 138 removed from its package 116 , in a manner described with reference to FIG. 1, is then guided axially through the rotatable spindle 140 on which the sixth disc 134 is mounted and the three cover yarns are wrapped around the core yarn in a manner similar to that illustrated in FIG. 2 a . The arrangement of draw rollers 86 , a covered package 88 and package drive 90 are also as described above.
Various modifications can be made without departing from the scope of the invention, for example the mounting means of the various packages can be modified, provided that the packages are held against rotation as the yarn is drawn off from them. The discs and arrangement of guide means in them can be modified. Rather than having passages extending through the discs, yarn guide means could be mounted above and/or below the discs to guide yarn over the surface of the discs. A further guide passing through the disc near its periphery guides the yarn from the radial to the axial direction. The discs could be lightened by removing sections therefrom but it is important to ensure that the discs remain statically and dynamically balanced to ensure smooth operation of the apparatus. Directions of rotation can be amended giving different covering effects and by varying the tensions of the core yarn and the covering yarn or yarns, different effects can be achieved in the covered yarn. The discs can be made from reinforced synthetic resinous material.
Additional apparatus, which is standard in this art, can be employed between the draw rollers and the take-up package, for example, heaters to set the covered yarn, oiling rollers, air jet treatment apparatus. The arrangement of structural components, for example, bearings, yarn tensioners, yarn guides can be varied utilising alternatives known in the art.
It is possible, simply by altering the yarn guides within the discs, to arrange for the covering yarns to be applied to the core yarn at the same height or at differing heights.
The apparatus shown in FIG. 3 can be modified by adding or subtracting cover yarn package assemblies therefrom. If the lower cover yarn package assembly is removed a double covered core yarn will be obtained and if more cover yarn package assemblies are added between the lowermost cover yarn package assembly and the core yarn package assembly a multi covered core yarn will be obtained. Each additional cover package assembly will have discs with correspondingly extra passages.
It will be realised that the apparatus produces a package of covered yarn which is considerably longer than that produced by existing apparatus without the need to knot lengths of yarn together, re-spooling etc. It is possible for the present apparatus to ensure that there is no twist in the cover yarn. As the cover yarn is always guided through a pair of discs, any twist which is induced by one disc is removed by the other disc which, it will be recalled, is rotating in the same direction and at the same speed.
In general terms, the apparatus is more compact than existing apparatus even although the yarn packages that it can accommodate are of a much greater size than those used in existing apparatus.
As a result of the relatively close spacing of the discs and the control which can be exerted on the cover yarns, the discs can be made to rotate at a speed much greater than that normally encountered in apparatus of this nature.
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A method of covering a core yam with a cover yarn characterised in that it includes supplying a package of core yam on a member which is fixed against rotation, supplying a package of cover yam, guiding the cover yarn to form a loop which on rotation about an axis defines an envelope which surrounds the core yarn package, drawing off core yarn along the axis of rotation of the envelope in the direction away from the cover package so that when the core yarn intercepts the envelope it is covered by cover yarn.
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This is a continuation of co-pending application No. 07/277,647 filed on Nov. 7, 1988 now U.S. Pat. No. 4,855,531 related to the same separation of m-diisopropylbenzene from p-diisopropylbenzene using different agents.
FIELD OF THE INVENTION
This invention relates to a method for separating m-diisopropylbenzene from p-diisopropylbenzene using certain alcohols as the agent in azeotropic distillation.
DESCRIPTION OF PRIOR ART
Azeotropic distillation is the method of separating close boiling compounds from each other by carrying out the distillation in a multiplate rectification column in the presence of an added liquid, said liquid forming an azeotrope with one or both of the compounds to be separated. Its presence on each plate of the rectification column alters the relative volatility in a direction to make the separation on each plate greater and thus require either fewer plates or effect the same separation or make possible a greater degree of separation with the same number of plates. The azeotrope forming agent is introduced with the feed to a continous column. The azeotrope forming agent and the more volatile component are taken off as overhead product and the less volatile compound comes off as bottoms product. The usual methods of separating the azeotrope former from the more volatile component are cooling and phase separation or solvent extraction.
In the manufacture of cumene, also called isopropylbenzene, by the alkylation of benzene with propylene, the most prevalent by-products are the diisopropylbenzenes with the meta and para isomers comprising most of the by-product. m-Diisopropylbenzene (m-DIPB) boils at 203.2° C. m-Diisopropylbenzene (p-DIPB) boils at 210.3° C. and these two have a relative volatility of 1.14. The difficulty of separating these two by rectification can be shown by the data in Table 1. Table 1 shows
TABLE 1______________________________________Plates Required To Effect Separation In 99% PurityRelative Theoretical Actual Plates,Volatility Plates 75% Efficiency______________________________________1.14 71 951.22 47 631.25 41 551.29 36 48______________________________________
that rectification of m-DIPB from p-DIPB in 99% purity requires 95 actual plates. Using azeotropic distillation with an agent yielding a relative volatility of 1.29 would require only 48 actual plates. Thus azeotropic distillation would be an attractive method of effecting the separation of these isomers if agents can be found that (1) will increase the relative volatility of m-DIPB to p-DIPB and (2) are easy to recover from the p-DIPB.
Azeotropic distillation typically requires the addition of about as much agent as m-DIPB to be boiled up in the column which increases the heat requirement as well as somewhat larger diameter plates to accomodate the increase of liquid and vapor in the column. In addition, a solvent extraction column is usually provided to recover and recycle the azeotrope forming agent.
OBJECTIVE OF THE INVENTION
The objective of this invention is to provide a process or method of azeotropic distillation that will enhance the relative volatility of m-DIPB from p-DIPB in their separation in a rectification column. It is a further object of this invention to identify organic compounds which in addition to the above constraints, are stable, can be separated from m-DIPB by solvent extraction and can be recycled to the azeotropic distillation and reused with little decomposition.
SUMMARY OF THE INVENTION
The objects of this invention are provided by a process for separating m-DIPB from m-DIPB which entails the use of certain alcohols in an azeotropic distillation process.
DETAILED DESCRIPTION OF THE INVENTION
I have discovered that certain alcohols will effectively enhance the relative volatility of m-DIPB from p-DIPB and permit the separation of m-DIPB from p-DIPB by rectification when employed as the agent in azeotropic distillation. Table 2 lists the alcohols that I have found to be effective.
TABLE 2______________________________________Effective Azeotrope Forming Agents - Alcohols Azeotrope RelativeCompound B.P., °C. Volatility______________________________________o-Isopropyl phenol 200 1.34Diethylene glycol butyl ether 200 1.29Dipropylene glycol methyl ether 186 1.28Propylene glycol 168 1.28Diethylene glycol methyl ether 182 1.282-Ethyl hexanol 183 1.27Ethylene glycol hexyl ether 195 1.26o-Cresol 184 1.26p-Cresol 188 1.25Diethylene glycol ethyl ether 185 1.251-Butoxy ethoxy-2-propanol 200 1.25Phenol 174 1.24n-Nonyl alcohol 196 1.23o-sec. Butyl phenol 205 1.23Isononyl alcohol 194 1.22Tetrahydrofurfuryl alcohol 171 1.21Diisobutyl carbinol 180 1.20o-tert. Butyl phenol 205 1.20Butoxypropanol 173 1.18Propoxypropanol 198 1.18m-Cresol 189 1.17Butoxyethoxypropanol 199 1.17______________________________________
TABLE 3______________________________________Ineffective Alcohols RelativeCompound Volatility______________________________________Dipropylene glycol methyl ether 1.061-Octanol 1.14Benzyl alcohol 1.112-Octanol 1.10Phenethyl alcohol 1.06Methyl benzyl alcohol 1.16Ethylene glycol butyl ether 0.6n-Hexanol 1.10Diacetone alcohol 1.13Ethylene glycol phenyl ether 1.14Isooctanol 1.15______________________________________
Table 3 lists some alcohols found to be ineffective. The data in Tables 2 and 3 were obtained in a vapor-liquid equilibrium still. In each case, the starting material was a mixture containing 50 % alcohol, 25 % m-DIPB and 25 % p-DIPB. The boiling points of the azeotropes at 640 mm. Hg are shown. The relative volatilities are listed for each of the alcohols investigated.
The alcohols which are effective are o-isopropyl phenol, diethylene glycol butyl ether, dipropylene glycol methyl ether, propylene glycol, 2-ethyl hexanol, ethylene glycol hexyl ether, phenol, o-cresol, m-cresol, p-cresol, diethylene glycol ethyl ether, 1-butoxy ethoxy-2-propanol, diethylene glycol methyl ether, n-nonyl alcohol, isononyl alcohol, o-sec. butyl phenol, o-tert. butyl phenol, tetrahydrofurfuryl alcohol, diisobutyl carbinol, butoxypropanol, propoxypropanol and butoxyethoxypropanol.
The data in Table 2 indicates, for example, that one part of 2-ethyl hexanol mixed with one part of m-DIPB - p-DIPB mixture gives a relative volatility of 1.27.
THE USEFULNESS OF THE INVENTION
The usefulness or utility of this invention can be demonstrated by referring to the Tables 1, 2 and 3. All of the successful azeotropic agents show that m-DIPB can be separated from p-DIPB by means of distillation in a rectification column and that the ease of separation as measured by relative volatility is considerable. Without these azeotropic agents, only a slight improvement will occur in a rectification column.
WORKING EXAMPLES
EXAMPLE 1
Forty grams of m-DIPB - p-DIPB mixture and 40 grams of diethylene glycol butyl ether were charged to an Othmer type vapor-liquid equilibrium still and refluxed for thirteen hours. Analysis by gas chromatography gave a vapor composition of 68.9% m-DIPB, 31.1% p-DIPB; a liquid decomposition of 63.2% p-DIPB, 36.8% p-DIPB. This indicates a relative volatility of m-DIPB to p-DIPB of 1.29.
EXAMPLE 2
Forty grams of m-DIPB - p-DIPB mixture and 40 grams of diethylene gylcol methyl ether were charged to the vapor-liquid equilibrium still and refluxed for eleven hours. Analysis indicated a vapor composition of 66.7% m-DIPB, 33.3% p-DIPB; a liquid composition of 60.9% p-DIPB which is a relative volatility of 1.28.
EXAMPLE 3
A two foot long rectification column packed with Berl saddles was calibrated with m-DIPB and p-DIPB which possesses a relative volatility of 1.14 and found to have 2.3 theoretical plates. A solution comprising 80 grams of m-DIPB, 20 grams of p-DIPB and 40 grams of o-isopropyl phenol was placed in the stillpot and heated. After two hours of refluxing a total reflux, analysis was made by gas chromatography. The overhead composition was 78% m-DIPB, 22% p-DIPB and the stillpot analysis was 62.7% m-DIPB, 37.3% p-DIPB. Using these compositions in the Fenske equation with the number of theoretical plates in the column being 2.3 gave an average relative volatility of 1.34 for each theoretical plate.
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Meta and para-diisopropylbenzenes cannot be easily separated from each other by distillation because of the closeness of their vapor pressures. m-Diisopropylbenzene can be readily removed from p-diisopropylbenzene by azeotropic distillation using certain alcohols. Typical effective azeotropic distillation agents are diethylene glycol butyl ether, diethylene glycol methyl ether and o-isopropyl phenol.
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PRIORITY TO RELATED APPLICATIONS
[0001] This application claims the benefit of Provisional Application(s) Ser. No. 60/682,997 filed May 20, 2005, and Ser. No. 60/602,175 filed Aug. 17, 2005.
FIELD OF THE INVENTION
[0002] The present invention relates to hydantoin derivatives as inhibitors of the two protein kinases commonly known as MEK1 and MEK2 for the treatment of human diseases such as cancer. MEK is a commonly used abbreviation for MAP kinase/ERK kinase which is in turn an abbreviation for mitogen activated protein/extracellular signal regulated kinase kinase. MEK is also sometimes referred to as MAPK kinase or MAP kinase.
BACKGROUND OF THE INVENTION
[0003] Cancer is a disease characterized by the proliferation of malignant cells and tumors which have the potential for unlimited growth, local expansion and systemic metastasis. This uncontrolled growth is derived from abnormalities in the signal transduction pathways and the response to various growth factors, which differ from those found in normal cells. The abnormalities include changes in the intrinsic activity or in the cellular concentration of one or more signaling proteins in the signaling cascade. These changes are frequently caused by genetic mutations or over expression of intracellular signaling proteins which can lead to spurious mitogenic signals within the cells.
[0004] The mitogen activated protein (MAP) kinase pathway represents one of the best characterized signaling pathways involved in the development and progression of human cancers (J. M. English et al., Trends in Pharm. Sci. 2002, 23(1), 40). This pathway, via the Ras/Raf/MEK/ERK signal cascade, is responsible for transmitting and amplifying mitogenic signals from the cell surface to the nucleus where activated transcription factors regulate gene expression and determine cell fate. The constitutive activation of this pathway is sufficient to induce cellular transformation. Dysregulated activation of the MAP kinase pathway due to aberrant receptor tyrosine kinase activation, Ras mutations or Raf mutations has frequently been found in human cancers, and represents a major factor determining abnormal growth control. In human malignances, Ras mutations are common, having been identified in about 30% of cancers (J. L. Bos, Cancer Res. 1989, 49, 4682). The Ras family of GTPase proteins (proteins which convert guanosine triphosphate to guanosine diphosphate) relay signals from activated growth factor receptors to downstream intracellular partners. Prominent among the targets recruited by active membrane-bound Ras are the Raf family of serine/threonine protein kinases. The Raf family is composed of three related kinases (A-, B- and C-Raf) that act as downstream effectors of Ras. Ras-mediated Raf activation in turn triggers activation of MEK1 and MEK2 (MAP/ERK kinases 1 and 2) which in turn phosphorylate ERK1 and ERK2 (extracellular signal-regulated kinases 1 and 2) on both tyrosine-185 and threonine-183. Activated ERK1 and ERK2 translocate and accumulate in the nucleus, where they can phosphorylate a variety of substrates, including transcription factors that control cellular growth and survival (A. Bonni et al, Science 1999, 286, 1358). Recently, B-Raf somatic mutations in the kinase domain were also found in 66% of malignant melanomas, and at a lower frequency in a wider range of human cancers (H. Davies et al. Nature 2002, 417, 949). Like mutated Ras, constitutively active mutated Raf can transform cells in vitro and induce malignancies in a variety of animal models (H. Davies et al., Nature 2002, 417, 949). Given the importance of the Ras/Raf/MEK/ERK pathway in the development of human cancers, the kinase components of this signaling cascade are emerging as potentially important targets for the modulation of disease progression in cancer and other proliferative diseases (R. Herrera et al. Trends Mol. Med. 2002, 8(4, Suppl.), S27).
[0005] MEK1 and MEK2 are members of a larger family of dual-specificity kinase (MEK1-7) that phosphorylate threonine and tyrosine residues of various MAP kinases. MEK1 and MEK2 are encoded by distinct genes, but they share high homology (80%) both within the C-terminal catalytic kinase domains and most of the N-terminal regulatory region (C. F. Zheng et al., J. Biol. Chem. 1993, 268, 11435). Oncogenic forms of MEK1 and 2 have not been found in human cancers. However, constitutive activation of MEK has been shown to result in cellular transformation (S. Cowley et al., Cell 1994, 77, 841). In addition to Raf, MEK can also be activated by other oncogenes as well. So far, the only known substrates of MEK1 and 2 are ERK1 and 2 (R. Seger et al., J. Biol. Chem. 1992, 267, 14373). This unusual substrate specificity in addition to the unique ability to phosphorylate both tyrosine and threonine residues places MEK1 and 2 at a critical point in the signal transduction cascade which allows them to integrate many extracellular signals into the MAPK pathway.
[0006] Previously reported studies with the MEK inhibitor 2-(2-chloro-4-iodo-phenylamino)-N-cyclopropylmethoxy-3,4-difluoro-benzamide, also known as Cl-1040 (Pfizer Inc., described in PCT publication No. WO 99/01426) provides further evidence that MEK1 and 2 represent an attractive target for pharmacological intervention in cancer or other human diseases characterized by the hyperactivity of MEK and diseases regulated by the MAPK pathway.
[0007] Compounds related to the compounds of the present invention have previously been reported as glucokinase activators (F. Hoffmann-La Roche AG, PCT publication No. WO 01/83478). The compounds which have been previously reported were defined as containing a methylene spacer (CH 2 group) between the hydantoin ring and additional substituents which included an unsubstituted or a substituted aryl ring amongst other defined substituents. The compounds claimed in the present invention are defined to include compounds where there is no methylene spacer between the hydantoin ring and substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl group rings.
SUMMARY OF THE INVENTION
[0008] This invention relates to at least one compound of the formula I
or pharmaceutically acceptable salts thereof,
wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are described in this application. These compounds are believed to inhibit MEK 1/2, a dual specificity protein kinase which is an essential component of the MAP kinase signal transduction pathway and as such the compounds will have anti-hyperproliferative cellular activity.
DETAILED DESCRIPTION OF THE INVENTION
[0009] The present compounds are new compounds of the formula I
wherein:
R 1 is selected from the group consisting of a substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl group; R 2 is hydrogen R 3 is selected from a mono- or di-alkyl group; R 4 is selected from the group consisting of a substituted or unsubstituted aryl, hydroxyl, alkoxy, substituted alkoxy or a substituted or unsubstituted heteroaryl or alkyl group; R 5 is selected from the group consisting of COOR, COR, CON(R 7 ) 2 or CHOHR wherein R is alkyl or alkyl substituted by an alkoxy group; and R 6 and R 7 are selected from hydrogen or an alkyl group or the pharmaceutically acceptable salts or esters or prodrugs thereof.
[0016] Preferred are compounds of formula I wherein R 3 is an alkyl group, R 4 is substituted or unsubstituted aryl and R 6 is hydrogen.
[0017] More preferred are compounds wherein R 3 is a methyl group and R 4 is phenyl.
[0018] Most preferred are compounds of the formulas:
(2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-hydroxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-hydroxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-((R)-4-{4-[2-(2-methoxy-ethoxy)-ethoxy]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-ethoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-dimethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; compound with trifluoro-acetic acid (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-diethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; compound with trifluoro-acetic acid (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-ethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(S)-4-[4-(2-dimethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; compound with trifluoro-acetic acid (4-{1-[(1S,2S)-1-(4-Acetyl-thiazol-2-ylcarbamoyl)-2-phenyl-propyl]-2,5-dioxo-imidazolidin-4-yl}-phenyl)-phosphonic acid diethyl ester; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[4-(4-dimethylamino-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; (2S,3S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-pentanoic acid (4-acetyl-thiazol-2-yl)-amide; (2S,3S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-[(R)-4-(2,3-Dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-[(R)-4-(4-Ethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-[(R)-4-(4-Hydroxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{(R)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{(S)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{(R)-4-[4-(2-Hydroxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-((R)-4-{4-[2-(2-Methoxy-ethoxy)-ethoxy]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{(R)-4-[4-(2-Ethoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{(R)-4-[4-(2-Dimethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; compound with trifluoro-acetic acid (4-{(R)-2,5-Dioxo-1-[(1S,2S)-2-phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propyl]-imidazolidin-4-yl}-phenoxymethyl)-phosphonic acid dimethyl ester; (2S,3S)-N-(4-Isobutyryl-thiazol-2-yl)-2-{4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; (2S,3S)-N-(4-Isobutyryl-thiazol-2-yl)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; (2S,3S)-2-{(S)-4-[4-(2-Dimethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; compound with trifluoro-acetic acid; (2S,3S)-2-{2,5-Dioxo-4-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{4-[4-(2-Morpholin-4-yl-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-3-(3-Fluoro-phenyl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-[(R)-4-(4-Methoxy-3-methyl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{(S)-4-[4-(2-Hydroxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-((R)-2,5-Dioxo-4-phenyl-imidazolidin-1-yl)-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-[4-(4-Dimethylamino-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-[4-(4-Morpholin-4-yl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{4-[4-(4-Hydroxy-piperidin-1-yl)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-(4-{4-[(2-Methoxy-ethyl)-methyl-amino]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-N-(4-Cyclopropanecarbonyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; (2S,3S)-2-{4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-methyl-pentanoic acid (4-propionyl-thiazol-2-yl)-amide; (2S,3R)-3-Benzyloxy-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-N-[4-(2-Methoxy-acetyl)-thiazol-2-yl]-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; 2-{(2S,3S)-2-[(R)-4-(2,3-Dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-[(2S,3S)-2-((R)-2,5-Dioxo-4-phenyl-imidazolidin-1-yl)-3-phenyl-butyrylamino]-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3S)-2-[(R)-4-(4-Hydroxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-((2S,3S)-2-{(R)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester; 2-((2S,3S)-2-{(R)-4-[4-(2-Hydroxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3S)-2-[(R)-4-(4-Isopropoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3S)-2-[(R)-4-(4-Methoxy-3-methyl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-((2S,3S)-2-{(R)-4-[4-(Dimethoxy-phosphorylmethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3S)-3-(2-Methoxy-phenyl)-2-[4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-((2S,3S)-3-(4-Fluoro-phenyl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-pentanoylamino}-thiazole-4-carboxylic acid methyl ester; 2-[(2S,3S)-2-((R)-2,5-Dioxo-4-phenyl-imidazolidin-1-yl)-3-methyl-pentanoylamino]-thiazole-4-carboxylic acid methyl ester; 2-((2S,3S)-2-{(R)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-methyl-pentanoylamino)-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3R)-3-Hydroxy-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-((2S,3R)-3-Hydroxy-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester; 2-((2S,3R)-3-tert-Butoxy-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3R)-3-Methoxy-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-((2S,3R)-3-Methoxy-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester; 2-((2S,3R)-3-Benzyloxy-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester; 2-((2S,3R)-3-(4-Chloro-benzyloxy)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester 2-{(2S,3R)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazol idin-1-yl]-3-methyl-pentanoylamino}-thiazole-4-carboxylic acid methyl ester 2-((2S,3R)-2-{(R)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-methyl-pentanoylamino)-thiazole-4-carboxylic acid methyl ester; 2-((2S,3R)-2-{(R)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-methyl-pentanoylamino)-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3S)-2-[4-(4-Methanesulfonyl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-{(S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3R)-2-[(R)-4-(2,3-Dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester; 2-{(2S,3S)-2-[(R)-4-(4-Acetylamino-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester; N-[4-(1-Hydroxy-1-methyl-ethyl)-thiazol-2-yl]-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; (2S,3S)-2-[(R)-4-(2,3-Dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-N-[4-(1-hydroxy-propyl)-thiazol-2-yl]-3-phenyl-butyramide; (2S,3S)-N-[4-(1-Hydroxy-ethyl)-thiazol-2-yl]-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; 2-{(2S,3S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid dimethylamide; (2S,3S)-N-(4-Ethylsulfanyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; (2S,3S)-N-(4-Ethanesulfinyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl ]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; (2S,3S)-N-(4-Ethanesulfonyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; (2S,3S)-N-[4-(2-Hydroxy-acetyl)-thiazol-2-yl]-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; (4-{(R)-1-[(1S,2S)-1-(4-Acetyl-thiazol-2-ylcarbamoyl)-2-phenyl-propyl]-2,5-dioxo-imidazolidin-4-yl}-phenoxy)-acetic acid methyl ester; (4-{(R)-2,5-Dioxo-1-[(1S,2S)-2-phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propyl]-imidazolidin-4-yl}-phenoxy)-acetic acid methyl ester; (4-{2,5-Dioxo-1-[(1S,2S)-2-phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propyl]-imidazolidin-4-yl}-phenoxy)-acetic acid; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-dimethylcarbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-methylcarbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-carbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-((R)-4-{4-[(2-methoxy-ethylcarbamoyl)-methoxy]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-((R)-4-{4-[(2-methoxy-ethylcarbamoyl)-methoxy]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-morpholin-4-yl-2-oxo-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide; (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-2,5-dioxo-4-[4-(2-oxo-2-pyrrolidin-1-yl-ethoxy)-phenyl]-imidazolidin-1-yl}-3-phenyl-butyramide; (2S,3S)-2-[(R)-4-(4-Dimethylcarbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-[(R)-4-(4-Methylcarbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-((R)-4-{4-[(2-Methoxy-ethylcarbamoyl)-methoxy]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{(R)-4-[4-(2-Morpholin-4-yl-2-oxo-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{(R)-2,5-Dioxo-4-[4-(2-oxo-2-pyrrolidin-1-yl-ethoxy)-phenyl]-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide; (2S,3S)-2-{(R)-4-[4-(2-Azetidin-1-yl-2-oxo-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide and (2S,3S)-N-(4-Cyclopropanecarbonyl-thiazol-2-yl)-2-[(R)-4-(4-methylcarbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide.
[0113] “Alkyl” denotes a straight-chained, branched or cyclic saturated aliphatic hydrocarbon. Preferably, alkyl denotes a lower alkyl group i.e., a C 1 -C 6 alkyl group and includes methyl, ethyl, propyl, isopropyl, butyl, t-butyl, 2-butyl, pentyl, hexyl, and the like. Generally, lower alkyl is preferably C 1 -C 4 alkyl, and more preferably C 1 -C 3 alkyl. Examples of cycloalkyl groups are moieties having 3 to 10, preferably 3 to 7 carbon atoms including cyclopropyl, cyclopentyl and cyclohexyl groups.
[0114] “Aryl” means a monovalent, monocyclic or bicyclic, aromatic carbocyclic hydrocarbon radical, preferably a 6-10 member aromatic ring system. Preferred aryl groups include, but are not limited to, phenyl, naphthyl, tolyl, and xylyl.
[0115] “Hetero atom” means an atom selected from N, O and S.
[0116] “Heteroaryl” means an aromatic heterocyclic ring system containing up to two rings. Preferred heteroaryl groups include, but are not limited to, thienyl, furyl, indolyl, pyrrolyl, pyridinyl, pyrazinyl, oxazolyl, thiaxolyl, quinolinyl, pyrimidinyl, imidazole and tetrazolyl.
[0117] As mono-, di- or tri-substituents on the aryl or heteroaryl rings one can include hydroxyl, alkoxy, hydroxyl alkoxy, halogen, alkylamines, aniline derivatives, amide derivatives of the aniline derivatives, carboxylic acids, carboxylic acid esters, carboxylic acid amides and methanesulfonyl. When two or more substituents are present on an aryl or heteroaryl ring they may also be present in the form of a fused ring. Such fused rings include, but are not limited to, 3,4-methylenedioxyphenyl and 3,4-ethylenedioxyphenyl.
[0118] “Alkoxy or lower alkoxy” refers to any of the above lower alkyl groups attached to an oxygen atom. Typical lower alkoxy groups include methoxy, ethoxy, isopropoxy or propoxy, butyloxy and the like. Further included within the meaning of alkoxy are multiple alkoxy side chains, e.g. ethoxy ethoxy, methoxy ethoxy, methoxy ethoxy ethoxy and the like and substituted alkoxy side chains, e.g., dimethylamino ethoxy, diethylamino ethoxy, dimethoxy-phosphoryl methoxy and the like. Also included within the meaning of alkoxy are alkoxy side chains bearing additional substituents such as carboxylic acids, carboxylic acid esters and carboxylic acid amides.
[0119] “Pharmaceutically acceptable ester” refers to a conventionally esterified compound of formula I having a carboxyl group, which esters retain the biological effectiveness and properties of the compounds of formula I and are cleaved in vivo (in the organism) to the corresponding active carboxylic acid.
[0120] Information concerning esters and the use of esters for the delivery of pharmaceutical compounds is available in Design of Prodrugs. Bundgaard Hans ed. (Elsevier, 1985). See also, Ansel et. al., Pharmaceutical Dosage Forms and Drug Delivery Systems (6th Ed. 1995) at pp. 108-109; Krogsgaard-Larsen, et al., Textbook of Drug Design and Development (2d Ed. 1996) at pp. 152-191.
[0121] “Pharmaceutically acceptable salt” refers to conventional acid-addition salts or base-addition salts that retain the biological effectiveness and properties of the compounds of the present invention and are formed from suitable non-toxic organic or inorganic acids or organic or inorganic bases. Sample acid-addition salts include those derived from inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfamic acid, phosphoric acid and nitric acid, and those derived from organic acids such as p-toluenesulfonic acid, salicylic acid, methanesulfonic acid, oxalic acid, succinic acid, citric acid, malic acid, lactic acid, fumaric acid, trifluoro acetic acid and the like. Sample base-addition salts include those derived from ammonium, potassium, sodium and, quaternary ammonium hydroxides, such as for example, tetramethylammonium hydroxide. Chemical modification of a pharmaceutical compound (i.e. drug) into a salt is a technique well known to pharmaceutical chemists to obtain improved physical and chemical stability, hygroscopicity, flowability and solubility of compounds. See, e.g., Ansel et al., Pharmaceutical Dosage Forms and Drug Delivery Systems (6th Ed. 1995) at pp. 196 and 1456-1457.
[0122] “Pharmaceutically acceptable,” such as pharmaceutically acceptable carrier, excipient, etc., means pharmacologically acceptable and substantially non-toxic to the subject to which the particular compound is administered.
[0123] “Substituted,” as in substituted aryl or heteroaryl, means that the substitution can occur at one or more positions and, unless otherwise indicated, that the substituents at each substitution site are independently selected from the specified options.
[0124] “Therapeutically effective amount” means an amount of at least one designated compound that significantly inhibits proliferation and/or prevents differentiation of a human tumor cell, including human tumor cell lines.
[0125] The compounds of the present invention are useful in the treatment or control of cell proliferative disorders such as inflammatory/autoimmune disorders, e.g., restenosis, cognative disorders e.g., dementia and Alzeheimer's disease. CNS disorders, e.g., neuropathic pain and, in particular, oncological disorders. These compounds and formulations containing said compounds may be useful in the treatment or control of solid tumors, such as, for example, breast, colon, lung and prostate tumors.
[0126] The compounds of formula I as well as their salts have at least one asymmetric carbon atom and therefore may be present as mixtures of different stereoisomers. The various isomers can be isolated by known separation methods, e.g., chromatography.
[0127] A therapeutically effective amount of a compound in accordance with this invention means an amount of compound that is effective to prevent, alleviate or ameliorate symptoms of disease or prolong the survival of the subject being treated. Determination of a therapeutically effective amount is within the skill in the art.
[0128] The therapeutically effective amount or dosage of a compound according to this invention can vary within wide limits and may be determined in a manner known in the art. Such dosage will be adjusted to the individual requirements in each particular case including the specific compound(s) being administered, the route of administration, the condition being treated, as well as the patient being treated. In general, in the case of oral or parenteral administration to adult humans weighing approximately 70 Kg, a daily dosage of about 10 mg to about 10,000 mg, preferably from about 200 mg to about 1,000 mg, should be appropriate, although the upper limit may be exceeded when indicated. The daily dosage can be administered as a single dose or in divided doses, or for parenteral administration, it may be given as continuous infusion.
Reaction Schemes
[0129] Compounds of formula 6, where R8=alkyl or substituted alkyl, can be prepared according to the method outlined in scheme 1. As set forth in scheme 1, the known compound 1 when treated with di-tert-butyl dicarbonate in refluxing pyridine gave compound 2. Compound 2 was then hydrolyzed with lithium hydroxide in a mixture of tetrahydrofuran and water to give the corresponding carboxylic acid 3. Compound 3 was first reacted with 2-chloro-4,5-dimethoxy-1,3,5-triazine and N-methylmorpholine in tetrahydrofuran, then with the N,O-dimethylhydroxylamine hydrochloride and triethylamine to give the compound with formula 4. Compound 4 can be converted to ketones of formula 5 using alkyl magnesium chloride or bromide salts (Grignard reagents) in ethereal solvents. Compounds of formula 6 are then obtained after treatment of compounds of formula 5 with acid to effect removal of the tert-butyloxycarbonyl group e.g trifluoroacetic acid.
[0130] As set forth in scheme 2, an alternative method of functionalizing compound 4 is via formation of the bis-tert-butoxycarbonylamino derivative 7 with di-tert-butyl dicarbonate and potassium carbonate. Compound 7 can then be converted into ketones of formula 8 by reaction with the appropriate organometallic reagent e.g. organolithium reagents. Compounds of formula 6 are obtained from compounds of formula 8 after treatment with acid to effect removal of the tert-butyloxycarbonyl group e.g. trifluoroacetic acid.
[0131] In the case where the substituent R8 contains a reactive functional group further modification of this substituent may be possible by appropriate use of known methods and chemical transformations by one knowledgable in the field. Such modifications may be possible immediately after introduction of the R8 substituent or on any subsequent derivative bearing this substituent.
[0132] In addition, the ketone functional group present in compounds of formula 5, 6 and 8 is a reactive functional group and may be amenable to further chemical transformations using methods known in the field of organic chemistry and by one knowledgable in the field. Such modifications may be possible immediately after formation of the ketone functional group or on any subsequent derivative bearing this substituent.
[0133] As set forth in scheme 3, a solution of substituted 2-propenoic acid 9 and triethylamine in dry tetrahydrofuran at low temperature, e.g. −78° C., is treated with trimethylacetyl chloride and then with the anion of (S)-(+)-4-phenyl-2-oxazolidinone anion (generated with n-butyl lithium) to give a compounds of formula 10. Compounds of formula 10 react with an appropriate Grignard reagents in the presence of copper(I) bromide-dimethyl sulfide complex to give compounds of formula 11. The Grignard reagents utilized in this transformation may contain aryl, substituted aryl, heteroaryl or substituted heteroaryl groups which are incorporated in to compounds of formula 11. Compounds of formula 11 were converted to compounds of formula 12 by treatment first with a strong base e.g. potassium hexamethyldisilazane followed by treatment with 2,4,6 triisopropylphenylsulfonyl azide. Compounds of formula 12 were hydrogenolyzed in the presence of di-tert-butyl dicarbonate and palladium on charcoal to give compounds of formula 13. Compounds of formula 14 were obtained from compounds of formula 13 by treatment with hydrogen peroxide and lithium hydroxide.
[0134] The R9 group shown in scheme 3 can be either alkyl or substituted alkyl. In the case where R9 is substituted alkyl, the substituent may be unreactive to the conditions employed in subsequent chemical transformations on remote parts of the molecule so that the R9 group persists into the compounds claimed in the present invention in a chemically unchanged form. Alternatively, the R9 group may contain a potentially reactive functional group present in a protected form from which the functional group may be liberated at an appropriate point during subsequent chemical transformations. For a more complete description of the utility of protecting groups see Protecting Groups in Organic Synthesis, 3 rd Edition, T. W. Greene and P. G. M. Wuts, Wiley-Interscience.
[0135] The R10 group shown in scheme 3 can be either hydrogen, alkyl, substituted alkyl or halogen.
[0136] As set forth in scheme 4, compounds of formula 14 were converted to the acyl fluorides of formula 15 using cyanuric fluoride in the presence of pyridine in dichloromethane. Compounds of formula 15 were treated with compounds of formula 6 in the presence of N-methyl morpholine and the reaction catalyzed by the addition of 4-dimethylaminopyridine and microwave irradiation to give an internal reaction temperature between 100 and 120° C. Compounds of formula 6 may be known compounds, e.g. R8=OMe, or compounds prepared according to known methods, or compounds prepared according to the methods outlined in schemes 1 and 2. In this way, compounds of formula 16 were obtained. Compounds of formula 16 were deprotected with trifluoroacetic acid to give a compounds of formula 17. Compounds of formula 17 were coupled with α-amino acid derivatives, preferably an enantiomerically enriched phenyl glycine derivative (either a known compound or a compound prepared by known methods), with 1-hydroxybenzotriazole and O-benzotriazol-1-yl-N,N,N′,N′-tetramethyluroniumhexaflurorophosphate to give compounds of formula 18. In the case when the α-amino acid derivative used is a phenyl glycine derivative R11 may be hydroxy, alkoxy, substituted alkoxy, acylated amine, substituted sulfone and phosphate. In the case when the α-amino acid derivatives is an enantiomerically enriched phenyl glycine derivative these compounds may be conveniently prepared from 4-hydroxyphenyl glycine for which both enantiomers are commercially available. Compounds of formula 18 were reacted with trifluoroacetic acid to give compounds of formula 19 by removal of the tert-butylcarbamate protecting group. Compounds of formula 19 were treated with diphosgene and diisopropylethyl amine to give substituted hydantoins of formula 20 in a solvent such as dichloromethane, tetrahydrofuran or a mixture of tetrahdrofuran and toluene.
[0137] The reaction conditions for the above reactions can vary to a certain extent.
[0138] Methods to perform the above described reactions and processes are known in the art or can be deduced in analogy from the examples. Starting materials are commercially available or can be made by methods analogous to those described in the examples.
[0139] The following examples shall illustrate preferred embodiments of the present invention but are not intended to limit the scope of the invention.
EXAMPLE 1
(2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0140]
[0141] (1) 1-(2-Amino-thiazol-4-yl)-ethanone was prepared using the 3 step procedure outlined in steps (1a) to (1c) and then converted into (2S,3S)-N-(4-acetyl-thiazol-2-yl)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide according to the procedures outlined in steps (2) to (7).
[0142] (1a) Sulfuryl chloride (97% purity) (18.7 mL, 226 mmol) was added dropwise over 1 hour to a stirred solution of 2,3-butanedione (97% purity) (20 g, 225 mmol) in benzene (80 mL) at 60° C. and the mixture left to stir at this temperature overnight. The benzene was removed in vacuo and the residue was purified by distillation to give 1-chloro-2,3-butanedione as a yellow liquid, b.p.=95 to 105° C. (≈10 mmHg), (16.2 g, 60%).
[0143] (1b) To a stirred mixture of thiourea (8.87 g, 115 mmol) in ethanol (20.9 mL) was added 1-chloro-2,3-butanedione (13.90 g, 115 mmol) dropwise, a slight exothermic reaction resulted. The mixture was stirred at ambient temperature for 1 hour. The reaction mixture was filtered and the precipitate washed with ethyl ether (2×). The tan solid was air dried then dried under high vacuum overnight to give 1-(2-amino-thiazol-4-yl)-ethanone hydrochloride as a tan solid (21.5 g, 97%).
[0144] (1c) 1-(2-Amino-thiazol-4-yl)-ethanone hydrochloride (5.6 g 29.1 mmol) was dissolved in water (15 mL) and cooled in an ice bath. To this was added dropwise 17 N ammonium hydroxide (15 mL, 105 mmol). The resulting mixture was stirred for 15 minutes than filtered and washed with cold water (3×), cold methanol (3×50 mL), ethyl ether (3×10 mL). The precipitate was dried first by passing air through the material and then in vacuo to give 1-(2-amino-thiazol-4-yl)-ethanone as a pale yellow solid (2.6 g, 57%).
[0145] (2S,3S)-2-tert-Butoxycarbonylamino-3-phenyl-butyric acid (1.94 g, 6.93 mmol) and pyridine (0.63 mL, 7.74 mmol) were dissolved in dichloromethane (50 mL) at −10° C. Cyanuric fluoride (1.80 mL, 21.1 mmol) was added dropwise. The mixture was stirred for 1 hour and ice-water was added. The mixture was extracted with dichloromethane (2×). The organic extracts were washed with water, brine and dried (sodium sulfate). Evaporation of the solvents gave crude ((1S,2S)-1-fluorocarbonyl-2-phenyl-propyl)-carbamic acid tert-butyl ester (2.2 g) as a cloudy oil which was used in the next step.
[0146] Crude ((1S,2S)-1-fluorocarbonyl-2-phenyl-propyl)-carbamic acid tert-butyl ester (2.2 g, ≈6.93 mol), 1-(2-amino-thiazol-4-yl)-ethanone (1.0 g, 7.0 mmol), 4-methyl morpholine (1.56 mL, 14 mmol) and N,N-dimethylaminopyridine (10 mg, 0.082 mmol) were dissolved in tetrahydrofuran (20 mL). The mixture was microwaved at 120° C. for 15 minutes. The solution was diluted with ethyl acetate and washed with 1.5 M aqueous potassium hydrogen sulfate, water and brine. After drying (sodium sulfate), filtration and evaporation of the solvents, [(1S,2S)-1-(4-acetyl-thiazol-2-ylcarbamoyl)-2-phenyl-propyl]-carbamic acid tert-butyl ester (2.8 g, 89%) was obtained as a yellow foam.
[0147] [(1S,2S)-1-(4-Acetyl-thiazol-2-ylcarbamoyl)-2-phenyl-propyl]-carbamic acid tert-butyl ester (2.8 g, 6.25 mmol) was dissolved in dichloromethane (42 mL) in an ice bath. Trifluoroacetic acid (35 mL) was added. After 30 minutes, the reaction mixture was evaporated and the residue was precipitated with hexanes/ether. The mixture was stirred vigorously for 10 minutes and then filtered. The solid was partitioned between aqueous sodium bicarbonate and dichloromethane. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic extracts were washed with brine and dried (sodium sulfate). Evaporation of the solvents gave (2S,3S)-N-(4-acetyl-thiazol-2-yl)-2-amino-3-phenyl-butyramide (1.9 g, 95%) as a white solid.
[0148] (5) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-amino-3-phenyl-butyramide (1.8 g, 5.64 mmol), (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine (prepared according to the procedure of Hyun, M. H., et al. J. Liq. Chrom . & Rel. Technol. 2002, 25, 573-588.) (1.67 g, 5.9 mmol), O-benzotriazol-1-yl-N,N,N′,N′-tetramethyluronium hexaflurorophosphate (2.35 g, 6.2 mmol) and diisopropylethyl amine were dissolved in dimethylformamide (20 mL) in an ice bath. 1-Hydroxybenzotriazole (0.84 g, 6.2 mmol) in dimethylformamide (5 mL) was added dropwise. Stirring was continued for 30 minutes at 0° C. The reaction mixture was diluted with ethyl acetate and the mixture washed with water and brine. The organic layer was diluted with an equal volume of dichloromethane, filtered through a pad of silica gel with a layer of sodium sulfate on the top and then eluted with 1:1 ethyl acetate/dichloromethane. Evaporation of the solvents gave a white solid which was triturated with ether/hexane to give [(R)-[(1S,2S)-1-(4-acetyl-thiazol-2-ylcarbamoyl)-2-phenyl-propylcarbamoyl]-(4-methoxy-phenyl)-methyl]-carbamic acid tert-butyl ester (3.1 g, 97%).
[0149] (6) [(R)-[(1S,2S)-1-(4-Acetyl-thiazol-2-ylcarbamoyl)-2-phenyl-propylcarbamoyl]-(4-methoxy-phenyl)-methyl]-carbamic acid tert-butyl ester (3.1 g, 5.2 mmol) was stirred in dichloromethane (50 mL) in an ice-bath. Trifluoroacetic acid (50 mL) was added and the solution was stirred for 1 hour. The reaction mixture was evaporated and the residue was precipitated with hexanes/ether. The mixture was stirred vigorously for 10 minutes and then filtered. The solid was partitioned between aqueous sodium bicarbonate and dichloromethane. The organic layer was separated and the aqueous layer extracted with dichloromethane. The combined organic extracts were washed with brine and dried (sodium sulfate). Evaporation of the solvents gave (2S,3S)-N-(4-acetyl-thiazol-2-yl)-2-[(R)-2-amino-2-(4-methoxy-phenyl)-acetylamino]-3-phenyl-butyramide (2.7 g, 90% pure) as a white solid.
[0150] (7) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-2-amino-2-(4-methoxy-phenyl)-acetylamino]-3-phenyl-butyramide (2.7 g, 90% purity, 5.2 mmol) and diisopropylethylamine (4.2 mL, 23.6 mmol) in tetrahydrofuran (50 mL) were added to a solution of diphosgene (0.48 mL, 4 mmol) in a mixture of toluene (50 mL) and tetrahydrofuran (50 mL) over 10 minutes at 0° C. The mixture was stirred at 0° C. for 20 minutes and diluted with ethyl acetate. The mixture was washed with water, brine and dried (sodium sulfate). Evaporation of the solvents and chromatography of the residue over silica gel with 0.4-1% v/v methanol in dichloromethane gave (2S,3S)-N-(4-acetyl-thiazol-2-yl)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide (2.36 g, 92%) as a white solid.
[0151] HRMS: Obs. Mass, 493.1538. Calcd. Mass, 493.1540 (M+H).
EXAMPLE 2
[0152] In a manner similar to that described in Example 1, the following compounds were prepared.
a) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-hydroxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0153]
[0154] HRMS: Obs. Mass, 479.1385. Calcd. Mass, 479.1384 (M+H).
b) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-hydroxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide
[0155]
(R)-tert-Butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared as follows. (R)-tert-butoxycarbonylamino-(4-hydroxy-phenyl)-acetic acid (2.67 g, 10 mmol) (Salituro, G. M.; Townsend, C. A. J. Am. Chem. Soc. 1990, 112, 760-770.) was dissolved in dimethylformamide (70 mL) in an ice bath. Sodium hydride (0.88 g, 60% in mineral oil, 22 mmol) was added in small portions. The mixture was warmed up to 10° C. for 1 hour. 2-(2-Bromo-ethoxy)-tetrahydropyran (1.7 mol, 11 mmol) in dimethylformamide (20 mL) was added drop wise. The reaction mixture was stirred for 24 hours and then diluted with ice-water. The mixture was extracted with ethyl acetate. The aqueous layer was cooled in an ice bath and acidified using 1.5 M aqueous potasium hydrogen sulfate to pH=2-3. The resulting mixture was extracted with ethyl acetate (5×), washed with water (5×), brine and dried (sodium sulfate). Evaporation of the solvents gave (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydropyran-2-yloxy)-ethoxy]-phenyl}-acetic acid as a solid white foam (3.2 g, 82%).
[0156] HRMS: Obs. Mass, 523.1645. Calcd. Mass, 523.1646 (M+H).
c) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide
[0157]
(R)-tert-Butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0158] HRMS: Obs. Mass, 537.1803. Calcd. Mass, 537.1803 (M+H).
d) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-((R)-4-{4-[2-(2-methoxy-ethoxy)-ethoxy]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-butyramide
[0159]
(R)-tert-Butoxycarbonylamino-{4-[2-(2-methoxy-ethoxy)-ethoxy]-phenyl}-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0160] HRMS: Obs. Mass, 581.2067. Calcd. Mass, 581.2065 (M+H).
e) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-ethoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide
[0161]
(R)-tert-Butoxycarbonylamino-[4-(2-ethoxy-ethoxy)-phenyl]-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0162] HRMS: Obs. Mass, 551.1963. Calcd. Mass, 551.1959 (M+H).
f) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-dimethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide, trifluoro-acetic acid salt
[0163]
(R)-tert-Butoxycarbonylamino-[4-(2-dimethylamino-ethoxy)-phenyl]-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-[4-(2-diethylamino-ethoxy)-phenyl]-acetic acid in Example 2g.
[0164] HRMS: Obs. Mass, 550.2117, Calcd. Mass, 550.2119 (M+H)
g) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-diethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide, trifluoro-acetic acid salt
[0165]
(R)-tert-Butoxycarbonylamino-[4-(2-diethylamino-ethoxy)-phenyl]-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared as follows:
[0166] To a suspension of sodium hydride (43.8 mg, 95% Aldrich) in anhydrous N,N-dimethylformamide (4 mL), was added dropwise a solution of (R)-tert-butoxycarbonylamino-(4-hydroxyphenyl)-acetic acid (200.0 mg, 0.749 mmol) at 0° C. After addition, the reaction mixture was allowed to stir at ambient temperature for 20 minutes. A cooled solution of 2-bromoethyl-N,N-diethylamine hydrochloride (234 mg, 0.91 mmol) in N,N-dimethylformamide (2 mL), was treated with sodium hydride (23 mg, 1.00 mmol), and was then added slowly to the above suspension at 0° C. The reaction was allowed to stir at ambient temperature for 17 hours before it was quenched and neutralized by pouring into 1N aqueous hydrochloric acid. The resulting mixture was lyophlized dry to give the product (contaminated with inorganic salts) which was used without further purification (61.9.5 mg).
[0167] HRMS: Obs. Mass, 578.2430, Calcd. Mass, 578.2432 (M+H).
h) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-ethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0168]
(R)-tert-Butoxycarbonylamino-(4-ethoxyphenyl)-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-(4-methoxyphenylglycine) in Example 1d), was prepared in a manner similar to that described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b).
[0169] HRMS: Obs. Mass, 507.1696. Calcd. Mass, 507.1697 (M+H).
i) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(S)-4-[4-(2-dimethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide, trifluoro-acetic acid salt
[0170]
(2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(S)-4-[4-(2-dimethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide was isolated as the minor isomer following the last step in the preparation described in Example 2f.
[0171] HRMS: Obs. Mass, 550.2118, Calcd. Mass, 550.2119 (M+H).
j) (4-{1-[(1S,2S)-1-(4-Acetyl-thiazol-2-ylcarbamoyl)-2-phenyl-propyl]-2,5-dioxo-imidazolidin-4-yl}-phenyl)-phosphonic acid diethyl ester
[0172]
(±)-tert-Butoxycarbonylamino-{4-phenyl phosphonic acid diethyl ester}-acetic acid, which was used in place of (R)-N-(tert-butyloxycarbonyl-(4-methoxyphenylglycine) in Example 1d, was prepared as follows.
[0173] (1) To a cold solution of (R)-tert-butoxycarbonylamino-(4-hydroxyphenyl)-acetic acid benzyl ester (prepared as described in J. Med. Chem. 1991, 34, 956-968) (2.0 g, 5.60 mmol) in dry methylene chloride (60 mL) was added N-phenylbis(trifluoromethanesulphonamide) (4.03 g, 11.28 mmol) and diisopropylethylamine (1.0 mL, 5.74 mmol). The reaction mixture was stirred at room temperature for 48 hours. The solvent was removed in vacuo and the residue was dissolved in ethyl acetate, washed with 10% aqueous potassium carbonate (2×), water and brine and dried over sodium sulfate. The solvent was removed in vacuo, and the product was purified by chromatography over silica gel eluted first with 50% methylene chloride in hexanes and then with 30% ethyl acetate in hexanes to afford tert-butoxycarbonylamino-(4-trifluoromethane-sulfonyloxy-phenyl)-acetic acid benzyl ester (2.62 g, 96%).
[0174] To a solution of tert-butoxycarbonylamino-(4-trifluoromethane-sulfonyloxy-phenyl)-acetic acid benzyl ester (2.2 g, 4.50 mmol) in acetonitrile (10 mL) was added diethylphosphite (643 μL, 5.00 mmol) followed by N-methylmorpholine (691 μL, 6.30 mmol). The mixture was purged with nitrogen and tetrakis-triphenylphosphine palladium (260 mg, 0.23 mmol, 15 mol %) was added. The reaction mixture was heated to 75° C. overnight then cooled to room temperature and diluted with ethyl acetate (50 mL). The mixture was poured into a separatory funnel containing ethyl acetate (100 mL) and washed with 0.2M aqueous hydrochloric acid (2×), water (2×), brine and dried over sodium sulfate. The solvent was removed in vacuo, and the product was chromatographed over silica gel gradient eluted between 10 to 75% ethyl acetate in hexanes to afforded tert-butoxycarbonylamino-[4-(diethoxy-phosphoryl)-phenyl]-acetic acid benzyl ester (2.0 g, 93%).
[0175] To solution of tert-butoxycarbonylamino-[4-(diethoxy-phosphoryl)-phenyl]-acetic acid benzyl ester (2.0 g, 4.2 mmol) in ethanol (20 mL) was added 10% palladium on activated carbon (200 mg). The mixture was stirred under an atmosphere of hydrogen at atmospheric pressure for two days. The reaction mixture was filtered through a pad of Celite®. The solids were washed with ethanol and the combined ethanolic filtrate was concentrated in vacuo to afford (±)-tert-butoxycarbonylamino-{4-phenyl phosphonic acid diethyl ester}-acetic acid (1.5 g; 92%). HRMS: Obs. Mass, 388.1516. Calcd. Mass, 388.1520 (M+H).
[0176] HRMS: Obs. Mass, 599.1722. Calcd. Mass, 599.1724 (M+H).
k) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[4-(4-dimethylamino-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0177]
Prepared as described in Example 1 except that tert-butoxycarbonylamino-(4-dimethylamino-phenyl)-acetic acid was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine.
[0178] HRMS: HRMS: Obs. Mass, 506.1858. Calcd. Mass, 506.1857 (M+H)
EXAMPLE 3
(2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-pentanoic acid (4-acetyl-thiazol-2-yl)-amide
[0179]
[0180] (1) To a solution of 2-pentenoic acid (5.44 g, 54 mmol) and triethylamine (6 g, 60 mmol) in anhydrous tetrahydrofuran (120 mL) under nitrogen at −78° C. was added trimethylacetyl chloride (7.36 mL, 60 mmol). The reaction mixture was stirred at −78° C. for 10 minutes, 0° C. for 1 hour, then re-cooled to −78° C. At the same time, in a seperate flask charged with a solution of (S)-(+)-4-phenyl-2-oxazolidinone (8.86 g, 54 mmol) in anhydrous tetrahydrofuran (130 mL) under nitrogen at −78° C. was added dropwise a solution of n-butyl lithium (22 mL, 54 mmol, 2.5 M in hexanes). The mixture was stirred at −78° C. for 20 minutes and then transferred via a cannula into the reaction flask containing the mixed anhydride at −78° C. The reaction mixture was stirred at 0° C. for 1 hour, then warmed to room temperature and stirred for 18 hours. The mixture was quenched with saturated aqueous ammonium chloride solution (200 mL), concentrated to about half of its original volume under reduced pressure to remove tetrahydrofuran. The remaining mixture was extracted with ethyl acetate (2×250 mL). The organic layer was separated, combined, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by chromatography over silica gel eluted with 2:1 ethyl acetate/hexanes to give (S)-3-((E)-pent-2-enoyl)-4-phenyl-oxazolidin-2-one as a white foam (9.9 g, 75%).
[0181] (2) To a suspension of copper (I) bromide dimethyl sulfide complex (12.4 g, 60.6 mmol) in dry tetrahydrofuran (150 mL) at −10° C. was added phenyl magnesium chloride solution (30.3 mL, 60.6 mmol, 2 M in tetrahydrofuran). The reaction mixture was stirred at −10° C. for 1 hour, then a solution of (S)-3-((E)-pent-2-enoyl)-4-phenyl-oxazolidin-2-one (9.9 g, 40.4 mmol) in tetrahydrofuran (100 mL) was added dropwise via cannula. The reaction mixture was stirred at −10° C. for 0.5 hours, then at room temperature for 2 hours. The mixture was quenched with saturated aqueous ammonium chloride solution (150 mL), concentrated under reduced pressure to half of its volume. The mixture was extracted with ethyl acetate (2×250 mL). The organic layer was separated, combined and dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by chromatography over silica gel eluted with 2:1 ethyl acetate/hexanes to give (S)-4-phenyl-3-((R)-3-phenyl-pentanoyl)-oxazolidin-2-one as a colorless oil which solidified on standing at room temperature (9.56 g, 73%).
[0182] (3) To a solution of (S)-4-phenyl-3-((R)-3-phenyl-pentanoyl)-oxazolidin-2-one (8:81 g, 27.2 mmol) in dry tetrahydrofuran (200 mL) under nitrogen at −78° C. was added potassium hexamethyldisilazide (45 mL, 40.8 mmol, 0.91 M in tetrahydrofuran). The reaction mixture was stirred at −78° C. for 1 hour, then a pre-cooled solution of 2,4,6-triisopropylbenzenesulfonyl azide (9.6 g, 31 mmol) in tetrahedrofuran (200 mL) at −78° C. was added dropwise via cannula. The reaction mixture was stirred at −78° C. for 1.5 hours and then acetic acid (7.5 g, 125 mmol) was added. The reaction mixture was warmed to 35° C. in a water bath and stirred for 2 hours, during which period of time thin layer chromatography analysis indicated the formation of desired product as a major component. The reaction mixture was concentrated to a smaller volume, then poured into water, and extracted with ethyl acetate (2×200 mL). The organic layers were separated, combined, dried over sodium sulfate and concentrated. The residue was purified by chromatography over silica gel eluted with 2:1 dichloromethane/hexanes to give (S)-3-((2S,3S)-2-azido-3-phenyl-pentanoyl)-4-phenyl-oxazolidin-2-one as a white solid. Further purification by precipitation of an ethyl acetate solution with hexanes yielded the product as a white solid (6.08 g, 36%).
[0183] (4) To a solution of (S)-3-((2S,3S)-2-azido-3-phenyl-pentanoyl)-4-phenyl-oxazolidin-2-one (4.0 g, 11 mmol) and di-tert-butyl dicarbonate (4.8 g, 22 mmol) in ethyl acetate (100 mol) was added 10% palladium on carbon (2 g) under nitrogen. The resulting suspension was vigorously shaken under an atmosphere of hydrogen (55 psi) in a Parr apparatus for 20 hours. The mixture was then filtered through a short pad of celite and the filtrate was concentrated. The residue was purified by chromatography over silica gel eluted with 1:4 ethyl acetate/hexanes to give [(1S,2S)-1-((S)-2-oxo-4-phenyl-oxazolidine-3-carbonyl)-2-phenyl-butyl]-carbamic acid tert-butyl ester as a white foam (4.38 g, 90%).
[0184] (5) To a solution of [(1S,2S)-1-((S)-2-oxo-4-phenyl-oxazolidine-3-carbonyl)-2-phenyl-butyl]-carbamic acid tert-butyl ester (4.38 g, 10 mmol) in a mixture of tetrahydrofuran and water (3:1, 60 mL) at −10° C. was added sequentially a solution of hydrogen peroxide in water (11 mL, 100 mmol, 30%) and an aqueous solution (15 mL) of lithium hydroxide monohydrate (1.23 g, 30 mmol). The reaction mixture was stirred at −10° C. and the progress of the reaction was monitored by thin layer chromatography. After 3 hours, TLC analysis indicated almost complete consumption of starting material. Saturated aqueous sodium sulfite solution (100 mL) was added. The mixture was concentrated to half of its original volume under reduced pressure to remove tetrahydrofuran and then extracted with dichloromethane (2×100 mL). The aqueous layer was separated, acidified to pH=2-3 with aqueous citric acid solution and extracted with ethyl acetate (2×300 mL). The organic layers were separated, combined and dried over sodium sulfate, concentrated under reduced pressure and dried in vacuo to give (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-pentanoic acid as a white foam (1.7 g, 58%).
[0185] (6) In a manner similar to that described in Example 1, (2S,3S)-N-(4-acetyl-thiazol-2-yl)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-pentanoic acid (4-acetyl-thiazol-2-yl)-amide (RO4922706) was prepared from (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-pentanoic acid and 1-(2-amino-thiazol-4-yl)-ethanone.
[0186] HRMS: Obs. Mass, 507.1701. Calcd. Mass, 507.1697 (M+H).
EXAMPLE 4
(2S,3S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0187]
[0188] (1) 2-Amino-thiazole-4-carboxylic acid ethyl ester (Kumar, R.; Rai, D. et al. Heterocyclic Communications 2002, 8, 521-530) (34.44 g, 0.20 mol) and di-tert-butyl dicarbonate (65.47 g, 0.30 mol) in pyridine (1000 mol) were heated at reflux for 4.5 hours. More di-tert-butyl dicarbonate (65.47 g, 0.3 mol) was added and refluxing continued for 1.5 hours. The reaction mixture was partitioned between ethyl acetate and water. The organic phase was washed well with water, dried (magnesium sulfate) and evaporated. Chromatography of the residue over silica gel using 3:1 ethyl acetate/dichloromethane gave 2-tert-butoxycarbonylamino-thiazole-4-carboxylic acid ethyl ester as a tan solid (52.35 g, 96%).
[0189] (2) Lithium hydroxide monohydrate (20.16 g, 0.48 mol) was added to a stirred solution of 2-tert-butoxycarbonylamino-thiazole-4-carboxylic acid ethyl ester (52.35 g, 0.192 mol) in a mixture of tetrahydrofuran (800 mL) and water (200 mL). The mixture was stirred over night. 1 N Aqueous hydrochloric acid (480 mL) was added and the reaction mixture concentrated in vacuo to remove tetrahydrofuran. The mixture was then diluted with water and filtered. The solid was washed with water, ether and dried overnight to give 2-tert-butoxycarbonylamino-thiazole-4-carboxylic acid (43.9 g, 94%).
[0190] (3) A solution of 2-tert-butoxycarbonylamino-thiazole-4-carboxylic acid (14 g, 0.0573 mol), 2-chloro-4,6-dimethoxy-1,3,5-triazine (10.06 g, 0.0573 mol) and N-methyl morpholine (5.79 g, 0.0573 mol) in tetrahydrofuran was stirred for 2 hours at room temperature. N,O-Dimethylhydroxylamine hydrochloride (5.59 g, 0.0573 mmol) and triethylamine (5.59 g, 0.0573 mol) were added and the mixture was stirred for 3 days. The reaction mixture was evaporated and ethyl acetate was added. The reaction mixture was washed with 1 N aqueous hydrochloric acid and then washed with saturated aqueous sodium bicarbonate. [4-(Methoxy-methyl-carbamoyl)-thiazol-2-yl]-carbamic acid tert-butyl ester (14.5 g, 88%) was obtained as a tan tar after drying (magnesium sulfate) and evaporation.
[0191] (4) A solution of ethyl magnesium chloride (126 mL, 0.252 mol, 2 M in tetrahydrofuran) was stirred and cooled to −70° C. on a dry ice/acetone bath. A solution of [4-(methoxy-methyl-carbamoyl)-thiazol-2-yl]-carbamic acid tert-butyl ester (14.5 g, 0.0504 mol) in tetrahydrofuran (200 mL) was added dropwise over approximately 5 minutes. The mixture was stirred for 1 hour. The cooling bath was removed and stirring continued for an additional 2 hours. The mixture was poured into a mixture of ice and saturated aqueous ammonium chloride solution and then extracted with ethyl acetate. The organic extracts were combined, washed with brine, dried over magnesium sulfate and evaporated to give an off white solid which was purified by chromatography over a 350 g pad of silica gel eluted with 4:1 ethyl acetate/dichloromethane to afford (4-propionyl-thiazol-2-yl)-carbamic acid tert-butyl ester (7.09 g, 55%) as an off white solid.
[0192] (5) (4-Propionyl-thiazol-2-yl)-carbamic acid tert-butyl ester (5.0 g, 19.5 mmol) was suspended in dichloromethane (100 mL) at 0° C. Trifluoroacetic acid (100 mL) was added and the mixture was stirred at 0° C. for 1.5 hours. The cooling bath was removed and stirring was continued for 1 hour prior to concentration of the reaction mixture in vacuo. The residue was triturated with ether and filtered. The solid was dissolved in a mixture of dichloromethane and saturated aqueous sodium bicarbonate solution. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic extracts were washed with brine, dried over sodium sulfate and evaporated to give 1-(2-amino-thiazol-4-yl)-propan-1-one (2.3 g, 75%).
[0193] (6) In a similar manner as that described in Example 1, (2S,3S)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide was prepared from (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid and 1-(2-amino-thiazol-4-yl)-propan-1-one.
[0194] HRMS: Obs. Mass, 507.1697. Calcd. Mass, 507.1097 (M+H).
EXAMPLE 5
[0195] In a manner similar to that described in Example 4, the following compounds were prepared.
a) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0196]
(2R)-tert-Butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid was prepared according to the procedure described by Bohme, E. H. W. et al., J. Med. Chem. 1980, 23, 405412.
[0197] HRMS: Obs. Mass, 535.1645. Calcd. Mass, 535.1646 (M+H).
b) (2S,3S)-2-[(R)-4-(4-Ethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0198]
(R)-tert-Butoxycarbonylamino-{4-ethoxyphenyl}-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-(4-methoxyphenylglycine) in Example 1d, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0199] HRMS: Obs. Mass, 611.2166. Calcd. Mass, 611.2170 (M+H).
c) (2S,3S)-2-[(R)-4-(4-Hydroxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0200]
[0201] LR-MS: 493 (M+H).
d) (2S,3S)-2-{(R)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0202]
(R)-tert-Butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0203] HRMS: Obs. Mass, 551.1958. Calcd. Mass, 551.1959 (M+H).
[0204] e) (2S,3S)-2-{(S)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide was isolated as a by product from the synthesis of (2S,3S)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide.
[0205] HRMS: Obs. Mass, 551.1692. Calcd. Mass, 551.1959 (M+H).
f) (2S,3S)-2-{(R)-4-[4-(2-Hydroxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0206]
(R)-tert-Butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared in Example 2b.
[0207] HRMS: Obs. Mass, 537.1804. Calcd. Mass, 537.1803 (M+H).
g) (2S,3S)-2-((R)-4-{4-[2-(2-Methoxy-ethoxy)-ethoxy]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0208]
(R)-tert-Butoxycarbonylamino-{4-[2-(2-methoxy-ethoxy)-ethoxy]-phenyl}-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0209] HRMS: Obs. Mass, 595.2217. Calcd. Mass, 595.2221 (M+H).
h) (2S,3S)-2-{(R)-4-[4-(2-Ethoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0210]
(R)-tert-Butoxycarbonylamino-[4-(2-ethoxy-ethoxy)-phenyl]-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0211] HRMS: Obs. Mass, 565.2120. Calcd. Mass, 565.2116 (M+H).
i) (2S,3S)-2-{(R)-4-[4-(2-Dimethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide, trifluoro-acetic acid salt
[0212]
(R)-tert-Butoxycarbonylamino-[4-(2-dimethylamino-ethoxy)-phenyl]-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-[4-(2-diethylamino-ethoxy)-phenyl]-acetic acid in Example 2g.
[0213] HRMS: Obs. Mass, 564.2266, Calcd. Mass, 564.2275 (M+H).
j) (4-{(R)-2,5-Dioxo-1-[(1S,2S)-2-phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propyl]-imidazolidin-4-yl}-phenoxymethyl)-phosphonic acid dimethyl ester
[0214]
(R)-tert-Butoxycarbonylamino-{4-phenoxymethyl)-phosphonic acid dimethyl ester}-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methoxyphenylglycine in Example 1, was prepared as described in example 8h.
[0215] HRMS: Obs. Mass, 615.1670. Calcd. Mass, 615.1673 (M+H).
k) (2S,3S)-N-(4-Isobutyryl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide
[0216]
(R)-tert-Butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid, which was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine in Example 1d, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0217] 1-(2-Amino-thiazol-4-yl)-2-methyl-propan-1-one, which was used in place of 1-(2-amino-thiazol-4-yl)-ethanone in Example 1c, was prepared in a similar manner as described for the synthesis 1-(2-amino-thiazol-4-yl)-propan-1-one in Example 4.
[0218] HRMS: Obs. Mass, 565.2116. Calcd. Mass, 565.2116 (M+H).
l) (2S,3S)-N-(4-Isobutyryl-thiazol-2-yl)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0219]
1-(2-Amino-thiazol-4-yl)-2-methyl-propan-1-one, which was used in place of 1-(2-amino-thiazol-4-yl)-ethanone in Example 1c, was prepared in a similar manner as described for the synthesis 1-(2-amino-thiazol-4-yl)-propan-1-one in Example 4.
[0220] HRMS: Obs. Mass, 521.1852. Calcd. Mass, 521.1853 (M+H).
m) (2S,3S)-2-{(S)-4-[4-(2-Dimethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide, trifluoro-acetic acid
[0221]
(2S,3S)-2-{(S)-4-[4-(2-Dimethylamino-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide was isolated as the minor isomer following the last step in the preparation described in Example 5i.
[0222] HRMS: Obs. Mass, 564.2274, Calcd. Mass, 564.2275 (M+H).
n) (2S,3S)-2-{2,5-Dioxo-4-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0223]
(1) A solution of (R)-N-(tert-butyloxycarbonyl-(4-hydroxyphenylglycine) (1 g, 3.74 mmol) in dry N,N-dimethylformamide (35 mL) was treated with sodium hydride (60% suspention in mineral oil) (470 mg, 11.97 mmol) at 0° C. After 10 minutes the reaction mixture was warmed to room temperature stirred for an additional 10 minutes at that temperature and then treated with 1-(2-chloroethyl)piperidine hydrochloride (720 mg, 2.93 mmol) and potassium iodide (310 mg, 1.87 mmol). After stirring for 15 minutes, additional of dry N,N-dimethylformamide (50 mL) was added and and the resulting slurry was allowed to stir for 27.5 hours. The reaction mixture was then partitioned between ethyl acetate and water and the aqueous layer adjusted to pH=7 with 1N aqueous hydrochloric acid. The aqueous layer was then lyophilized to give a solid residue that was suspended in tetrahydrofuran and filtered. The solids were washed with tetrafydrofuran (2×) and the combined filtrates concentrated to afford crude (R)-tert-butoxycarbonylamino-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-acetic acid (1.9 g) which was used immediately without further purification.
[0225] (2) (R)-tert-Butoxycarbonylamino-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-acetic acid (740 mg, =1.96 mmol) was dissolved in tetrahydrofuran (30 mL) and (2S,3S)-2-amino-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide (250 mg, 0.78 mmol) (prepared as described in example 4) was added followed by 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (180 mg, 0.94 mmol) at 0° C. The reaction mixture was allowed to slowly warm to room temperature. After stirring for 3.5 hours additional (R)-tert-butoxycarbonylamino-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-acetic acid (320 mg, =0.85 mmol) was added to the reaction mixture. After stirring for an additional 1.5 hours an additional aliquot of (R)-tert-butoxycarbonylamino-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-acetic acid (300 mg, ≈0.82 mmol) was added to the reaction mixture along with additional 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (90 mg, 4.72 mmol). After stirring at room temperature for an additional 1 hour the mixture was partitioned between ethyl acetate and brine, the organic extract was dried over sodium sulfate, concentrated in vacuo and the resulting residue purified by chromatography over silica gel eluted first with ethyl acetate and then gradient eluted with dichloromethane containing from 0 to 10% methanol. {(R)-[(1S,2S)-2-Phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propylcarbamoyl]-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-methyl}-carbamic acid tert-butyl ester was obtained as a white solid (120 mg, 24%).
[0226] HRMS: Obs. Mass, 678.3323. Calcd. Mass, 678.3320 (M+H).
[0227] (3) {(R)-[(1S,2S)-2-Phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propylcarbamoyl]-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-methyl}-carbamic acid tert-butyl ester (110 mg, 0.16 mmol) was dissolved in a 30% v/v solution of trifluoroacetic acid in dichloromethane (5 mL) at 0° C. After stirring for 1.5 hours the reaction mixture was partitioned between ethyl acetate and saturated aqueous sodium bicarbonate solution. The aqueous layer was adjusted to pH=8 by the addition of solid sodium bicarbonate. The aqueous layer was again extracted with ethyl acetate (2×). The combined organic layers was dried over sodium sulfate, filtered and concentrated in vacuo to give crude (2S,3S)-2-{(R)-2-amino-2-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-acetylamino}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide which was used immediately and without further purification.
[0228] (4) Crude (2S,3S)-2-{(R)-2-amino-2-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-acetylamino}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide (≈0.16 mmol) was dissolved in tetrahydrofuran (10 mL) that contained diisopropylethylamine (142 μL, 105 mg, 0.81 mmol) and was transferred via cannula to a solution of diphosgene (14 μL, 23 mg, 0.12 mmol) in tetrahydrofuran (15 mL) at 0° C. The reaction mixture was stirred for 20 minutes and then partitioned between ethyl acetate and water. The organic layer was separated and dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by chromatography over silica gel eluted first with ethyl acetate and then gradient eluted with dichloromethane containing from 0 to 10% methanol. Precipitation of the isolated product from dichloromethane with an excess of hexanes gave (2S,3S)-2-{2,5-dioxo-4-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide as a white solid (26 mg, 27%).
[0229] HRMS: Obs. Mass, 604.2591. Calcd. Mass, 604.2588 (M+H).
o) (2S,3S)-2-{4-[4-(2-Morpholin-4-yl-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0230]
[0231] (1) A solution of (R)-N-(tert-butyloxycarbonyl-(4-hydroxyphenylglycine) (1 g, 3:74 mmol) in dry N,N-dimethylformamide (70 mL) was treated with sodium hydride (60% suspention in mineral oil) (470 mg, 11.97 mmol) at 0° C. After 10 minutes the reaction mixture was warmed to room temperature stirred for an additional 10 minutes at that temperature and then treated with N-(2-chloroethyl)morpholine hydrochloride (720 mg, 2.93 mmol) and potassium iodide (61 mg, 0.37 mmol). The reaction mixture was stirred at ambient temperature for 27.5 hours and then partitioned between ethyl acetate and water. The aqueous layer was adjusted to pH=7 with 1N aqueous hydrochloric acid. The aqueous layer was then lyophilized to give a solid residue that was suspended in tetrahydrofuran and filtered. The solids were washed with tetrafydrofuran (2×) and the combined filtrates concentrated to afford crude (R)-tert-butoxycarbonylamino-[4-(2-morpholin-4-yl-ethoxy)-phenyl]-acetic acid which was used immediately without further purification.
[0232] (2) (R)-tert-butoxycarbonylamino-[4-(2-morpholin-4-yl-ethoxy)-phenyl]-acetic acid (≈2.93 mmol) was dissolved in tetrahydrofuran (60 mL) and (2S,3S)-2-amino-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide (500 mg, 1.58 mmol) (prepared as described in example 4) was added followed by 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (600 mg, 3.12 mmol) at 0° C. The reaction mixture was allowed to slowly warm to room temperature. After stirring for 5.5 hours the reaction mixture was partitioned between ethyl acetate and brine, the organic extract was dried over sodium sulfate and concentrated in vacuo. The resulting residue purified by chromatography over silica gel eluted first with ethyl acetate and then gradient eluted with dichloromethane containing from 0 to 10% methanol. {(R)-[4-(2-Morpholin-4-yl-ethoxy)-phenyl]-[(1S,2S)-2-phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propylcarbamoyl]-methyl}-carbamic acid-tert-butyl ester was obtained as a white solid (146 mg, 14%).
[0233] HRMS: Obs. Mass, 680.3118. Calcd. Mass, 680.3113 (M+H).
[0234] (3) {(R)-[4-(2-Morpholin-4-yl-ethoxy)-phenyl]-[(1S,2S)-2-phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propylcarbamoyl]-methyl}-carbamic acid-tert-butyl ester (0.19 mmol) was dissolved in a 30% v/v solution of trifluoroacetic acid in dichloromethane (5 mL) at 0° C. After stirring for 2 hours the reaction mixture was partitioned between ethyl acetate and saturated aqueous sodium bicarbonate solution. The aqueous layer was adjusted to pH=8 by the addition of solid sodium bicarbonate. The aqueous layer was again extracted with ethyl acetate (2×). The combined organic layers was dried over sodium sulfate, filtered and concentrated in vacuo to give crude (2S,3S)-2-{(R)-2-amino-2-[4-(2-morpholin-4-yl-ethoxy)-phenyl]-acetylamino}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide which was used immediately and without further purification.
[0235] (4) Crude (2S,3S)-2-{(R)-2-amino-2-[4-(2-morpholin-4-yl-ethoxy)-phenyl]-acetylamino}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide (≈0.19 mmol) was dissolved in tetrahydrofuran (10 mL) that contained diisopropylethylamine (160 μL, 122 mg, 0.94 mmol) and was transferred via cannula to a solution of diphosgene (16 μL, 26 mg, 0.13 mmol) in tetrahydrofuran (15 mL) at 0° C. The reaction mixture was stirred for 20 minutes and then partitioned between ethyl acetate and water. The organic layer was separated and dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by chromatography over silica gel gradient eluted with 0-100% ethyl acetate in hexanes and the isolated material further purified by preparative thin layer chromatography using silica gel eluted with ethyl acetate. Precipitation of the isolated product from dichloromethane with an excess of hexanes gave (2S,3S)-2-{4-[4-(2-morpholin-4-yl-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide as an off white solid (32 mg, 29%).
[0236] HRMS: Obs. Mass, 606.2384. Calcd. Mass, 606.2381 (M+H).
p) (2S,3S)-3-(3-Fluoro-phenyl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-N-(4-propionyl-thiazol-2-yl)-butyramide
[0237]
(2S,3S)-2-tert-Butoxycarbonylamino-3-(4-fluoro-phenyl)-butyric acid was prepared in a similar manner as the synthesis of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-pentanoic acid as described in Example 3.
[0238] HRMS: Obs. Mass, 569.1866. Calcd. Mass, 569.1865 (M+H).
q) (2S,3S)-2-[(R)-4-(4-Methoxy-3-methyl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0239]
(R)-tert-Butoxycarbonylamino-(4-methoxy-3-methyl-phenyl)-acetic acid was prepared as described in Example 8g.
[0240] HRMS: Obs. Mass, 543.1672. Calcd. Mass, 543.1672 (M+H).
r) (2S,3S)-2-{(S)-4-[4-(2-Hydroxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0241]
Prepared in a similar way as (2S,3S)-2-{(R)-4-[4-(2-hydroxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide (Example 5f) except that (S)-4-hydroxyphenylglycine was used in place of (R)-4-hydroxyphenylglycine.
[0242] HRMS: Obs. Mass, 537.1802. Calcd. Mass, 537.1803 (M+H).
s) (2S,3S)-2-((R)-2,5-Dioxo-4-phenyl-imidazolidin-1-yl)-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0243]
[0244] Prepared as described in Example 4 except that (R)-tert-butyloxycarbonylamino-phenylglycine was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine.
[0245] HRMS: Obs. Mass, 477.1595. Calcd. Mass, 477.1591 (M+H).
t) (2S,3S)-2-[4-(4-Dimethylamino-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0246]
Prepared as described in Example 4 except that tert-butoxycarbonylamino-(4-dimethylamino-phenyl)-acetic acid was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine.
[0247] HRMS: Obs. Mass, 520.2015. Calcd. Mass, 520.2013 (M+H).
u) (2S,3S)-2-[4-(4-Morpholin-4-yl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0248]
Prepared as described in Example 4 except that tert-butoxycarbonylamino-(4-morpholin-4-yl-phenyl)-acetic acid was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine. tert-Butoxycarbonylamino-(4-morpholin-4-yl-phenyl)-acetic acid was prepared in a similar way as that described in Example 9, step 1, except that 4-morpholin-4-yl-benzaldehyde was used in place of 4-thiomethylbenzaldehyde. 4-Morpholin-4-yl-benzaldehyde was prepared as follows:
[0249] A mixture of 2-(4-iodo-phenyl)-[1,3]dioxolane (960 mg, 3.477 mmol), 18-crown-6 ether (1.021 g, 3.85 mmol), tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct (36.35 mg, 0.0348 mmol), rac-2,2′-bis(diphenylphosphino)-1-1′-binaphthyl (65.54 mg, 0.104 mmol) and sodium-t-butoxide (447.9 mg, 4.52 mmol) were thoroughly degassed with argon. To this mixture under argon was added an argon degassed solution of freshly distilled morpholine (324.6 mg, 3.651 mmol) in dry tetrahydrofuran (8 mL). It was stirred at room temperature for 2 hours, and then heated to reflux for 2 hours. The mixture was cooled to room temperature, taken into ethyl acetate (50 mL) and washed with water (3×50 mL) and back extracted with ethyl acetate (50 mL). The combined organic extracts were dried over sodium sulfate, filtered and concentrated to a residue (1.06 g). The residue was purified by chromatography over a methanol deactivated silica gel column gradient eluted in 5% steps from 0 to 25% ethyl acetate in hexanes. 4-(4-[1,3]Dioxolan-2-yl-phenyl)-morpholine eluted from the column with 20 to 25% ethyl acetate in hexanes. Upon concentration 4-(4-[1,3]dioxolan-2-yl-phenyl)-morpholine was obtained as a tan solid (690 mg, 84.3%).
[0250] A mixture of 4-(4-[1,3]dioxolan-2-yl-phenyl)-morpholine (690 mg, 2.933 mmol) in methanol (5 mL) was treated with 10 drops concentrated aqueous hydrochloric acid. The mixture was stirred at room temperature for 1 hour. To this solution was added 5 drops of water and stirring was continued for 2 hours at ambient temperature. The solution was then poured into ethyl acetate (50 mL) and washed with saturated aqueous sodium bicarbonate (2×50 mL) and extracted with ethyl acetate (2×50 mL). The combined organic extracts were dried over sodium sulfate, filtered and concentrated to give 4-morpholin-4-yl-benzaldehyde as a tan waxy solid (550 mg, 98%).
[0251] HRMS: Obs. Mass, 562.2120. Calcd. Mass, 562.2119 (M+H).
v) (2S,3S)-2-{4-[4-(4-Hydroxy-piperidin-1-yl)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0252]
Prepared as described in Example 4 except that tert-butoxycarbonylamino-[4-(4-hydroxy-piperidin-1-yl)-phenyl]-acetic acid was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine. tert-Butoxycarbonylamino-[4-(4-hydroxy-piperidin-1-yl)-phenyl]-acetic acid was prepared in way similar to that described in Example 5u except that piperidin-4-ol was used in place of morpholine.
[0253] HRMS: Obs. Mass, 576.2275. Calcd. Mass, 576.2275 (M+H).
w) (2S,3S)-2-(4-{4-[(2-Methoxy-ethyl)-methyl-amino]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0254]
Prepared as described in Example 4 except that tert-butoxycarbonylamino-{4-[(2-methoxy-ethyl)-methyl-amino]-phenyl}-acetic acid was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine. tert-Butoxycarbonylamino-{4-[(2-methoxy-ethyl)-methyl-amino]-phenyl}-acetic acid was prepared in a similar way as that described in Example 5u except that (2-methoxy-ethyl)-methyl-amine was used in place of morpholine.
[0255] HRMS: Obs. Mass, 564.2279. Calcd. Mass, 564.2275 (M+H)
x) (2S,3S)-N-(4-Cyclopropanecarbonyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide
[0256]
Prepared as described in Example 4 except that cyclopropyl magnesium chloride was used in place of ethyl magnesium chloride in step 4 and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in example 2c) was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine.
[0257] HRMS: Obs. Mass, 563.1955. Calcd. Mass, 563.1959 (M+H).
y) (2S,3S)-2-{4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-methyl-pentanoic acid (4-propionyl-thiazol-2-yl)-amide
[0258]
Prepared as described in Example 4 except that (2S,3S)-2-tert-butoxycarbonylamino-3-methyl-pentanoic acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in Example 2c) was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine.
[0259] HRMS: Obs. Mass, 503.1961 Calcd. Mass, 503.1959 (M+H).
z) (2S,3R)-3-Benzyloxy-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-N-(4-propionyl-thiazol-2-yl)-butyramide
[0260]
Prepared as described in Example 4 except that (2S,3R)-3-benzyloxy-2-tert-butoxycarbonylamino-butyric acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in Example 2c) was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine.
[0261] HRMS: Obs. Mass, 581.2063 Calcd. Mass, 581.2065 (M+H).
EXAMPLE 6
(2S,3S)-N-[4-(2-Methoxy-acetyl)-thiazol-2-yl]-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0262]
[0263] (1) To a solution of [4-(methoxy-methyl-carbamoyl)-thiazol-2-yl]-carbamic acid-tert-butyl ester (17.0 g, 59.2 mmol) (prepared as described in example 4a-4c) in acetonitrile (250 mL) were added potassium carbonate (40.8 g, 295.2 mmol) and 4-dimethylaminopyridine (1.4 g, 11.5 mmol) followed by di-tert-butyl dicarbonate (27.1 g, 124.2 mmol) at room temperature. After stirring for 12 hours, the reaction was filtered through celite and the solvent was removed under vacuum. The crude product was purified by chromatography over silica gel gradient eluted with 30% up to 40% ethyl acetate in hexane to give [4-(methoxy-methyl-carbamoyl)-thiazol-2-yl]-bis-(carbamic acid-tert-butyl ester) (20.1 g, 88% yield).
[0264] (2) To a solution of lithium diisopropylamide (13.3 g, 124.1 mmol) in anhydrous tetrahydrofuran (100 mL) chilled to −78° C. was added dropwise, methyl methoxyacetate (12.9 g, 124.3 mmol) in anhydrous tetrahydrofuran (20 mL) at −78° C. The mixture was stirred at −78° C. for 15 minutes. [4-(Methoxy-methyl-carbamoyl)-thiazol-2-yl]-bis-(carbamic acid-tert-butyl ester) (6.0 g, 15.5 mmol) in anhydrous tetrahydrofuran (20 mL) was added dropwise to the anion at −78° C. The mixture was stirred for 30 minutes then quenched with saturated aqueous sodium bicarbonate, extracted with ethyl acetate, washed with brine and dried over sodium sulfate. The crude product was purified by chromatography over silica gel gradient eluted with 10% up to 30% ethyl acetate in hexanes. 3-(2-Bis-tert-butoxycarbonylamino-thiazol-4-yl)-2-methoxy-3-oxo-propionic acid methyl ester was obtained as a white foam (1.54 g, 23%).
[0265] (3) To a solution of 3-(2-bis-tert-butoxycarbonylamino-thiazol-4-yl)-2-methoxy-3-oxo-propionic acid methyl ester (1.54 g, 3.6 mmol) in dichloromethane (15 mL) was added trifluoroacetic acid (7.2 mL) at 0° C. The reaction was warmed to room temperature and stirred for 4 hours. The solvent was removed under vacuum and the residue was partitioned between ethyl acetate and saturated aqueous sodium bicarbonate. The aqueous layer was extracted with ethyl acetate and the combined extracts were washed with brine and dried over sodium sulfate. The solvent was removed to give 3-(2-amino-thiazol-4-yl)-2-methoxy-3-oxo-propionic acid methyl ester as an oil (800 mg, 97% yield).
[0266] (4) To a solution of 3-(2-amino-thiazol-4-yl)-2-methoxy-3-oxo-propionic acid methyl ester (765 mg, 3.3 mmol) in tetrahydrofuran (25 ml) was added 1M aqueous sodium hydroxide (4.0 ml, 4.0 mmol) at room temperature. The mixture was stirred for 2 hours then cooled to 0° C. 1 N aqueous sulfuric acid (33 mL, 33.2 mmol) was added and the reaction was warmed to 40° C. for 30 minutes. The reaction mixture was then cooled to 0° C. and made basic with saturated aqueous sodium bicarbonate. The suspension was extracted with ethyl acetate, the combined organic extracts washed with water, brine and dried over magnesium sulfate. The crude product was purified by chromatography over silica gel eluted with 7:3 ethyl acetate/hexanes to give 1-(2-amino-thiazol-4-yl)-2-methoxy-ethanone as a yellow oil (240 mg, 42% yield).
[0267] (5) In a manner similar as described in example 1, (2S,3S)-N-[4-(2-methoxy-acetyl)-thiazol-2-yl]-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide was prepared from 1-(2-amino-thiazol-4-yl)-2-methoxy-ethanone.
[0268] HRMS: Obs. Mass, 507.2888. Calcd. Mass, 507.2887 (M+H).
EXAMPLE 7
2-{(2S,3S)-2-[(R)-4-(2,3-Dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0269]
[0270] (1) 2-Amino-thiazole-4-carboxylic acid ethyl ester (38 g) (prepared as described in Example 4) in methanol (400 mL) was cooled in an ice bath and to it was added 25% sodium methoxide over 0.5 hours. The ice bath was removed after 0.5 hours. A small amount of isoluble material was removed by filtration and to the yellow solution was added saturated aqueous ammonium chloride and the reaction mixture concentrated to remove excess methanol. The mixture was basified to pH=9.0 with saturated aqueous sodium bicarbonate and extracted with 1:1 ether/tetrahydrofuran (3×200 mL). The combined organic extracts were washed with water. The organic solution was dried over sodium sulfate and concentrated to give a pale yellow solid which still contained some residual solvent. The solid was suspended in hexanes, filtered on a 5.5 cm funnel then dried in vacuo to give 2-amino-thiazole-4-carboxylic acid methyl ester (15.6 g) as a pale yellow solid.
[0271] (2) 2-Amino-thiazole-4-carboxylic acid methyl ester (0.57 g, 3.62 mmol) and (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid (Acros) (1.01 g, 3.62 mmol), 1-hydroxybenzotriazole and (0.59 g, 4.34 mmol) and O-benzeotrazol-1-yl-N,N,N′,N′-tetramethyluroniumhexaflurorophosphate (1.65 g, 4.34 mmol) in N,N-dimethylformamide (8 mL) were stirred at ambient temperature for 24 hours. The mixture was diluted with ethyl acetate, washed with water, brine and dried (magnesium sulfate). Evaporation of the solvents and chromatography of the residue over silica gel gradient eluted with 0.2-1.5% methanol in dichloromethane gave 2-((2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester (0.65 g, 43%).
[0272] (3) 2-((2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester (0.65 g, 1.54 mmol) was mixed in dichloromethane (5 mL) in an ice-bath. Trifluoroacetic acid (5 mL) was added and the solution was stirred for 2 hours. The reaction mixture was evaporated and the residue was precipitated with ether. The mixture was stirred vigorously for 10 minutes and then filtered. The solid was partitioned between aqueous sodium bicarbonate and dichloromethane. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic extracts were washed with brine and dried (sodium sulfate). Evaporation of the solvents gave 2-((2S,3S)-2-amino-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester (0.35 g, 71%).
[0273] (4) 2-((2S,3S)-2-Amino-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester (0.255 g, 0.80 mmol), (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid (prepared according to the procedure of Bohme, E. H. W. et al., J. Med. Chem. 1980, 23,405-412), O-benzotriazol-1-yl-N,N,N′,N′-tetramethyluronium hexaflurorophosphate (0.364 g, 0.96 mmol) and diisopropylethyl amine (0.56 mol, 3.2 mmol) were dissolved in N,N-dimethylformamide (3 mL) in an ice bath. 1-Hydroxybenzotriazole (0.13 g, 9.6 mmol) in N,N-dimethylformamide (1 mL) was added dropwise. Stirring was continued for 30 min at 0° C. The reaction mixture was diluted with ethyl acetate and the mixture was washed with water and brine. The organic layer was diluted with an equal volume of dichloromethane, filtered through a pad of silica gel with a layer of sodium sulfate on the top and eluted with 1:1 ethyl acetate/dichloromethane. Evaporation of the solvents gave a white solid which was triturated with ether/hexane to give crude 2-{(2S,3S)-2-[(R)-2-tert-butoxycarbonylamino-2-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (0.49 g).
[0274] (5) 2-{(2S,3S)-2-[(R)-2-tert-Butoxycarbonylamino-2-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (0.49 g, 0.80 mmol) was stirred in dichloromethane (8 mL) in an ice bath. Trifluoroacetic acid (8 mL) was added and the solution was stirred for 2 hours. The reaction mixture was evaporated and the residue was precipitated with hexanes/ether. The mixture was stirred vigorously for 10 minutes and then filtered. The resulting solid was partitioned between aqueous sodium bicarbonate and dichloromethane. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic extracts were washed with brine and dried (sodium sulfate). Evaporation of the solvents gave 2-{(2S,3S)-2-[(R)-2-amino-2-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (0.384 g, 94%).
[0275] (6) A solution of 2-{(2S,3S)-2-[(R)-2-amino-2-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (0.380 g, 0.75 mmol)) and diisopropylethylamine (0.52 mL, 3 mmol) in tetrahydrofuran (7.5 mL) were added to a solution of diphosgene (0.48 mL, 4 mmol) in a mixture of toluene (7.5 mol) and tetrahydrofuran (7.5 mol) over 10 minutes at 0° C. The mixture was stirred at 0° C. for 20 minutes and then diluted with ethyl acetate. The mixture was washed with water, brine and dried (sodium sulfate). Evaporation of the solvents and chromatography of the residue over silica gel gradient eluted with 0.2-1% methanol in dichloromethane gave (2-{(2S,3S)-2-[(R)-4-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (0.22 g, 55%).
[0276] HRMS: Obs. Mass, 537.1438. Calcd. Mass, 537.1439 (M+H).
EXAMPLE 8
[0277] In a manner similar to that described in Example 7, the following compounds were prepared.
a) 2-[(2S,3S)-2-((R)-2,5-Dioxo-4-phenyl-imidazolidin-1-yl)-3-phenyl-butyrylamino]-thiazole-4-carboxylic acid methyl ester
[0278]
[0279] Anal. Calcd. for C 24 H 22 N 4 O 5 S.0.2 C 6 H 14 : C, 61.05; H, 5.04; N, 11.30; S, 6.47. Found: C, 61.27; H, 5.25; N, 10.95; S, 6.10.
b) 2-{(2S,3S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0280]
(R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine (Hyun, M. H.; Cho, Y. K. et al. J. Liq. Chrom . & Rel. Technol. 2002, 25, 573-588.) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in Example 7 (step 4).
[0281] HRMS: Obs. Mass, 509.1485. Calcd. Mass, 509.1490 (M+H).
c) 2-{(2S,3S)-2-[(R)-4-(4-Hydroxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0282]
[0283] HRMS: Obs. Mass, 495.1334. Calcd. Mass, 495.1333 (M+H).
d) 2-((2S,3S)-2-{(R)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester
[0284]
(R)-tert-Butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid, which was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in Example 7 (step 4) was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0285] HRMS: Obs. Mass, 553.1753. Calcd. Mass, 553.1752 (M+H).
e) 2-((2S,3S)-2-{(R)-4-[4-(2-Hydroxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester
[0286]
(R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid, which was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in Example 7 (step 4), was prepared as described in Example 2b.
[0287] HRMS: Obs. Mass, 539.1595. Calcd. Mass, 539.1595 (M+H).
f) 2-{(2S,3S)-2-[(R)-4-(4-Isopropoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0288]
(R)-tert-Butoxycarbonylamino-[4-(1-methyl-ethoxy)-phenyl]-acetic acid, which was used in place of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 8e, was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0289] HRMS: Obs. Mass, 537.1803. Calcd. Mass, 537.1803 (M+H).
g) 2-{(2S,3S)-2-[(R)-4-(4-Methoxy-3-methyl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0290]
(R)-tert-Butoxycarbonylamino-(4-methoxy-3-methyl-phenyl)-acetic acid was prepared as follows.
[0291] (1) To a solution of (4-methoxy-3-methyl-phenyl)-acetic acid (5.04 g, 27.97 mmol) and triethylamine (3.9 mL, 27.97 mmol) in anhydrous tetrahydrofuran (100 mL) under nitrogen at −78° C. was added trimethylacetyl chloride (3.44 mL, 27.97 mmol). The reaction mixture was stirred at −78° C. for 10 minutes, 0° C. for 1 hour, then re-cooled to −78° C. At the same time, to a separate flask charged with a solution of (R)-(+)-4-benzyl-2-oxazolidinone (4.96 g, 27.97 mmol) in anhydrous tetrahydrofuran (100 mL) under nitrogen at −78° C. was added dropwise a solution of n-butyllithium (14 mL, 28 mmol, 2 M in hexanes). The second reaction mixture was stirred at −78° C. for 20 minutes, then transferred via cannula into the first reaction flask containing the mixed anhydride at −78° C. The reaction mixture was stirred at 0° C. for 1 hour, then warmed to room temperature and stirred for 18 hours. The mixture was quenched with saturated aqueous ammonium chloride solution (200 mL), concentrated to about half of its original volume under reduced pressure to remove tetrahydrofuran. The remaining mixture was extracted with ethyl acetate (2×250 mL). The organic layers were separated, combined, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by chromatography over silica gel eluted with 1:1 ethyl acetate/hexanes to give (R)-4-benzyl-3-[2-(4-methoxy-3-methyl-phenyl)-acetyl]-oxazolidin-2-one as a pale yellow oil (8.5 g, 89%).
[0292] (2) To a solution of (R)-4-benzyl-3-[2-(4-methoxy-3-methyl-phenyl)-acetyl]-oxazolidin-2-one (8.5 g, 25 mmol) in dry tetrahydrofuran (120 mL) under nitrogen at −78° C. was added potassium hexamethyldisilazide (36 mL, 32.6 mmol, 0.91M in tetrahydrofuran). The reaction mixture was stirred at −78° C. for 1 hour, then a pre-cooled solution of 2,4,6-triisopropylbenzenesulfonyl azide (8.8 g, 28.6 mmol) in tetrahydrofuran (80 mL) at −78° C. was added dropwise via cannula. The reaction mixture was stirred at −78° C. for 1.5 hours, then acetic acid (5.4 equiv, 8.2 g, 136 mmol) was added. The reaction mixture was warmed to 35° C. in a water bath and stirred for 2 hours, during which period of time analysis by thin layer chromatography indicated the formation of the desired product as a major component. The reaction mixture was concentrated to a smaller volume, then poured into water, and extracted with ethyl acetate (2×200 mL). The organic layers were separated, combined, dried over sodium sulfate and concentrated. The residue was purified by chromatography over silica gel eluted with 2:1 dichloromethane/hexanes to give (R)-3-[(R)-2-azido-2-(4-methoxy-3-methyl-phenyl)-acetyl]-4-benzyl-oxazolidin-2-one as a yellow oil (8.0 g, 84%).
[0293] (3) To a solution of (R)-3-[(R)-2-azido-2-(4-methoxy-3-methyl-phenyl)-acetyl]-4-benzyl-oxazolidin-2-one (8 g, 21 mmol) and di-tert-butyl dicarbonate (9.2 g, 42 mmol) in ethyl acetate (100 mL) was added 10% palladium on charcol (3 g) under nitrogen. The resulting suspension was vigorously shaken under hydrogen at 55 psi pressure in a Parr apparatus for 24 hours. The mixture was then filtered through a short pad of celite, and the filtrate was concentrated. The residue was purified by chromatography over silica gel eluted with 1:4 ethyl acetate/hexanes to give [(R)-2-((R)-4-benzyl-2-oxo-oxazolidin-3-yl)-1-(4-methoxy-3-methyl-phenyl)-2-oxo-ethyl]-carbamic acid tert-butyl ester as a yellow oil (6.05 g, 63%).
[0294] (4) To a solution of [(R)-2-((R)-4-benzyl-2-oxo-oxazolidin-3-yl)-1-(4-methoxy-3-methyl-phenyl)-2-oxo-ethyl]-carbamic acid tert-butyl ester (6.05 g, 13.3 mmol) in 4:1 tetrahdydrofuran/water (200 mL) at −10° C. was added sequentially 30% aqueous hydrogen peroxide (15 mL, 133 mmol) and a solution of lithium hydroxide monohydrate (1.63 g, 40 mmol) in water (20 mL). The reaction mixture was stirred at −10° C., and the progress of the reaction was monitored by thin layer chromatography. After 4 hours, thin layer chromatography indicated almost complete consumption of starting material. Saturated aqueous sodium sulfite solution (100 mL) was added. The mixture was concentrated to half of its original volume under reduced pressure to remove tetrahydrofuran, then extracted with dichloromethane (2×100 mL). The aqueous layer was separated and acidified to pH=4 with aqueous citric acid solution, extracted with ethyl acetate (2×250 mL). The organic layers were separated, combined, dried over sodium sulfate, concentrated under reduced pressure and dried in vacuo to give (R)-tert-butoxycarbonylamino-(4-methoxy-3-methyl-phenyl)-acetic acid as a white foam (2.2 g, 58%).
[0295] HRMS: Obs. Mass, 523.1646. Calcd. Mass, 523.1646 (M+H).
h) 2-((2S,3S)-2-{(R)-4-[4-(Dimethoxy-phosphorylmethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester
[0296]
tert-Butoxycarbonylamino-[(R)-4-(dimethoxy-phosphorylmethoxy)-phenyl]-acetic acid was prepared as follows.
[0297] Dimethyl phosphite (2.0 g, 18.2 mmol), paraformaldehyde (574 mg, 19.1 mmol) and triethylamine (0.25 mL, 1.8 mmol) were combined and heated to 70° C. to give a clear solution. After 1 hour the reaction was cooled and concentrated in vacuo overnight to afford the crude hydroxymethyl-phosphonic acid dimethyl ester (2.5 g).
[0298] (2) To a solution of hydroxymethyl-phosphonic acid dimethyl ester (2.0 g, 14.5 mmol) in anhydrous dichloromethane (50 mL) at −20° C. was added pyridine (1.4 mL, 16.7 mmol) followed by trifluoromethanesulfonic anhydride (2.7 mL, 15.9 mmol). After stirring at 0° C. for 0.5 hours, the mixture was filtered through celite with a thin layer of silica gel. The filtrate was washed with cold 1.0 N aqueous hydrochloric acid, water, saturated aqueous sodium bicarbonate and dried over sodium sulfate. The solvents were removed to give trifluoro-methanesulfonic acid dimethoxy-phosphorylmethyl ester as an oil (2.1 g, 53%).
[0299] (3) Sodium hydride (18.9 mg, 0.79 mmol) was added to (R)-tert-butoxycarbonylamino-(4-hydroxy-phenyl)-acetic acid (100 mg, 0.37 mmol) in anhydrous dimethylformamide (2.5 mL) in an ice bath. The mixture was allowed to warm to room temperature followed by the addition of trifluoro-methanesulfonic acid dimethoxy-phosphorylmethyl ester (122 mg, 0.45 mmol). Stirring was continued overnight at room temperature. The reaction was poured into 0.2 M aqueous hydrochloric acid (10 mL) and the mixture extracted with ethyl acetate. The combined extracts were washed with saturated aqueous sodium bicarbonate, brine and dried over sodium sulfate. Evaporation of the solvents gave tert-butoxycarbonylamino-[(R)-4-(dimethoxy-phosphorylmethoxy)-phenyl]-acetic acid (120 mg, 83% yield).
[0300] HRMS: Obs. Mass, 617.1459. Calcd. Mass, 617.1466 (M+H).
i) 2-{(2S,3S)-3-(2-Methoxy-phenyl)-2-[4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0301]
(2S,3S)-2-tert-Butoxycarbonylamino-3-(2-methoxy-phenyl)-butyric acid was prepared in a similar manner as the synthesis of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-pentanoic acid as described in Example 3.
[0302] HRMS: Obs. Mass, 539.1591. Calcd. Mass, 539.1595 (M+H).
j) 2-((2S,3S)-3-(4-Fluoro-phenyl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester
[0303]
(2S,3S)-2-tert-Butoxycarbonylamino-3-(4-fluoro-phenyl)-butyric acid was prepared in a similar manner as the synthesis of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-pentanoic acid as described in Example 3.
[0304] (R)-tert-Butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid, which was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in Example 7 (step d), was prepared in a similar manner as described for the synthesis of (R)-tert-butoxycarbonylamino-{4-[2-(tetrahydro-pyran-2-yloxy)-ethoxy]-phenyl}-acetic acid in Example 2b.
[0305] HRMS: Obs. Mass, 571.1655. Calcd. Mass, 571.1657 (M+H).
k) 2-{(2S,3S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-pentanoylamino}-thiazole-4-carboxylic acid methyl ester
[0306]
Prepared as described in Example 7 except that (2S,3S)-2-tert-butoxycarbonylamino-3-methyl-pentanoic acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine (prepared as described in example 1, step 5) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4.
[0307] HRMS: Obs. Mass, 483.1312. Calcd. Mass, 483.1309 (M+Na).
l) 2-[(2S,3S)-2-((R)-2,5-Dioxo-4-phenyl-imidazolidin-1-yl)-3-methyl-pentanoylamino]-thiazole-4-carboxylic acid methyl ester
[0308]
Prepared as described in Example 7 except that (2S,3S)-2-tert-butoxycarbonylamino-3-methyl-pentanoic acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butyloxycarbonylamino-phenylglycine was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4.
[0309] HRMS: Obs. Mass, 453.1205 Calcd. Mass, 453.1203 (M+Na).
m) 2-((2S,3S)-2-{(R)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-methyl-pentanoylamino)-thiazole-4-carboxylic acid methyl ester
[0310]
Prepared as described in Example 7 except that (2S,3S)-2-tert-butoxycarbonylamino-3-methyl-pentanoic acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in Example 2c) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4.
[0311] HRMS: Obs. Mass, 505.1758 Calcd. Mass, 505.1752 (M+H).
n) 2-{(2S,3R)-3-Hydroxy-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0312]
Prepared as described in Example 7 except that (2S,3R)-3-tert-butoxy-2-tert-butoxycarbonylamino-butyric acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine (prepared as described in example 1, step 5) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4. Prior to reaction with (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine both tert-butyl groups were removed from 2-((2S,3R)-3-tert-butoxy-2-tert-butoxycarbonylamino-butyrylamino)-thiazole-4-carboxylic acid methyl ester with 1:1 v/v trifluoroacetic in methylene chloride at 0° C. for approximately 30 minutes. After removing the solvent the compound was dissolved in methylene chloride and washed with saturated sodium bicarbonate and saturated aqueous sodium chloride. The organic layer was dried over sodium sulfate filtered and concentrated. The crude product thus obtained was used without further purification.
[0313] HRMS: Obs. Mass, 449.1125 Calcd. Mass, 449.1126 (M+H).
o) 2-((2S,3R)-3-Hydroxy-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester
[0314]
Prepared as described in Example 7 except that (2S,3R)-3-tert-butoxy-2-tert-butoxycarbonylamino-butyric acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in Example 2c) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4. Prior to reaction with (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid both tert-butyl groups were removed from 2-((2S,3R)-3-tert-butoxy-2-tert-butoxycarbonylamino-butyrylamino)-thiazole-4-carboxylic acid methyl ester with 1:1 v/v trifluoroacetic acid in methylene chloride at 0° C. for approximately 30 minutes. After removing the solvent the compound was dissolved in methylene chloride and washed with saturated aqueous sodium bicarbonate and saturated sodium chloride. The organic layer was dried over sodium sulfate filtered and concentrated. The crude product thus obtained was used without further purification.
[0315] HRMS: Obs. Mass, 515.1210 Calcd. Mass, 515.1207 (M+H).
p) 2-((2S,3R)-3-tert-Butoxy-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester
[0316]
Prepared as described in Example 7 except that (2S,3R)-3-tert-butoxy-2-tert-butoxycarbonylamino-butyric acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in Example 2c) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4. Prior to reaction with (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid the carbamate tert-butyl group was removed from 2-((2S,3R)-3-tert-butoxy-2-tert-butoxycarbonylamino-butyrylamino)-thiazole-4-carboxylic acid methyl ester with 1:2 v/v trifluoroacetic acid in methylene chloride at 0° C. for approximately 30 minutes. Saturated aqueous sodium bicarbonate and ethyl acetate were added to the rapidly stirring reaction solution to quench the reaction. After further dilution with ethyl acetate and water the organic layer was separated and washed with saturated sodium chloride, dried over sodium sulfate filtered and concentrated.
[0317] HRMS: Obs. Mass, 549.2015 Calcd. Mass, 549.2014 (M+H).
q) 2-{(2S,3R)-3-Methoxy-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0318]
Prepared as described in Example 7 except that (2S,3R)-2-tert-butoxycarbonylamino-3-methoxy-butyric acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine (prepared as described in example 1, step 5) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4.
[0319] HRMS: Obs. Mass, 463.1284 Calcd. Mass, 463.1282 (M+H).
r) 2-((2S,3R)-3-Methoxy-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester
[0320]
Prepared as described in Example 7 except that (2S,3R)-2-tert-butoxycarbonylamino-3-methoxy-butyric acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in Example 2c) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4.
[0321] HRMS: Obs. Mass, 507.1547 Calcd. Mass, 507.1544 (M+H).
s) 2-((2S,3R)-3-Benzyloxy-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester
[0322]
Prepared as described in Example 7 except that (2S,3R)-3-benzyloxy-2-tert-butoxycarbonylamino-butyric acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in Example 2c) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4.
[0323] HRMS: Obs. Mass, 583.1860 Calcd. Mass, 583.1857 (M+H).
t) 2-((2S,3R)-3-(4-Chloro-benzyloxy)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-butyrylamino)-thiazole-4-carboxylic acid methyl ester
[0324]
Prepared as described in Example 7 except that (2S,3R)-2-tert-butoxycarbonylamino-3-(4-chloro-benzyloxy)-butyric acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in Example 2c) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4.
[0325] HRMS: Obs. Mass, 617.1465 Calcd. Mass, 617.1468 (M+H).
u) 2-{(2S,3R)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-pentanoylamino}-thiazole-4-carboxylic acid methyl ester
[0326]
Prepared as described in Example 7 except that (2S,3R)-2-tert-butoxycarbonylamino-3-methyl-pentanoic acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine (prepared as described in Example 1, step 5) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4.
[0327] HRMS: Obs. Mass, 461.1490 Calcd. Mass, 461.1490 (M+H).
v) 2-((2S,3R)-2-{(R)-4-[4-(2-Methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-methyl-pentanoylamino)-thiazole-4-carboxylic acid methyl ester
[0328]
Prepared as described in Example 7 except that (2S,3R)-2-tert-butoxycarbonylamino-3-methyl-pentanoic acid was used in place of (2S,3S)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid in step 2 and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in Example 2c) was used in place of (2R)-tert-butoxycarbonylamino-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-acetic acid in step 4.
[0329] HRMS: Obs. Mass, 505.1754 Calcd. Mass, 505.1752 (M+H).
EXAMPLE 9
2-{(2S,3S)-2-[4-(4-Methanesulfonyl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0330]
[0331] (1) A solution of 4-thiomethylbenzaldehyde (2.0 g, 13.00 mmol) in trimethylsilyl cyanide (7 mL, 52.5 mmol) was treated with a catalytic amount of zinc iodide and stirred at room temperature for 18 hours. The solvent was then removed under reduced pressure and the residue was dissolved a 7 N solution of ammonia in methanol (9 mL). The resulting mixture was heated at 45° C. for 2 hours in a sealed tube and then cooled to −20° C. The precipitated solid was collected by filtration, washed with ether, air dried and then dissolved in 6 N aqueous hydrochloric acid. The mixture was heated for 5 hours at 110° C. in a sealed tube and then cooled and concentrated under reduced pressure to give a solid residue. The solid was triturated with ether, air dried and suspended in dioxane. The suspension was treated with saturated aqueous sodium carbonate (10 mL) and di-tert-butyl dicarbonate (3.4 g, 15.6 mmol) and stirred overnight. The mixture was partitioned between ethyl acetate and 2 N aqueous hydrochloric acid. The organic layer was dried over sodium sulfate, filtered, concentrated and the solid residue was triturated with hexanes to afford tert-butoxycarbonylamino-(4-methylsulfanyl-phenyl)-acetic acid, as a yellow/brown solid (2.3 g, 59%).
[0332] (2) A solution of 2-((2S,3S)-2-amino-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester (75 mg, 0.24 mmol) and tert-butoxycarbonylamino-(4-methylsulfanyl-phenyl)-acetic acid (77 mg, 0.26 mmol) in dichloromethane (10 mL) at 0° C. was treated with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (50 mg, 0.26 mmol). The reaction was allowed to slowly warm to room temperature and stirred for 60 hours. The mixture was then partitioned between ethyl acetate and water. The organic layer was dried over sodium sulfate, filtered and concentrated. The residue was purified by chromatography over silica gel gradient eluted up to 7:3 ethyl acetate/hexane. The material obtained after chromatography was further treated by precipitation of dichloromethane solution with exess of hexanes to give 2-{(2S,3S)-2-[2-tert-butoxycarbonylamino-2-(4-methylsulfanyl-phenyl)-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester as a white amorphous solid (115 mg, 80%).
[0333] (3) 2-{(2S,3S)-2-[2-tert-Butoxycarbonylamino-2-(4-methylsulfanyl-phenyl)-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (110 mg, 0.18 mmol) was dissolved at 0° C. in a 30% solution of trifluoroacetic acid in dichloromethane. After 2.5 hours the reaction mixture was partitioned between ethyl acetate and aqueous saturated sodium bicarbonate. The aqueous layer was adjusted to pH=8 by the addition of solid sodium bicarbonate and then extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated to an off white solid. The solid was dissolved in a solution of diisopropyl ethyl amine (0.16 mL, 0.92 mmol) in dichloromethane (5 mL) and the resulting solution was added in a dropwise manner to a 0° C. mixture of diphosgene (16 μL, 0.13 mmol) in dichloromethane (5 mL). The mixture was stirred for 20 minutes and then partitioned between dichloromethane and water. The organic layer was dried over sodium sulfate, filtered and concentrated to the crude product. After purification by chromatography over silica gel gradient eluted up to 3:2 ethyl acetate/hexanes and precipitation of the material obtained from chromatography from dichloromethane with excess hexanes, 2-{(2S,3S)-2-[4-(4-methylsulfanyl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester, was isolated as a white amorphous solid (45 mg, 46%).
[0334] (4) A solution of 2-{(2S,3S)-2-[4-(4-methylsulfanyl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (RO4919362-000) (40 mg, 0.08 mmol) in a 1:1 mixture of tetrahydrofuran and dichloromethane (20 mL) was treated with 3-chloroperbenzoic acid (75% purity) (40 mg, 0.17 mmol) at 0° C. After stirring for 30 minutes additional tetrahydrofuran (6 mL) was added and then the mixture was allowed to slowly warm to room temperature and was stirred for an additional 6 hours. The reaction mixture was then partitioned between ethyl acetate and aqueous saturated sodium carbonate. The organic layer was dried over sodium sulfate, filtered, concentrated and the residue was purified by chromatography over silica gel gradiet eluted up to 1:1 ethyl acetate in dichloromethane. Precipitation of the material obtained after chromatography from a dichloromethane solution with excess hexanes afforded 2-{(2S,3S)-2-[4-(4-methanesulfonyl-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester, as a white amorphous solid (29 mg, 65%).
[0335] HRMS: Obs. Mass, Calcd. Mass, (M+H).
EXAMPLE 10
2-{(S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0336]
2-{(S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester was prepared in a similar manner as that described in Example 1 using (S)-N-tert-butoxycarbonyl-3,3-dimethylphenylalanine which was prepared according to the procedure of Nieman, J. A.; Coleman, J. E. et al. J. Nat. Prod. 2003, 66, 183-199.
[0337] HRMS: Obs. Mass, 523.1645. Calcd. Mass, 523.1646 (M+H).
EXAMPLE 11
2-{(2S,3R)-2-[(R)-4-(2,3-Dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0338]
[0339] (1) Triethylamine (1.3 mL, 9.1 mmol) was added to (S)-3-phenylbutyric acid (1.0 g, 6.1 mmol) in anhydrous tetrahydrofuran (60 mL) at −78° C. followed by the dropwise addition of pivaloyl chloride (0.83 ml, 6.7 mmol) to give a white solid. The reaction was allowed to warm to room temperature for 10 minutes then cooled back down to −78° C. In a separate flask, n-butyllithium (4.6 mL, 11.6 mmol, 2.5 M F in hexanes) was added to (S)-(+)-4-phenyl-2-oxazolidinone (2.0 g, 12.2 mmol) in anhydrous tetrahydrofuran at −78° C. and allowed to stir for 10 minutes. The lithiated oxazolidinone was transfered via cannula to the mixed anhydride at −78° C. and stirring continued for 2 hours. The reaction was quenched with water (25 mL) and extracted with ethyl acetate. The combined extracts were washed with water, brine and dried over sodium sulfate. The crude product was purified by chromatography over silica gel eluted with 2:3 ethyl acetate/hexanes and the resulting solid was recrystallized from ethyl acetate/hexanes to afford (S)-4-phenyl-3-((S)-3-phenyl-butyryl)-oxazolidin-2-one (1.63 g, 88% yield).
[0340] (2) Potassium bis(trimethylsilyl)amide (2.0 mL, 1.8 mmol, 0.91 M in tetrahydrofuran) was added to (S)-4-phenyl-3-((S)-3-phenyl-butyryl)-oxazolidin-2-one (500 mg, 1.6 mmol) in anhydrous tetrahydrofuran (8 mL) at −78° C. and stirred for 1 hour. In a separate flask, a solution of 2,4,6-triisopropylbenzenesulphonyl azide (625 mg, 2.0 mmol) in anhydrous tetrahydrofuran (10 mL) at −78° C. was added via cannula to the anion at −78° C. and stirring continued for 2 hours. Acetic acid (0.45 mL, 7.8 mmol) was added to the reaction at −78° C., the mixture warmed to room temperature and stirred overnight. The mixture was poured into water (30 mL) and extracted with ethyl acetate. The combined extracts were washed with brine and dried over sodium sulfate. The crude product was purified on silica gel with 2:1 dichloromethane/hexane to give (S)-3-((2S,3R)-2-azido-3-phenyl-butyryl)-4-phenyl-oxazolidin-2-one (230 mg, 41%).
[0341] (3) To a solution of the (S)-3-((2S,3R)-2-azido-3-phenyl-butyryl)-4-phenyl-oxazolidin-2-one (595 mg, 1.7 mmol) in ethyl acetate (25 mL) was added di-tert-butyl dicarbonate (815 mg, 3.7 mmol) followed by 10% palladium on carbon (90 mg). The mixture was hydrogenated overnight at atmospheric pressure and room temperature. The mixture was filtered through celite and the solvent was removed to give [(1S,2R)-1-((S)-2-oxo-4-phenyl-oxazolidine-3-carbonyl)-2-phenyl-propyl]-carbamic acid tert-butyl ester as an oil (710 mg, 99%).
[0342] (4) To a solution of [(1S,2R)-1-((S)-2-oxo-4-phenyl-oxazolidine-3-carbonyl)-2-phenyl-propyl]-carbamic acid tert-butyl ester (710 mg, 1.7 mmol) in tetrahydrofuran (18 mL) and water (4 ml) at 0° C. was added 30% aqueous hydrogen peroxide (1.5 mL, 15.1 mmol) followed by 1M aqueous lithium hydroxide (5.0 mL, 5.0 mmol). The mixture was stirred overnight at room temperature. The excess hydrogen peroxide was quenched with 2.0 M aqueous sodium hydrogen sulfite (15 mL, 30.1 mmol). Stirring was continued for 1 hour followed by extraction with dichloromethane. The aqueous layer was acidified with 10% aqueous citric acid and extracted with ethyl acetate. The combined ethyl acetate extracts were washed with water, brine and dried over magnesium sulfate and evaporated to give (2S,3R)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid (420 mg, 90% yield).
[0343] (5) In a manner similar as described in Example 1, 2-{(2S,3R)-2-[(R)-4-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester was prepared from (2S,3R)-2-tert-butoxycarbonylamino-3-phenyl-butyric acid. HRMS: Obs. Mass, 537.1439. Calcd. Mass, 537.1439 (M+H).
EXAMPLE 12
2-{(2S,3S)-2-[(R)-4-(4-Acetylamino-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester
[0344]
(1) To a solution of amino-(4-amino-phenyl)-acetic acid dihydrochloride (600 mg, 2.51 mmol) (prepared as described in U.S. Pat. No. 3,527,793) and triethylamine (1.1 mL, 7.53 mmol) in a 3:1 mixture of tetrahydrofuran/water (60 mL) was added di-tert-butyldicarbonate (1.4 g, 6.27 mmol). The reaction mixture was allowed to stir overnight and then partitioned between ethyl acetate and 1N aqueous hydrochloric acid. The organic layer was dried over sodium sulfate, filtered and concentrated. The residue was dissolved in a small amount of dichloromethane and precipitated with an excess of hexanes to afford (R)-tert-butoxycarbonylamino-(4-tert-butoxycarbonylamino-phenyl)-acetic acid as a white solid (730 mg, 79%).
[0346] HRMS: Obs. Mass, 389.1681. Calcd. Mass, 389.1683 (M+H).
[0347] (2) To a solution of (R)-tert-butoxycarbonylamino-(4-tert-butoxycarbonylamino-phenyl)-acetic acid (420 mg, 1.13 mmol) and (2S,3S)-2-(2-amino-3-phenyl-butyrylamino)-thiazole-4-carboxylic acid methyl ester (300 mg, 0.94 mmol) (prepared as described in Example 7) in dichloromethane (50 mL) was added 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (220 mg, 1.13 mmol) at 0° C. The reaction mixture was allowed to warm to ambient temperature slowly, stirred overnight and then partitioned between dichloromethane and water. The organic layer was dried over sodium sulfate, filtered and concentrated to give the crude product. Purification by chromatography over silica gel gradient eluted between 0 and 60% ethyl acetate in hexanes followed by a precipitation of the product from dichloromethane with excess hexanes gave 2-{(2S,3S)-2-[(R)-2-tert-butoxycarbonylamino-2-(4-tert-butoxycarbonylamino-phenyl)-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester as a white solid (520 mg, 82%).
[0348] HRMS: Obs. Mass, 668.2746. Calcd. Mass, 668.2749 (M+H).
[0349] (3) 2-{(2S,3S)-2-[(R)-2-tert-butoxycarbonylamino-2-(4-tert-butoxycarbonylamino-phenyl)-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (510 mg, 0.76 mmol) was dissolved in 30% v/v trifluoroacetic acid in dichloromethane solution (10 mL) at 0° C. The mixture was stirred at 0° C. for 2.5 hours and then partitioned between ethyl acetate and saturated aqueous sodium carbonate. The aqueous layer was adjusted to pH=9 by the addition of solid sodium carbonate and the organic layer collected, dried over sodium sulfate, filtered and concentrated. The residue was without further purification dissolved in tetrahydrofuran (50 mL) and the resulting solution cooled to 0° C. A solution of di-tert-butyldicarbonate (167 mg, 0.76 mmol) in tetrahydrofuran (5 mL) was added dropwise and after stirring overnight the reaction mixture was evaporated and the residue was purified by chromatography over silica gel gradient eluted with 0 to 100% ethyl acetate in hexanes to afford 2-{(2S,3S)-2-[(R)-2-(4-amino-phenyl)-2-tert-butoxycarbonylamino-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester as a white solid (250 mg, 58%).
[0350] HRMS: Obs. Mass, 568.2223. Calcd. Mass, 568.2225 (M+H).
[0351] (4) To a cold solution of 2-{(2S,3S)-2-[(R)-2-(4-amino-phenyl)-2-tert-butoxycarbonylamino-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (100 mg, 0.177 mmol) in dichloromethane (10 mL) was added triethylamine (50 μL, 0.354 mmol) followed by acetic anhydride (22 μL 0.212 mmol). The reaction mixture was then stirred overnight at room temperature. The solvent was removed in vacuo and the residue was purified by chromatography over silica gel gradient eluted from 10% to 75% ethyl acetate in hexanes to afforded 2-{(2S,3S)-2-[(R)-2-(4-acetylamino-phenyl)-2-tert-butoxycarbonylamino-acetylamino]-3-phenyl-butyryl-amino}-thiazole-4-carboxylic acid methyl ester which was used immediately in the following step of the synthesis (107 mg, 98%).
[0352] (5) To a cold solution of 2-{(2S,3S)-2-[(R)-2-(4-acetylamino-phenyl)-2-tert-butoxycarbonylamino-acetylamino]-3-phenyl-butyryl-amino}-thiazole-4-carboxylic acid methyl ester (107 mg, 0.175 mmol) in dichloromethane (6 mL), was added trifluoroacetic acid (4 mL). The reaction mixture was stirred at room temperature for 45 minutes, followed by removal of volatiles in vacuo. To the residue was added diethyl ether (10 mL) and the resulting suspension was separated by centrifugation. The solid was dissolved in ethyl acetate and washed with saturated aqueous sodium bicarbonate. The aqueous layer was extracted with ethyl acetate (2×50 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated to give crude 2-{(2S,3S)-2-[(R)-2-(4-acetylamino-phenyl)-2-amino-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester which was used immediately in the following step of the synthesis.
[0353] (6) Crude 2-{(2S,3S)-2-[(R)-2-(4-acetylamino-phenyl)-2-amino-acetylamino]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (≈0.175 mmol) was dissolved in dichloromethane (10 mL) and diisopropylethyllamine (72 μL, 0.41 mmol) was added. The resulting mixture was added to an ice cooled solution of diphosgene (13 μL, 0.109 mmol) in dichloromethane (10 mL). The reaction mixture was stirred for 15 minutes, diluted with ethyl acetate (100 mL) and washed with 0.2M aqueous hydrochloric acid, saturated aqueous sodium bicarbonate, brine and dried over sodium sulfate. The solution was filtered and the solvent removed in vacu. The residue was purified by chromatography over silica gel gradient eluted from 50% to 100% ethyl acetate in hexanes to afford 2-{(2S,3S)-2-[(R)-4-(4-acetylamino-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid methyl ester (70 mg, 74%).
[0354] HRMS: Obs. Mass, 536.1599. Calcd. Mass, 536.1599 (M+H).
EXAMPLE 13
N-[4-(1-Hydroxy-1-methyl-ethyl)-thiazol-2-yl]-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0355]
[0356] (1) (4-Acetyl-thiazol-2-yl)-carbamic acid tert-butyl ester was prepared in a similar manner as that described for (4-propionyl-thiazol-2-yl)-carbamic acid tert-butyl ester in example 4a-4d.
[0357] (2) (4-Acetyl-thiazol-2-yl)-carbamic acid tert-butyl ester (500 mg, 2.06 mmol) was taken in to dry tetrahydrofuran (8 mL) and cooled in an ice bath. To this was added a 3 M solution of methyl magnesium bromide (2.752 mL, 8.256 mmol) in diethyl ether over 5 minutes. After 30 minutes, more 3 M solution of methyl magnesium bromide (1 mL, 3 mmol) in diethyl ether was added. After 30 minutes, an additional aliquot of 3 M methyl magnesium bromide (1 mL, 3 mmol) in diethyl ether was added. No further change in the reaction mixture composition was observed after an additional 30 minutes. The reaction mixture was diluted with tetrahydrofuran (5 mL) and allowed to warm to room temperature. After 2 hours thin layer chromatography indicated no change in the composition of the reaction mixture. The reaction mixture was cooled in an ice bath and saturated aqueous ammonium chloride was added slowly. The mixture was diluted with water, extracted with ethyl acetate and washed with brine. The combined organic extracts were dried over sodium sulfate and concentrated to give a viscous oil. The crude product was purified by chromatography over silica gel gradient eluted from 1:19 upto 1:4 ethyl acetate/dichloromethane to give [4-(1-hydroxy-1-methyl-ethyl)-thiazol-2-yl]-carbamic acid tert-butyl ester as a white foam (250 mg, 47%).
[0358] (3) [4-(1-Hydroxy-1-methyl-ethyl)-thiazol-2-yl]-carbamic acid tert-butyl ester (250 mg, 0.92 mmol) was taken into dry dichloromethane and cooled in an ice bath. To this was added trifluoroacetic acid and the mixture stirred at 0° C. for 4 hours. The mixture was evaporated and the residue partitioned between dichloromethane and saturated aqueous sodium bicarbonate. The organic layer was separated out and the aqueous layer was extracted with dichloromethane. The combined organic extracts were dried over sodium sulfate and evaporated. Chromatography of the residue over silica gel gradient eluted with 1:99 up to 3:97 methanol in dichloromethane gave [4-(1-hydroxy-1-methyl-ethyl)-thiazol-2-yl]-carbamic acid (56 mg, 39%) as a white solid.
[0359] (4) N-[4-(1-Hydroxy-1-methyl-ethyl)-thiazol-2-yl]-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide was prepared from [4-(1-hydroxy-1-methyl-ethyl)-thiazol-2-yl]-carbamic acid and 2-tert-butoxycarbonylamino-3-phenyl-butyric acid in a similar manner as described in Example 1.
[0360] HRMS: Obs. Mass, 509.1853. Calcd. Mass, 509.1853 (M+H).
EXAMPLE 14
(2S,3S)-2-[(R)-4-(2,3-Dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-N-[4-(1-hydroxy-propyl)-thiazol-2-yl]-3-phenyl-butyramide
[0361]
[0362] a) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide (from example 5a) (20 mg, 0.037 mmol) was dissolved in warm dry methanol (5 mL). The reaction mixture was then cooled in an ice bath and sodium borohydride (1.56 mg, 0.041 mmol) was added. The reaction was stirred at 5° C. for 30 minutes, additional sodium borohydride (1.56 mg, 0.041 mmol) was added and stirring continued for 1 hour. The clear solution was treated with 1.5 N aqueous potassium hydrogen phosphate (1 mL) and the cloudy mixture was stirred for a few minutes, then diluted with saturated brine and extracted with ethyl acetate (3×25 mL). The combined organic extracts were washed with saturated brine, dried over sodium sulfate and concentrated in vacuo. The pale yellow residue was taken into a small amount of dichloromethane (0.5 ml) then treated with diethyl ether (2 mL) and this turbid solution was further precipitated with of hexanes (3 mL). The mixture was stirred for 5 minutes then filtered over a 1.7 cm funnel, washed with hexanes and air dried to give (2S,3S)-2-[(R)-4-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-2,5-dioxo-imidazolidin-1-yl]-N-[4-(1-hydroxy-propyl)-thiazol-2-yl]-3-phenyl-butyramide as a white solid (14.5 mg, 73%).
[0363] HRMS: Obs. Mass, 537.1801. Calcd. Mass, 537.1803 (M+H).
b) (2S,3S)-N-[4-(1-Hydroxy-ethyl)-thiazol-2-yl]-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0364]
[0365] In a similar manner as that described in Example 14a, (2S,3S)-N-[4-(1-hydroxy-ethyl)-thiazol-2-yl]-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide was prepared from (2S,3S)-N-(4-acetyl-thiazol-2-yl)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide which was in turn prepared as described in Example 1.
[0366] HRMS: Obs. Mass, Calcd. Mass, (M+H).
EXAMPLE 15
2-{(2S,3S)-2-[(R)-4-(4-Methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid dimethylamide
[0367]
[0368] In a manner similar to that described in Example 1, 2-{(2S,3S)-2-[(R)-4-(4-methoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyrylamino}-thiazole-4-carboxylic acid dimethylamide was prepared from 2-amino-thiazole-4-carboxylic acid dimethylamide.
[0369] 2-Amino-thiazole-4-carboxylic acid dimethylamide was prepared as follows.
[0370] (1) A solution of 2-tert-butoxycarbonylamino-thiazole-4-carboxylic acid (0.5 g, 2 mmol) (prepared as described in Examples 4a and 4b) in thionyl chloride (10 mL) was heated at reflux (80° C.) for 2 hours. The reaction mixture was then concentrated under reduced pressure. To the residue was added a 2 M solution of dimethylamine in tetrahydrofuran (10 mL, 20 mmol) and methanol (10 mL). The reaction mixture was stirred at room temperature for 20 hours and concentrated. The residue was purified by chromatography over silica gel eluted with 2:1 ethyl acetate/hexanes to give (4-dimethylcarbamoyl-thiazol-2-yl)-carbamic acid tert-butyl ester as a yellow foam (0.26 g, 48%).
[0371] (2) To a solution of (4-dimethylcarbamoyl-thiazol-2-yl)-carbamic acid tert-butyl ester (0.26 g, 0.95 mmol) in dichloromethane (10 mL) was added trifluoroacetic acid (10 mL, 130 mmol). The reaction mixture was stirred at room temperature for 2 hours, then concentrated under reduced pressure. Saturated aqueous sodium bicarbonate solution (50 mL) was added to neutralize the residue. The mixture was extracted with ethyl acetate (2×100 mL). The organic layers were separated, combined and dried over sodium sulfate, concentrated under reduced pressure and dried in vacuo to give crude 2-amino-thiazole-4-carboxylic acid dimethylamide as a yellow gum which was used without further purification (0.14 g, 86%).
[0372] HRMS: Obs. Mass, 522.1803. Calcd. Mass, 522.1806 (M+H).
EXAMPLE 16
(2S,3S)-N-(4-Ethylsulfanyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide
[0373]
[0374] Prepared as described in Example 1 except that 4-ethylsulfanyl-thiazol-2-ylamine was used in place of 1-(2-amino-thiazol-4-yl)-ethanone and (R)-tert-butoxycarbonylamino-[4-(2-methoxy-ethoxy)-phenyl]-acetic acid (prepared as described in Example 2c) was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine. 4-Ethylsulfanyl-thiazol-2-ylamine was prepared as follows:
[0375] (1) N-tert-butoxycarbonyl-thiourea (0.600 g, 3.40 mmole) was suspended in ethanol (5 mL) and the mixture was cooled in an ice-water bath. To this mixture was added a solution of bromo-thioacetic acid S-ethyl ester (0.880 g [75% pure]; 3.61 mmole) in ethanol (5 mL). Following completion of the addition, the mixture was warmed to room temperature and stirred overnight. After 20 hours, the reaction was concentrated. The residue was partitioned between methylene chloride and water. The organic phase was washed with water and brine. The aqueous phases were then backwashed with methylene chloride. The two organic phases were combined, dried over sodium sulfate and concentrated. The crude material was purified by chromatography over silica gel eluted with 20% v/v ethyl acetate in hexanes, to give (4-ethylsulfanyl-thiazol-2yl)-carbamic acid tert-butyl ester (0.514 g, 58%).
[0376] (2) (4-Ethylsulfanyl-thiazol-2yl)-carbamic acid tert-butyl ester (0.583 g, 2.24 mmole) was dissolved in methylene chloride (9 mL) and the resulting solution was cooled in an ice-water bath. Trifluoroacetic acid (5 mL) was added dropwise to this solution. The solution was stirred under an argon atmosphere for 3 hours, allowing the cooling bath to slowly warm up. At the conclusion of the reaction, the bath temperature was 12° C. The reaction was concentrated. The residue was redissolved in methylene chloride and concentrated. This was repeated two additional times to remove most of the trifluoroacetic acid. Following the final concentration, the residue was dissolved again in methylene chloride and washed with saturated sodium bicarbonate, water and brine. The organic phase was dried over sodium sulfate and concentrated to yield 4-ethylsulfanyl-thiazol-2-ylamine (0.256 g, 65%).
[0377] HRMS: Obs. Mass, 555.1731. Calcd. Mass, 555.1731 (M+H).
EXAMPLE 17
(2S,3S)-N-(4-Ethanesulfinyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide
[0378]
[0379] (2S,3S)-N-(4-Ethylsulfanyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide (0.135 g, 0.24 mmole) (prepared as described in Example 16) was dissolved in anhydrous tetrahydrofuran (15 mL). To this solution was added a solution of m-chloroperbenzoic acid (0.066 g, 0.27 mmole) in tetrahydrofuran (8 mL). After stirring at room temperature for 30 minutes, the reaction was concentrated. The residue was dissolved in cold methylene chloride and washed twice with saturated sodium bicarbonate and twice with brine. Each aqueous phase was backwashed with a second portion of methylene chloride. The two organic phases were combined, dried over sodium sulfate and concentrated. The crude material was purified by chromatography over silica gel eluted with a gradient of 50-100% v/v ethyl acetate in hexanes followed by 5% v/v methanol in ethyl acetate to yield (2S,3S)-N-(4-ethanesulfinyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide (0.103 g, 75%). This material was combined with another batch of material, dissolved in methylene chloride and added to hexanes to precipitate the product, (2S,3S)-N-(4-ethanesulfinyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide (0.117 g).
[0380] HRMS: Obs. Mass, 571.1682. Calcd. Mass, 571.1680 (M+H).
EXAMPLE 18
(2S,3S)-N-(4-Ethanesulfonyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide
[0381]
[0382] (2S,3S)-N-(4-Ethylsulfanyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide (0.128 g, 0.23 mmole) (prepared as described in Example 16) was dissolved in anhydrous tetrahydrofuran (15 mL). To this solution was added a solution of m-chloroperbenzoic acid (0.133 g, 0.46 mmole) in tetrahydrofuran (8 mL). After stirring at room temperature for 18 minutes, the reaction was concentrated. The residue was dissolved in cold methylene chloride and washed twice with saturated aqueous sodium bicarbonate and twice with brine. Each aqueous phase was backwashed with a second portion of methylene chloride. The two organic phases were combined, dried over sodium sulfate and concentrated. The crude material was purified by chromatography over silica gel eluted with a gradient of 50-100% v/v ethyl acetate in hexanes followed by 5% v/v methanol in ethyl acetate. The pure fractions were combined and concentrated. The residue was dissolved in methylene chloride and the resulting solution was added to hexanes to precipitate out the product, (2S,3S)-N-(4-ethanesulfonyl-thiazol-2-yl)-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide (0.095 g, 68%).
[0383] HRMS: Obs. Mass, 587.1631. Calcd. Mass, 587.1629 (M+H).
EXAMPLE 19
(2S,3S)-N-[4-(2-Hydroxy-acetyl)-thiazol-2-yl]-2-{(R)-4-[4-(2-methoxy-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide
[0384]
[0385] Prepared as described in Example 2c except that 1-(2-amino-thiazol-4-yl)-2-hydroxy-ethanone was used in place of 1-(2-amino-thiazol-4-yl)-ethanone. 1-(2-Amino-thiazol-4-yl)-2-hydroxy-ethanone was prepared as described below.
[0386] (1) Ethyl 2-aminothiazol-4-ylglyoxylate (4 g, 19.38 mmol) was taken into methanol (50 mL) and treated with p-toluenesulfonic acid (0.94 g, 0.25 mmol) at 85° C. for 1 hour. To this was added p-toluenesulfonic acid (3.1 g, 0.75 mmol) and stirring continued for 24 hours. p-Toluenesulfonic acid was added in 500 mg lots (2 more additions after 24 and 48 h) then stirred at 85° C. for 72 hours during which time NMR indicated >50% conversion to desired product. The reaction mixture was concentrated to ˜10 mL and then diluted with ethyl acetate (200 mL) and washed 3 times with saturated aqueous sodium bicarbonate (˜100 mL each) and saturated brine (100 mL). The aqueous layers were back extracted 3 times with ethyl acetate (100 mL each). The combined organic layers were dried over sodium sulfate, filtered and concentrated to give a yellow residue which was absorbed onto silica gel and purified by chromatography over a methanol deactivated silica gel column gradient eluted in 10% steps from 40 to 70% v/v ethyl acetate in hexanes and then with 100% ethyl acetate. The product containing fractions were pooled and concentrated in vacuo to give (2-amino-thiazol-4-yl)-dimethoxy-acetic acid methyl ester (1.73 g, 39%).
[0387] (2) A solution of (2-amino-thiazol-4-yl)-dimethoxy-acetic acid methyl ester (850 mg, 3.66 mmol) in dry tetrahydrofuran (40 mL) was treated portion-wise with lithium aluminum hydride (73 mg, 1.83 mmol) over 5 minutes at room temperature. The mixture was stirred for 30 minutes then treated portionwise with lithium aluminum hydride (36 mg 0.91 mmol) and stirred for 4 hours. After storing overnight in a refrigerator the reaction mixture was treated with ice chips (˜10 g) then diluted with water (20 mL). The mixture was acidified with 2N aqueous sulfuric acid (˜0.5 mL), then concentrated in vacuo to remove the tetrahydrofuran. The aqueous mixture was neutralized to pH 7.0 with saturated aqueous sodium bicarbonate and extracted with ethyl acetate (8×50 mL). The organic solution was washed with brine and dried over sodium sulfate, filtered and concentrated to give a tacky foam (650 mg). The residue was purified by chromatography over a methanol deactivated silica gel column gradient eluted in 1% steps between 0 and 6% methanol in methylene chloride. The product eluted from the column in 4 to 6% methanol in methylene chloride. After concentration 1-(2-amino-thiazol-4-yl)-2-hydroxy-ethanone was obtained as a yellow foam (210 mg, 28%).
[0388] HRMS: Obs. Mass, 553.1752. Calcd. Mass, 553.1752 (M+H).
EXAMPLE 20
(4-{(R)-1-[(1S,2S)-1-(4-Acetyl-thiazol-2-ylcarbamoyl)-2-phenyl-propyl]-2,5-dioxo-imidazolidin-4-yl}-phenoxy)-acetic acid methyl ester
[0389]
[0390] Prepared as described in example 1 except that (R)-tert-butoxycarbonylamino-(4-methoxycarbonylmethoxy-phenyl)-acetic acid was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine. (R)-tert-Butoxycarbonylamino-(4-methoxycarbonylmethoxy-phenyl)-acetic acid was prepared in a way similar to that described in example 1 except that methyl bromoacetate was used in place of methyl iodide.
[0391] HRMS: Obs. Mass, 551.1597. Calcd. Mass, 551.1595 (M+H).
EXAMPLE 21
(4-{(R)-2,5-Dioxo-1-[(1S,2S)-2-phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propyl]-imidazolidin-4-yl}-phenoxy)-acetic acid methyl ester
[0392]
[0393] Prepared as described in example 4 except that (R)-tert-butoxycarbonylamino-(4-methoxycarbonylmethoxy-phenyl)-acetic acid was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine. (R)-tert-Butoxycarbonylamino-(4-methoxycarbonylmethoxy-phenyl)-acetic acid was prepared as described in example 20.
[0394] HRMS: Obs. Mass, 565.1754. Calcd. Mass, 565.1752 (M+H).
EXAMPLE 22
(4-{2,5-Dioxo-1-[(1S,2S)-2-phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propyl]-imidazolidin-4-yl}-phenoxy)-acetic acid
[0395]
[0396] Prepared by hydrolysis of (4-{(R)-2,5-dioxo-1-[(1S,2S)-2-phenyl-1-(4-propionyl-thiazol-2-ylcarbamoyl)-propyl]-imidazolidin-4-yl}-phenoxy)-acetic acid methyl ester (prepared as described in example 21) with lithium hydroxide monohydrate in aqueous tetrahydrofuran. Under the conditions employed for the hydrolysis of the methyl ester racemization occurred at the 4-position of the imidazolidinedione ring.
[0397] HRMS: Obs. Mass, 551.1598. Calcd. Mass, 551.1595 (M+H).
EXAMPLE 23
(2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-dimethylcarbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0398]
[0399] Prepared as described in example 1 except that (R)-tert-butoxycarbonylamino-(4-dimethylcarbamoylmethoxy-phenyl)-acetic acid was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine. (R)-tert-Butoxycarbonylamino-(4-dimethylcarbamoylmethoxy-phenyl)-acetic acid was prepared in a way similar to that described in example 1 except that the known compound 2-chloro-N,N-dimethyl-acetamide was used in place of methyl iodide.
[0400] HRMS: Obs. Mass, 564.1912. Calcd. Mass, 564.1912 (M+H).
EXAMPLE 24
[0401] In a manner similar to that described in Example 23, the following compounds were prepared.
a) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-methylcarbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0402]
(R)-tert-Butoxycarbonylamino-(4-methylcarbamoylmethoxy-phenyl)-acetic acid was prepared and used in a manner analogous to that described for (R)-tert-butoxycarbonylamino-(4-dimethylcarbamoylmethoxy-phenyl)-acetic acid.
[0403] HRMS: Obs. Mass, 550.1757. Calcd. Mass, 550.1755 (M+H).
b) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-[(R)-4-(4-carbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0404]
(R)-tert-Butoxycarbonylamino-(4-carbamoylmethoxy-phenyl)-acetic acid was prepared and used in a manner analogous to that described for (R)-tert-butoxycarbonylamino-(4-dimethylcarbamoylmethoxy-phenyl)-acetic acid.
[0405] HRMS: Obs. Mass, 532.1628. Calcd. Mass, 532.1625 (M+H).
c) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-((R)-4-{4-[(2-methoxy-ethylcarbamoyl)-methoxy]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-butyramide
[0406]
(R)-tert-Butoxycarbonylamino-{4-[(2-methoxy-ethylcarbamoyl)-methoxy]-phenyl}-acetic acid was prepared and used in a manner analogous to that described for (R)-tert-butoxycarbonylamino-(4-dimethylcarbamoylmethoxy-phenyl)-acetic acid.
[0407] HRMS: Obs. Mass, 594.2014. Calcd. Mass, 594.2017 (M+H).
d) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-4-[4-(2-morpholin-4-yl-2-oxo-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-butyramide
[0408]
(R)-tert-Butoxycarbonylamino-[4-(2-morpholin-4-yl-2-oxo-ethoxy)-phenyl]-acetic acid was prepared and used in a manner analogous to that described for (R)-tert-butoxycarbonylamino-(4-dimethylcarbamoylmethoxy-phenyl)-acetic acid.
[0409] HRMS: Obs. Mass, 606.2009. Calcd. Mass, 606.2017 (M+H).
e) (2S,3S)-N-(4-Acetyl-thiazol-2-yl)-2-{(R)-2,5-dioxo-4-[4-(2-oxo-2-pyrrolidin-1-yl-ethoxy)-phenyl]-imidazolidin-1-yl}-3-phenyl-butyramide
[0410]
(R)-tert-Butoxycarbonylamino-[4-(2-oxo-2-pyrrolidin-1-yl-ethoxy)-phenyl]-acetic acid was prepared and used in a manner analogous to that described for (R)-tert-butoxycarbonylamino-(4-dimethylcarbamoylmethoxy-phenyl)-acetic acid.
[0411] HRMS: Obs. HRMS: Obs. Mass, 590.2063. Calcd. Mass, 590.2068 (M+H).
EXAMPLE 25
(2S,3S)-2-[(R)-4-(4-Dimethylcarbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0412]
[0413] Prepared as described in Example 4 except that (R)-tert-butoxycarbonylamino-(4-dimethylcarbamoylmethoxy-phenyl)-acetic acid was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine. (R)-tert-butoxycarbonylamino-(4-dimethylcarbamoylmethoxy-phenyl)-acetic acid was prepared as described in Example 23.
[0414] HRMS: Obs. Mass, 578.2066. Calcd. Mass, 578.2068 (M+H).
EXAMPLE 26
[0415] In a manner similar to that described in Example 25, the following compounds were prepared.
a) (2S,3S)-2-[(R)-4-(4-Methylcarbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0416]
(R)-tert-Butoxycarbonylamino-(4-methylcarbamoylmethoxy-phenyl)-acetic acid was prepared as described in Example 24a.
[0417] HRMS: Obs. Mass, 5641915. Calcd. Mass, 564.1912 (M+H).
b) (2S,3S)-2-[(R)-4-(4-Carbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0418]
(R)-tert-Butoxycarbonylamino-(4-carbamoylmethoxy-phenyl)-acetic acid was prepared as described in Example 24b.
[0419] HRMS: Obs. Mass, 550.1755. Calcd. Mass, 550.1755 (M+H).
c) (2S,3S)-2-((R)-4-{4-[(2-Methoxy-ethylcarbamoyl)-methoxy]-phenyl}-2,5-dioxo-imidazolidin-1-yl)-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0420]
(R)-tert-Butoxycarbonylamino-{4-[(2-methoxy-ethylcarbamoyl)-methoxy]-phenyl}-acetic acid was prepared as described in Example 24c.
[0421] HRMS: Obs. Mass, 608.2169. Calcd. Mass, 608.2174 (M+H).
d) (2S,3S)-2-{(R)-4-[4-(2-Morpholin-4-yl-2-oxo-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0422]
(R)-tert-Butoxycarbonylamino-[4-(2-morpholin-4-yl-2-oxo-ethoxy)-phenyl]-acetic acid was prepared as described in Example 24d.
[0423] HRMS: Obs. Mass, 620.2166. Calcd. Mass, 620.2174 (M+H).
e) (2S,3S)-2-{(R)-2,5-Dioxo-4-[4-(2-oxo-2-pyrrolidin-1-yl-ethoxy)-phenyl]-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0424]
(R)-tert-Butoxycarbonylamino-[4-(2-oxo-2-pyrrolidin-1-yl-ethoxy)-phenyl]-acetic acid was prepared as described in Example 24e.
[0425] HRMS: Obs. Mass, 604.2222. Calcd. Mass, 604.2225 (M+H).
f) (2S,3S)-2-{(R)-4-[4-(2-Azetidin-1-yl-2-oxo-ethoxy)-phenyl]-2,5-dioxo-imidazolidin-1-yl}-3-phenyl-N-(4-propionyl-thiazol-2-yl)-butyramide
[0426]
(R)-[4-(2-Azetidin-1-yl-2-oxo-ethoxy)-phenyl]-tert-butoxycarbonylamino-acetic acid was prepared and used in a manner analogous to that described for (R)-tert-butoxycarbonylamino-(4-dimethylcarbamoylmethoxy-phenyl)-acetic acid (prepared as described in Example 23).
[0427] HRMS: Obs. Mass, 612.1890. Calcd. Mass, 612.1887 (M+Na)
EXAMPLE 27
(2S,3S)-N-(4-Cyclopropanecarbonyl-thiazol-2-yl)-2-[(R)-4-(4-methylcarbamoylmethoxy-phenyl)-2,5-dioxo-imidazolidin-1-yl]-3-phenyl-butyramide
[0428]
Prepared as described in example 5x except that (R)-tert-butoxycarbonylamino-(4-methylcarbamoylmethoxy-phenyl)-acetic acid (prepared as described in example 24a) was used in place of (R)-tert-butyloxycarbonylamino-4-methyoxyphenylglycine.
[0429] HRMS: Obs. Mass, 576.1910. Calcd. Mass, 576.1912 (M+H).
[0000] Compound IC 50 Determination in MEK Cascade Assay
[0430] The evaluation of the compounds as MEK inhibitor was performed in a bead-based FP assay termed IMAP assay with MEK cascade components. In brief, the assay was performed in a reaction solution containing 10 mM HEPES, pH 7.0, 10 mM MgCl 2 , 50 mM NaCl, 0.1 mM NaVO 4 , and 1 m M DTT in the presence of 50 uM ATP, 0.45 nM c-RAF, 11.25 nM MEK, 90.5 nM ERK, and 0.5 μM FITC-labeled ERK (FITC-Aca-Ala-Ala-Ala-Thr-Gly-Pro-Leu-Ser-Pro-Gly-Pro-Phe-Ala-NH2). C-RAF, MEK, ERK and the ERK peptide substrates were added sequentially into the reaction buffer. Activated c-Raf phosphorylates MEK, activated MEK phosphorylates ERK, and subsequently activated ERK phosphrylates its peptide substrate. The FITC-labeled peptide substrates, when phosphorylated by the kinase, bind to nanoparticles derivatized with trivalent metal cations through a metal-phospholigand interaction. The result of this bound fluoresceinated phosphorylated product is an increase in polarization signal caused by a decrease in the molecular mobility of the bound product. Ten-point serial dilutions of the compounds were added into the MEK cascade assays before mixing with ERK and ERK peptide substrates. The reaction was incubated at 37° C. for 20 minutes for MEK activation, 20 minutes for ERK activation, 30 minutes for ERK peptide substrate phosphorylation, then was incubated overnight at room temperature for binding of IMAP beads. The IMAP assay was performed in a 384-well plate format. The changes in fluorescence polarization were measured by LJL instrument at 485 nm for excitation and 530 for emission. Polarization value (MP) was calculated as the following:
( MP )=1000×(intensity vertical −intensity horizontal )/(intensity vertical +intensity horizontal ).
[0431] The IC 50 values were generated using Excel XLfit3 wizard. Percent activity and percent inhibition of reactions in the presence of a compound were calculated by comparing their MP values to those without a compound (as 100% activity). The compounds of formula I in the above assay exhibit IC 50 values of less than 25 micro molar.
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The present invention relates to compounds of the formula
which are useful in treating diseases characterized by the hyperactivity of MEK. Accordingly the compounds are useful in the treatment of diseases, such as, cancer, cognative and CNS disorders and inflammatory/autoimmune diseases.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application this application is a continuation of U.S. patent application Ser. No. 13/857,746, filed Apr. 5, 2013, which is a continuation of U.S. patent application Ser. No. 12/683,806, filed Jan. 7, 2010, now U.S. Pat. No. 8,446,454, which is a continuation-in-part of U.S. patent application Ser. No. 11/751,558, filed May 21, 2007, now U.S. Pat. No. 8,289,371. U.S. patent application Ser. No. 12/683,806 also claims priority to U.S. Provisional Patent Application Ser. No. 61/264,310, filed Nov. 25, 2009. The entire contents of all of the above are incorporated herein by reference for all purposes.
TECHNICAL FIELD
[0002] The present disclosure generally relates to the field of communication and more specifically to methods and systems for video conferencing.
BACKGROUND ART
[0003] Videoconferencing enables individuals located remote from each other to have face-to-face meetings on short notice using audio and video telecommunications. A videoconference can involve as few as two sites (point-to-point) or several sites (multi-point). A single participant may be located at a conferencing site or there may be several participants at a site, such as at a conference room. Videoconferencing can also be used to share documents, information, and the like.
[0004] Participants in a videoconference interact with participants at other sites via a videoconferencing endpoint. An endpoint is a terminal on a network, capable of providing real-time, two-way audio/visual/data communication with other terminals or with a multipoint control unit (MCU, discussed in more detail below). An endpoint may provide speech only; speech and video; or speech, data and video communications, etc. A common videoconferencing endpoint comprises a display unit on which video images from one or more remote sites can be displayed. Exemplary endpoints can include Polycom VSX series, HDX series, etc. (each available from Polycom, Inc.). The videoconferencing endpoint sends video and/or data from a local site to the remote site(s) and displays video and/or data received from the remote site(s) on a screen.
[0005] Video images displayed on a screen at a videoconferencing endpoint can be arranged in a layout. The layout may include one or more allocated areas (segments) for displaying video images. A segment can be a portion of the screen of a receiving endpoint that is allocated to a video image received from one of the sites participating in the session. For example, in a videoconference between two participants, a segment can cover the entire display area of the screen of the local endpoint. Another example can be in a video conference between a local site and multiple other remote sites if the videoconference is conducted in switching mode, i.e., such that video from only one other remote site is displayed at the local site at a single time and the displayed remote site can be switched, depending on the dynamics of the conference. In contrast, in a continuous presence (CP) conference, a conferee at a terminal can observe, simultaneously, several other participants' sites in the conference. Each site may be displayed in a different segment of the layout, wherein each segment may be the same size or a different size. The choice of the sites displayed and associated with the segments of the layout may vary among different conferees that participate in the same session. In a continuous presence (CP) layout, a received video image from a site can be scaled down in order to fit a segment size.
[0006] A multipoint control unit (MCU) can be used to manage a video communication session (i.e., a videoconference). An MCU is a conference controlling entity that can be located in a node of a network or in a terminal, which can receive and process several media channels, from access ports, according to certain criteria and distributes them to the connected channels via other ports. Examples of MCUs include the MGC-100 and RMX 2000 (available from Polycom Inc.). Some MCUs are composed of two logical units: a media controller (MC) and a media processor (MP). A more thorough definition of an endpoint and an MCU can be found in the International Telecommunication Union (“ITU”) standards, such as but not limited to the H.320, H.324, and H.323 standards. Additional information regarding the ITU standards can be found at the ITU website www.itu.int.
[0007] To present a video image within an allocated area (a segment) over a screen (a layout) of a receiving endpoint (site), the entire received video image can be manipulated, scaled down and displayed or a portion of the video image can be cropped by the MCU and be displayed, for example. An MCU can crop lines or columns from one or more edges of a received conferee video image in order to fit it to the area of a segment in the layout of the videoconferencing image. Another cropping method may crop the edges of the received image according to a region of interest in the image, as disclosed in U.S. patent application Ser. No. 11/751,558, the entire contents of which are incorporate herein by reference.
[0008] In a videoconferencing session the size of a segment in a layout may be defined according to a layout selected, by a conferee for example, to be used in the session. For example in a 2×2 layout, each segment is in the size of substantially a quarter of the display as illustrated in FIG. 1 . Layout 100 includes segments 112 , 114 , 116 and 118 . In a 2×2 layout if five sites are taking part in a session, conferees at each site can see the other four sites.
[0009] In the example illustrated in FIG. 1 , at a certain period of time only three quarters of the area of the display is used—segments 112 , 114 , and 116 —while the fourth quarter 118 is occupied by a background color, for example. Such a situation may occur when only four sites are active and each site sees the other three. Furthermore, segment 112 displays an empty room, while the sites presented in segment 114 and 116 each include a single conferee 130 . Consequently during this period of the session only half of the screen area is effectively used and the other half is ineffectively used. The area of segment 118 and segment 112 do not contribute to the conferees' experience and therefore are not exploited in a smart and effective manner.
[0010] Furthermore as can be seen in both segment 114 and 116 , a major area of the image is redundant. In other words, the video images capture a large portion of the room while the conferees' images 120 and 130 are small and located in a small area. In those cases as in many other examples a significant portion of the display area is wasted on uninteresting areas. Consequently, the area that is captured by the conferees' images is affected and the experience of the conferees viewing the layout of the video conference is poor.
[0011] Moreover, there are conference sessions in which one or more sites have a single participant, while in other sites there are two or more participants. In currently available layouts, each site receives similar segment sizes and as a result, each participant at a site with a plurality of conferees is displayed over a smaller area than a conferee in a site with less participants, degrading the experience of the viewer.
[0012] If during a conference call one of the conferees steps far from the camera, that conferee's image will seem smaller and again the experience of the conferees viewing the layout of the video conference is degraded. Likewise, if the conferees at a displayed site leave the room for a certain time and return afterward, the empty room is displayed on the layout during the conferees' absence.
[0013] In some known techniques the viewing conferees at the other sites can manually change the layout viewed at their endpoints to adjust to the dynamics of the conference. Changing the layout can be done manually by the conferees, but this requires the conferees to stop what they are doing and deal with a layout menu to make such an adjustment, for example.
SUMMARY OF INVENTION
[0014] We found that there is a need for a method and system that can offer a wide variety of layouts in which the area of the screen can be divided among the different conferees in a flexible way. Furthermore, there is a need for a dynamic adaptation of the layout to the content of the video images that are currently received from the endpoints that participate in the session.
[0015] Exemplary embodiments of the present disclosure provide a more natural, studio like, videoconferencing user experience. Exemplary embodiments of a system and method are disclosed for presenting an automatic and dynamic layout adaptation of a CP video conferencing layout that solves the needs in the art discussed above. The systems and methods automatically divide the area of a CP layout among a plurality of sites, wherein the segment location and size allocated to each site depends on the video content, and more specifically on a current region of interest (ROI) in the video images of the sites.
[0016] According to the present disclosure video images from different sites participating in the conferencing session are decoded and processed. Periodically (each decision period) a decision can be made regarding a region of interest (ROI) in each video image. The size and the location of each ROI can be calculated. The size can be calculated in pixels according to width and height (W; H), for example. Additional criteria can be used for selecting the sites to be displayed in an adaptive layout. An exemplary embodiment may consider an audio energy indication received from each site. Other embodiments may use management decisions such as the title/rank of the conferee in each site, etc.
[0017] Different algorithms can be used for determining the ROI in each site's image. From time to time, an exemplary embodiment can capture a single frame from each of the received video images and analyze the captured frame to define an ROI. An exemplary algorithm may analyze the hue of areas of the video image, to identify flesh tone colors to define regions in which a conferee is displayed. Such an embodiment may include a bank of flesh tones colors according to different races, for example.
[0018] Other embodiments may use a face detector algorithm for determining the location of a face of a conferee. Exemplary face detector algorithms include SHORE™, available from Fraunhofer IIS, Erlangen, Germany. SHORE is a highly optimized software library for face and object detection and fine analysis. Another exemplary algorithm can be VeriLook SDK, available from Neurotechnology, Vilnius, Lithuania. Yet another exemplary face detector algorithm includes OpenCV, available from INTEL Corporation. A reader who wishes to learn more on face detectors is invited to visit http://www.consortium.ri.cmu.edu/projOmega.php or http://www.consortium.ri.cmu.edu/projFace.php.
[0019] An exemplary automatic dynamic decision algorithm can use motion vector criteria to define a region of interest of a video image. Such an embodiment may utilize a motion detector for defining a region of interest. The motion detector algorithm may also implement filters for reducing effects of uninteresting (interference) types of movements such as movements of fans, clocks, etc. Some of the filters may use low pass filters for removing fans, for example. Other filters can be notch filters to remove the movement of clock pointers, digit of a clock display, etc. Other embodiments may use band-pass filter. The band-pass filter can match the frequency range of common movements of a conferee, for example.
[0020] Alternative embodiments may use methods other than video processing for determining the presence and/or location of a conferee in the room. For example, an RFID (radio frequency identification) can be used for determining the presence of a conferee in a room. Each participant can hold an RFID card and the system can include an RFID detector in the videoconferencing rooms, for example. Yet in an alternative embodiment audio received from two or more microphones located in the room can be used for determining the location of a speaker.
[0021] Based on the size and location of a detected face an exemplary embodiment may estimate the size of a region of interest around the detected face. For example after defining the size and the location of the face the size of the ROI can be defined as a multiple of the detected face size, for example. For example, if the size of a face in numbers of pixels width×height (W×H), the ROI might be defined as 3-6 times W×H. The ROI can surround the face from a little above the face and so on. In other embodiments the size of the segment is defined first and then the image is cropped around the ROI to fit the required segment size.
[0022] The area of a next CP layout that will be presented until the next image capture can be divided among the video images received from the sites, which include detected region of interest, conferees 120 and 130 for example. The size of a segment that is associated to each site in the CP layout can be substantially proportional to the size of the region of interest in the image received from that associated site. The rest of the received images from the sites that do not have a detected ROI can be removed from the adapted layout and not be displayed. Thus, images of an empty room at a conferencing site can be removed from the layout, for example.
[0023] FIG. 2 a illustrates an exemplary layout 200 of a period in time of the conference session presented in the prior art layout 100 ( FIG. 1 ) after implementing an exemplary technique of the present disclosure. The captured images received from the four sites are analyzed. Only two images were found that include an ROI—around conferees 120 and 130 . Therefore, the area of the adapted layout can be divided into two segments 214 and 216 instead of four. Segments 112 and 118 of FIG. 1 are thus removed from the layout and remaining segments 214 and 216 (corresponding to 114 and 116 of FIG. 1 , respectively) are displayed in an orientation (portrait or landscape) most appropriate for the ROI as illustrated in FIG. 2 a . The height (number of pixels) of each segment can be substantially similar to the height of its associated received video image, while the width of each segment can be cropped to include about half of the received image. Thus only the conferee in the image and his close surroundings are displayed instead of displaying the entire room, most of which is empty and therefore uninteresting.
[0024] Consequently the experience of the conferees receiving the adapted layout 200 is improved because the received images of the conferees presented in the layout 200 are bigger and no redundant areas are displayed. This can produce a similar effect as a zoom effect.
[0025] If the sum of the sizes, in pixels, of the ROIs of each received image is bigger than the size of the layout of the CP image, then the ROIs can keep their proportion and be scaled down, for example. Alternatively, the segment can be cropped to a smaller area around each ROI, or any combination of these two methods can be used.
[0026] An exemplary embodiment of the present disclosure can detect that a person has entered the site of an empty segment, such as segment 112 FIG. 1 . In case a conferee enters the room then an exemplary embodiment of the present invention can automatically change the adapted layout displayed. The bottom half of segments 214 and 216 can be cropped and instead a 3rd segment for presenting the new site region of interest can be added, for example (not shown in the drawings).
[0027] FIG. 2 b illustrates yet another automatic adaptive layout 250 that can be created by an embodiment of the present disclosure. During a certain decision point two sites were found with ROIs. However, one site features two conferees 258 and 260 while in the other site features only one conferee 254 . As a result of analyzing the captured images an asymmetric adaptive layout 250 can be created. In layout 250 a wide segment 256 can be allocated to the site with two conferees 258 and 260 while a narrower segment 252 can be allocated to the site with one conferee 254 . In both segments the video images have been automatically manipulated to display only the region of interest in methods as described above.
[0028] Another embodiment may use a face tracking mechanism. In such an embodiment an area which was defined as an ROI can be kept in the middle of a segment regardless even if the ROI moves, creating an effect that is similar to the effect of tracking a face with a video camera. In such an embodiment the displayed area can be dynamically and automatically updated according to the movement of the conferee, keeping the face in the center of the segment.
[0029] These and other aspects of the disclosure will be apparent in view of the attached figures and detailed description. The foregoing summary is not intended to summarize each potential embodiment or every aspect of the present invention, and other features and advantages of the present invention will become apparent upon reading the following detailed description of the embodiments with the accompanying drawings and appended claims.
[0030] Furthermore, although specific exemplary embodiments are described in detail to illustrate the inventive concepts to a person skilled in the art, such embodiments are susceptible to various modifications and alternative forms. Accordingly, the figures and written description are not intended to limit the scope of the inventive concepts in any manner.
BRIEF DESCRIPTION OF DRAWINGS
[0031] Exemplary embodiments of the present disclosure will be more readily understood from reading the following description and by reference to the accompanying drawings, in which:
[0032] FIG. 1 illustrates an exemplary prior art 2×2 layout displayed.
[0033] FIGS. 2 a and 2 b illustrates an exemplary layout adapted according to video content (ROI) according to the present disclosure teaching.
[0034] FIG. 3 is a block diagram illustrating elements of an exemplary multimedia multipoint conferencing system in which an exemplary embodiment of the present disclosure can be implemented.
[0035] FIG. 4 illustrates elements of an exemplary MCU 400 capable of implementing the system and method of dynamically and automatically adapting a CP layout, according to the present disclosure.
[0036] FIG. 5 is a block diagram illustrating elements of an exemplary region of interest detector (ROID) 500 , according to the present disclosure.
[0037] FIG. 6 is a flowchart illustrating exemplary steps of a method for defining regions of interests in a video image, according to the present disclosure.
[0038] FIGS. 7 a and 7 b are a flowchart illustrating exemplary steps of a method for automatically and dynamically adapting one or more CP layouts, according to the teaching of the present disclosure.
DESCRIPTION OF EMBODIMENTS
[0039] Turning now to the figures in which like numerals represent like elements throughout the several views, exemplary embodiments, aspects and features of the disclosed systems and methods are described. For convenience, only some elements of the same group may be labeled with numerals. The purpose of the drawings is to describe exemplary embodiments and not for production or limitation.
[0040] FIGS. 1, 2 a and 2 b were described above and will not be further described. FIG. 3 illustrates elements of an exemplary multimedia multipoint conferencing system 300 . System 300 can include a network 310 , one or more multipoint control unit (MCU) 320 and a plurality of endpoints in different sites 330 a - n . Network 310 can be a packet switched network, a circuit switched network or any combination of the two, for example. The multimedia communication over the network can be based on communication protocol such as, but not limited to: H.320, H.323, SIP, etc.
[0041] MCU 320 and endpoints 330 a - n can be adapted to operate according to embodiments of the present disclosure to improve the experience of a conferee looking at a CP video image of a multipoint video conferencing. In embodiments implementing a centralized architecture, MCU 320 can be adapted to perform the automatic display adaptation methods described herein. Alternatively, endpoint 330 a - n with or without MCU 320 can be adapted to perform the automatic display adaptation methods. More information about the operation of MCU 320 and endpoints 330 a - n according to different embodiments is disclosed below. FIG. 4 illustrates an exemplary MCU 400 , which is capable of dynamically and automatically adapting a CP layout. MCU 400 may include a network interface module (NI) 420 , an audio module 430 , a control module 440 and a video module 450 . The network interface module 420 can receive communication from a plurality of endpoints 330 a - n ( FIG. 3 ) via networks 310 ( FIG. 3 ). Network interface 420 can process the communication according to one or more communication standards such as, but not limited to: H.320, H.323, SIP, etc. Network interface 420 can also process the communication according to one or more compression standards such as, but not limited to: H.261, H.263, H.264, G711, G722; MPEG etc. Network interface 420 can receive and transmit control and data information to/from other MCUs and endpoints. More information concerning the communication between endpoint and the MCU over network 310 and information describing signaling, control, compression, and setting a video call can be found in the international telecommunication union (ITU) standards H.320, H.321, H.323, H.261, H.263, H.264 G711, G722, and MPEG etc.
[0042] Network interface module 420 can multiplex/de-multiplex the different signals, media and/or “signaling and control” that are communicated between the endpoints and the MCU. The compressed audio signal can be transferred to and from the audio module 430 . The compressed video signal can be transferred to and from the video module 450 . The “control and signaling” signals can be transferred to and from control module 440 . Furthermore, if a distributed architecture is used, network interface module 420 can be capable of handling automatic and dynamic CP layout adaptation related information that is transferred between the control module 440 and the endpoints 330 a - n ( FIG. 3 ).
[0043] In an exemplary embodiment in which the automatic and dynamic CP layout adaptation information is sent as a part of a predefined header of a payload of an RTP (Real-time Transport Protocol) packet, NI 420 can be adapted to process the predefine header to add automatic and dynamic CP layout adaptation information to the RTP packet. The automatic and dynamic CP layout adaptation information can include the size and location of a region of interest (ROI) in pixels, for example. In an alternate embodiment, ROI communication can be executed via the Far End Camera Control (FECC, not shown in FIG. 4 ) channel, for example.
[0044] Audio module 430 may receive, via network interface 420 compressed audio streams from the plurality of endpoint 330 a - n ( FIG. 3 ). The audio module 430 can decode the compressed audio streams, analyze the decoded streams, select certain streams and mix the selected streams. The mixed stream can be compressed and the compressed audio stream can be sent to the network interface 420 , which sends the compressed audio streams to the different endpoints 330 a - n ( FIG. 3 ). Audio streams that are sent to different endpoints can be different. For example the audio stream can be formatted according to a different communication standard and according to the needs of the individual endpoint. The Audio stream may not include the voice of the user associated with the endpoint to which the audio stream is sent. However, the voice of this user may be included in all other audio streams.
[0045] In some exemplary embodiments of the disclosure, an endpoint can be configured to define its audio energy and send the information on the audio energy in association to its compressed audio signal.
[0046] Audio module 430 can be adapted to analyze the received audio signals from the endpoints and determine the energy of each audio signal. Information on the signal energy can be transferred to the control module 440 . In some embodiments two or more microphones can be used in a certain site. The energy from each microphone can be used for determining the ROI of certain sites, for example. In some embodiments the energy level can be used as a selection parameter for selecting appropriate one or more endpoints as the source of the mixing of the audio and/or the video of the conference. The endpoints can be referred as selected endpoints or presented endpoints. Yet, in some other exemplary embodiments of distributed architecture an endpoint may have some of the functionality of the audio module 430 .
[0047] Video module 450 can receive compressed video streams from the plurality of endpoints 330 a - n ( FIG. 3 ), which are sent toward the MCU 400 via network 310 ( FIG. 3 ) and processed by network interface (NI) 420 . Video module 450 can create one or more compressed CP video images according to one or more layouts that are associated with one or more conferences currently being conducted by the MCU 400 . An exemplary video module 450 can have a plurality of input modules 451 a - c , a plurality of output modules 455 a - c and a video common interface 454 . Each input module 451 a - c can be associated with an endpoint. Each output module 455 a - c can be associated with one or more endpoints.
[0048] Control module 440 can be a logical unit that controls the operation of the MCU 400 . In addition to common operation of a typical MCU, MCU 400 is capable of additional functionality as result of having the control module 440 . Control module 440 can include an adaptive layout controller (ALC) 442 . An exemplary ALC 442 can be responsible to adapt the layout that will be displayed in each site. The ALC 442 can receive information and updates from the NI 420 . Such information can include, but is not limited to: the number of sites that will participate in the conference call, which site has departed, which sites have been added, and so on. Other information can be commands regarding the layout that one or more participants request, for example.
[0049] The ALC 442 can receive information and updates from the audio module 430 , such as audio signal strength measured from each site, for example. According to information received from the NI 420 and the audio module 430 , the ALC 442 can send command controls to the video module 450 . Exemplary commands can: identify an ROI in certain sites, scale down or scale up images from certain sites, crop certain images, build an updated layout with certain number of segments having certain sizes and format/proportion (landscape or portrait), and so on.
[0050] In an alternate exemplary embodiment in which decentralized (distributed) architecture is implemented, an exemplary ALC 442 can be capable of providing commands to the endpoints ( 330 a - n FIG. 3 ) themselves. In an exemplary embodiment the size, in pixels for example, of the ROI over each image in the layout is sent to the endpoint with a request to the endpoint to present a layout such that: certain number of segments with certain segments size will be displayed, the ROI size and place of each segment is optimized, and so on. Such communication with the endpoint can be out of band, over an Internet Protocol (IP) connection for example. In other embodiments the communication can be in band, for example as part of the predefined header of the payload of an RTP packet, or FECC, for example.
[0051] In an exemplary embodiment, an output module 455 a - c associated with an endpoint can be instructed to crop certain images around the ROI and place them in certain segments in the adaptive CP image. More information on the operation of ALC 442 is discussed below in conjunction with FIG. 7 . In some embodiments ALC 442 can be embedded within the video module 450 . Yet in another embodiment the ALC 442 can be a part of each one of the output module 455 a - c . In another exemplary embodiment of a distributed architecture ALC 442 can be located in an endpoint.
[0052] Exemplary video module 450 can comprise a plurality of input modules 451 a - c ; a plurality of output modules 455 a - c ; and a common interface 454 . Exemplary input module 451 a - c can include among other elements a decoder 452 and a region of interest detector (ROID) 453 . Exemplary ROID 453 may be a sub-module of input modules 451 a - c , or in an alternate embodiment ROD 453 can be a sub-module of video module 450 . An exemplary input module 451 a - c can be associated with an endpoint and may process compressed video images received from its associated endpoint. The decoder 452 can receive compressed video from an associated endpoint and can decode the compressed video into decoded video data. Usually the decoded video data is constructed from three components, YUV. The Y component reflects the brightness and the U and V components reflect the chrominance of the pixel, for example. The decoded information is stored in a decoder frame memory from which it is transferred toward one or more output modules 455 a - c via common interface 454 .
[0053] In an exemplary embodiment, the data of the decoder frame memory can be sampled by the ROID 453 . ROID 453 can be adapted to analyze the video image received from the associated endpoint and to define the coordinates of one or more ROIs. From time to time, periodically and/or upon receiving a command from the ALC 442 , the ROID 453 can sample, a captured frame of the decoded video. The ROID can then analyze the sampled image and identify the ROIs. The analysis can be done according to one or more different detection methods. Methods such as, but not limited to: motion detection, flesh tone detectors, audio energy indication of audio signal received from a plurality of microphones located in the same room, face detectors, or different combination of different detectors. The ROID 453 can output detected information on the ROI size and location to the ALC 442 via control line 444 , for example.
[0054] In some embodiments the ROID 453 may deliver parameters according to the size of the ROI as well as the number of participants in the video image. In distributed architecture, an exemplary ROID 453 can be located in an endpoint and may process the video data generated by its video camera. More information about the operation of ROID 453 is discussed below in conjunction with FIGS. 5 and 6 .
[0055] Among other elements an exemplary output module 455 a - c may include an editor 456 and an encoder 458 . Editor 456 can get decoded data of selected video images from the common interface 454 to be composed into a CP image created by the output module 455 . The editor 456 may scale, crop, and place the video data of each conferee into an editor frame memory according to the location and the size of the image in the layout associated with the composed video of the CP image. Cropping can be done according to the instructions received from ALC 442 . The cropping instruction takes into account the defined ROI. Editor 456 and encoder 458 may each be considered as modules, or as sub-modules of output modules 455 a - c.
[0056] When the editor frame memory is ready with all the selected conferee's images with or without an adapted cropped image, the data in the frame memory is ready to be encoded by encoder 458 and sent toward its associated endpoint. In a distributed architecture an exemplary endpoint can include an editor 456 . In such embodiment, the editor can be located after a decoder of the endpoint. The editor can be configured to collect the decoded video images received from a plurality of endpoints, to build the frames of the CP video images based on received ROI information regarding each video image, and send the composed CP video image toward a display unit of the endpoint. Additional functions of a video module such as 450 are described in U.S. patent application Ser. No. 10/144,561; U.S. Pat. No. 6,300,973; and International Application Serial No. PCT/IL01/00757, the contents of which are incorporate herein by reference.
[0057] FIG. 5 illustrates elements of an exemplary region of interest detector (ROID) 500 . An exemplary ROID 500 can include a scaler and frame memory (SCFM) 510 , a face detector processor (FDP) 520 , and an ROID controller (ROIDC) 530 . The face detector processor (FDP) 520 can be implemented on a DSP that is adapted to execute a known face detector method such as VeriLook SDK, available from Neurotechnology, or OPEN CV, available from INTEL, for example. In alternate embodiment, FDP 520 can be implemented in a built in hardware with face detection capabilities such as but not limited to Texas Instrument (TI) DM365. In an exemplary centralized architecture ROID 500 can be embedded in an MCU. In such an embodiment ROID 500 can be part of each input module 451 a - c ( FIG. 4 ). Yet in another embodiment ROID 500 can be part of the video unit 450 ( FIG. 4 ) and can get the decoded video data from the relevant input modules 451 a - c via the common interface 454 ( FIG. 4 ). In an alternate exemplary embodiment of the present disclosure, in which TI chip DM365 is used, ROID 500 can obtain compressed video generated by the relevant endpoints and process the compressed video in order to define the ROI.
[0058] Yet in another exemplary embodiment ROID 500 can be embedded within an endpoint 330 a - n ( FIG. 3 ). In such an endpoint the ROID 500 may be used to determine the ROI in a video image that is generated by the endpoint. The ROID can be associated with the input of an encoder of the endpoint (not shown in the drawings), for example. The ROID 500 can sample a frame of a video image used at the input of the encoder of the endpoint, for example. The indication on the ROI can be transferred to the ALC 442 via NI 420 ( FIG. 4 ). The ALC 442 may use the coordinates of the ROI to determine how to adapt the next CP layout.
[0059] In the exemplary embodiment of FIG. 5 , the ROID controller (ROIDC) 530 can receive a command from the ALC 442 ( FIG. 4 ) to detect and define an ROI of a site, for example. ALC 442 can decide in which sites to search for ROI according to different parameters such as audio signal strength, manual commands to change the layout, or a newly site has joined, and so on. ROIDC 530 can send a command to the face detector processor (FDP) 520 to find and determine an ROI in a frame of a video image received from a certain site. FDP 520 can command SCFM 510 to sample a frame of a decoded video image of the certain site. The decoded video image can be fetched by SCFM 510 from the common interface 454 ( FIG. 4 ) or from the decoder 452 ( FIG. 4 ) of the certain site. SCFM 510 can then scale down the video image according to the requirements of the FDP 520 , and save the result in a frame memory, for example.
[0060] A loop back path between FDP 520 and SCFM 510 can be established so that FDP 520 can request SCFM 510 to: scale down the image again, scale up the image, or fetch another sample, and so on. This loop back path can be limited to a predefined number of cycles. At the end of the cycle FDP 520 can transfer information on the ROI to ROIDC 530 . In case that no ROI was found, a message (such as site is vacant, for example) can be sent to the ROIDC 530 . The ROID 453 can output the detected information on the ROI size and location (coordinates and/or pixel from top left, for example) to the ALC 442 via control line 444 , for example.
[0061] Another exemplary embodiment of ROID 500 may comprise other units such as, but not limited to: motion detection, flesh tone detectors or different combination of different detectors. Some exemplary embodiments (not shown in the drawings) based on motion detectors may include one or more filters such as band-pass filters, low-pass filters or notch filters to remove interference motions such as clocks, fans, monitors, etc. Other embodiments may process the audio energy indication received from a plurality of microphones, etc. A person who wishes to learn more on the different ROI detectors can read U.S. patent application Ser. No. 11/751,558, filed May 21, 2007 (Publication No. 2008/0291265).
[0062] If ROID 500 is embedded within a video unit 450 ( FIG. 4 ) of MCU 400 ( FIG. 4 ), the communication between ROIDC 510 and control module 440 can be implemented over the control bus 444 connecting the control module 440 with a video module 450 . Alternatively in an embodiment in which ROID 500 is located at an endpoint 330 a - n ( FIG. 3 ) while control module 440 is located at the MCU 400 , the communication can be implemented out of band or in band. Out of band communication can be handled via a connection between the endpoints and the MCU over an Internet Protocol (IP) network, for example.
[0063] If multimedia communication is over a packet switched network, the communication between ROID 500 and control module 440 can be implemented using a predefined header of the payload of a Real-time Transport Protocol (RTP) video packet. In such an embodiment the coordinates of the ROI as well as the sampling command can be embedded within the predefined header of the payload of the RTP video packet. Other embodiments may use FECC channels for example.
[0064] If communication between ROID 500 and control module 440 is via one of the above methods, the network interface 420 ( FIG. 3 ) can be adapted to parse the received information, retrieve the coordinates of the ROI received from ROID 500 and deliver the coordinates of the ROI to control module 440 over the control bus that connects the control module 440 and network interface 420 . In the other direction the network interface 420 is adapted to receive sampling command and process it according to the used communication method and send it via the network 310 ( FIG. 3 ), for example.
[0065] FIG. 6 illustrates steps of method 600 that can be executed by an exemplary ROID 500 ( FIG. 5 ). Method 600 can be used for defining regions of interest in a video image. Method 600 can be initiated 602 upon power on of ROID 500 ( FIG. 5 ), for example. After initiation method 600 can reset 604 a frame counter (Fcnt) and a change-layout register (CHL) to zero. An exemplary frame counter (Fcnt) can count the frames at the output of an input module 451 a - c ( FIG. 4 ). CHL value can be 0 or 1. When CHL value equals 1 it means that a change in a layout was received from ALC 442 ( FIG. 4 ). ALC 442 ( FIG. 4 ) may request ROIDC 530 to search for an ROI in an image site due to change in audio signal strength, or due to management requests, a new conferee, etc. When CHL value equals 0 it means that no change in a layout has been indicated.
[0066] Next, method 600 may wait 610 to receive a new frame. If 610 a new frame is not received, then method 600 returns to step 610 . If 610 a new frame is received, then method 600 proceeds to step 612 and increases the Fcnt by one. Next if 620 Fcnt value does not equal N1, and CHL value equals 0, then method 600 returns to step 610 . If 620 Fcnt value equal N1, or CHL value equals 1, then method 600 proceeds to step 622 . N1 can be a configured number in the range between 1 and 100, for example.
[0067] At step 622 method 600 can instruct the FDP 520 ( FIG. 5 ) to search and define an ROI. Method 600 waits 624 till FDP 520 defines an ROI or informs that no ROI has been found. Once the FDP outputs 624 the ROI message, method 600 proceeds to step 626 . At step 626 method 600 can collect and process 626 the analyzed data from FDP 520 . Method 600 can determine 626 the existence of an ROI its size and location (in pixels from top left, for example). At this step Method 600 acts as an application program interface (API) between the face detector processor 520 ( FIG. 5 ) and the ALC 442 ( FIG. 4 ). The results are transferred 626 to ALC 442 ( FIG. 4 ), and method 600 returns to step 604 . In some exemplary embodiments, method 600 may repeat steps 622 to 626 a few times to check that the results are similar and if yes then an average ROI is transferred to the ALC 442 .
[0068] FIG. 7 a illustrates steps of method 700 . Method 700 can be used for automatically and dynamically adapting one or more CP layouts. Method 700 can be executed 702 by an exemplary ALC 442 ( FIG. 4 ). At initiation, method 700 can reset 704 Previous-ROI memory. Previous-ROI memory can be used for storing information on the previous found ROI in order to check the differences with the current ROI. Next, method 700 can reset 706 a timer (T) and wait 710 for timer T value to equal T1. T1 can be in the range of a few hundreds of msec. to few seconds, for example. Once timer T value equals T1, method 700 proceeds to step 712 .
[0069] At step 712 method 700 can collect information on the ROI from relevant ROIDs 453 ( FIG. 4 ). The relevant ROIDs are the ones that are associated to the conferees that were presented in the previous cycle looking for a change from the previous loop. For each presented conferee, method 700 can calculate 714 the difference of the current received ROI location and size compared to the previous ROI location and size (saved in Previous-ROI memory). Next a decision is made 720 whether there is a significant change in the current ROI location and size versus the previous ROI. A significant change can be a pre-defined delta in pixels or percentages, for example. An exemplary significant change can be in the range of 5 to 10%, for example. If in step 720 there is a significant change then method 700 proceeds to step 732 . If in step 720 there is no significant change then method 700 proceeds to step 722 .
[0070] At step 722 method 700 can check if there are management changes/requests regarding one of the sites, which has been requested by CM 440 ( FIG. 4 ). Examples of management changes/requests include, but are not limited to: a new conferee wishes to join, a conferee requests to leave, a speaker has changed (according to measured audio signal strength), etc. If in step 730 there are no management changes/requests, then method 700 returns to step 706 . If in step 730 there are one or more management changes/requests in a one or more sites then method 700 proceeds to step 732 .
[0071] Returning to steps 720 and/or 730 : if there was a significant change between the current received ROI and the last saved ROI or there were management changes/requests, then method 700 proceeds to step 732 stores the current received ROI location and size of each site video image in the Previous-ROI memory storage. Next, method 700 proceeds 734 to step 750 in FIG. 7 b in which an adapted layout is calculated.
[0072] As illustrated in FIG. 7 b , at step 750 a loop is started 760 for each output module 455 a - c ( FIG. 4 ). Method 700 can fetch 762 information on parameters related to the CP layout associated with the current output module. Such parameters include, but are not limited to: the layout size in number of pixels W×H, the layout format selected (2×2, 3×3, etc.), if existing, the identification of sites that have been selected to be presented based on management decision and/or audio energy, etc. Method 700 can also reset 762 a counter (CNT) that will count the number of trials.
[0073] Next method 700 can get 764 ROI information and parameters for each of the sites that were selected to be presented in the adaptive layout of the relevant output module 455 a - c ( FIG. 4 ). Exemplary parameters can be: the number of pixels of the ROI (height and width of the ROI), the top left location of the ROI in the received image, the number of participants in the ROI, and so on. According to the ROI and the video parameters of the current output module, method 700 can determine 764 which sites will be presented and in which layout format to present them. For example, if certain selected site does not include an ROI then method 700 can determine not to present that site.
[0074] Per each presented site method 700 can determine 766 the segment size (number of pixels) and shape that the site will be displayed in and the proportion and orientation of that segment in the layout. The proportion and orientation (landscape or portrait) can be based on the size and shape of the ROI (in pixels), for example. After allocating a segment to each one of the presented images, a trial and error loop between step 768 and 782 for embedding the segments in the layout can be initiated.
[0075] Next, method 700 can try to embed 768 the segments in the layout. An exemplary method can place the largest segment at the top left corner of the layout and then place the next largest size segment to the right of the largest segment if there is room, or below the largest segment if that is a better fit. Method 700 can proceed with the rest of the segments, until all segments are embedded or until there is no room to embed the next segment.
[0076] Another exemplary method may place 768 the largest segment in the top left corner of the layout and then search for a segment with a size that can fit in the rest of the space on the right of the largest image. The next largest size segment is embedded below the largest one and one or more segments with a width fitting in the space to the right border of the layout are embedded, and method 700 can proceed until all segments are embedded or until there is no room to embed the next segment.
[0077] At the end of step 768 method 700 can increase 768 the counter CNT value by one and a decision is made 780 whether all the selected ROIs can be embedded in the layout and be displayed in a CP image or whether the value of the counter equal N1. If 780 the answer is negative, then method 700 can calculate the missing space size and accordingly scale down 782 one or more ROI, or scale down 782 all ROIs, for example. Then method 700 can return to step 768 and start a next cycle in the loop with smaller ROIs. If 780 there is place for all selected ROI, or the counter equal N1, then the loop is terminated and method 700 proceeds to step 784 . N1 can be a configurable number in the range of 3-10, for example.
[0078] If 784 CNT value equals N1, then method 700 can select 786 a common layout that can fit the number of selected ROIs. If there are four images with ROI, then 2×2 layout can be selected and each segment can be in a quarter of the size of the layout, for example. Method 700 can define 786 the size and the location of the top-left pixel for each ROI in its associated segment and instructs 786 the editor 456 ( FIG. 4 ) how to crop, scale and place that ROI in its associated segment. In other embodiments the all image can be displayed instead of the ROI.
[0079] If 784 CNT value does not equals N1, which means that in the last loop a layout that includes all the ROIs was found. According to the final layout, instruction to the editor 456 ( FIG. 4 ) for building an adapted layout can be made. The instruction can define which decoded video image to get from the common interface 454 , how to crop it (if needed), scale it (if needed) and where to place the cropped and scaled image in the layout. Next method 700 checks 790 if there are additional output modules (ports) 455 a - c for defining their adapted layout. If 790 yes, then method 700 can return to step 760 . If 790 not, then method 700 can return to step 706 FIG. 7 a.
[0080] Some exemplary embodiments instead of using a loop (steps 760 - 790 ) may use a plurality of threads in parallel. Each thread can be associated with an output module.
[0081] In the present disclosure, the words “unit,” “element,” “module” and “logical module” may be used interchangeably. Anything designated as a unit or module may be a stand-alone unit or a specialized or integrated module. A unit or a module may be modular or have modular aspects allowing it to be easily removed and replaced with another similar unit or module. Each unit or module may be any one of, or any combination of, software, hardware, and/or firmware, ultimately resulting in one or more processors programmed to execute the functionality ascribed to the unit or module. Additionally, multiple modules of the same or different types can be implemented by a single processor. Software of a logical module can be embodied on a computer readable medium such as a read/write hard disc, CDROM, Flash memory, ROM, or other memory or storage, etc. In order to execute a certain task a software program can be loaded to an appropriate processor as needed.
[0082] In the description and claims of the present disclosure, “comprise,” “include,” “have,” and conjugates thereof are used to indicate that the object or objects of the verb are not necessarily a complete listing of members, components, elements, or parts of the subject or subjects of the verb.
[0083] It will be appreciated that the above described apparatus, systems and methods may be varied in many ways, including, changing the order of steps, and the exact implementation used. The described embodiments include different features, not all of which are required in all embodiments of the present disclosure. Moreover, some embodiments of the present disclosure use only some of the features or possible combinations of the features. Different combinations of features noted in the described embodiments will occur to a person skilled in the art. Furthermore, some embodiments of the present disclosure can be implemented by combination of features and elements that have been described in association to different exemplary embodiments along the discloser. The scope of the invention is limited only by the following claims and equivalents thereof.
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Dynamically adapting a continuous presence (CP) layout in a videoconference enhances a videoconferencing experience by providing optimum visibility to regions of interest within the CP layout and ignoring regions of no interest. Based on the CP layout, a CP video image can be built, in which a conferee at a receiving endpoint can observe, simultaneously, several other participants' sites in the conference. For example, more screen space within the CP layout is devoted to presenting the participants in the conference and little or no screen space is used to present an empty seat, an empty room, or an unused portion of a room. Aspect ratios of segments of the CP layout (e.g., landscape vs. portrait) can be adjusted to optimally present the regions of interest. The CP layout can be adjusted as regions of interest change depending on the dynamics of the video conference.
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CROSS-REFERENCE TO THE RELATED APPLICATIONS
The invention set forth in U.S. patent applications Ser. No. 923,865, filed Oct. 28, 1986, U.S. Pat. No. 4,787,357; Ser. No. 904,622, filed Sept. 8, 1986, U.S. Pat. No. 4,773,377; Ser. No. 14,266, filed Feb. 12, 1987, U.S. Pat. No. 4,763,629; and Ser. No. 42,505, filed Apr. 27, 1987, U.S. Pat. No. 4,727,845, are assigned to the same assignee of the instant application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to an air/fuel control system for automotive vehicles and, more particularly, to the air/fuel control system designed for a supercharged automotive engine to be operated with a combustible mixture having an air/fuel ratio that is higher than the stoichiometric ratio during a particular operating condition of the engine.
2. Description of the Prior Art
In an automotive power plant, it is generally well known that, although the supply of a lean air-fuel mixture, i.e., a combustible mixture having an air/fuel ratio higher than the stoichiometric value, to the automotive engine may bring about a reduction in the engine power output, it brings about a reduction in fuel consumption because of the substantially complete combustion of the mixture taking place in the engine and a reduction in NOx emission because of the lowering of the combustion temperature.
Based on this general notion, Japanese Laidopen Patent Publication No. 57-210137 discloses a so-called "lean-burn engine" provided with an air/fuel control system operable to provide a combustible mixture with an air/fuel ratio of, for example, 17 to 24 which is higher than the stoichiometric value (i.e., 14.7) during a normal practical drive condition when a high engine output is not required, thereby accomplishing the reduction in fuel consumption and also the reduction in NOx emission.
It has, however, been found that, during the practical drive condition of the engine when a relatively high amount of torque is required, the operation of the engine with the lean combustible mixture results in a shortage in engine power. Therefore, it is a general practice that, when the throttle opening attains a value greater than a predetermined value TVθ 1 as shown in the graph of FIG. 11 during the practical drive condition, the air/fuel mixing ratio of the combustible mixture is controlled to, for example, 13.7, which is lower than the stoichiometric value.
In the engine disclosed in the previously mentioned publication, since for a given torque to be produced, the degree of throttle opening is comparatively large when the lean combustible mixture is supplied to the engine, and therefore, the available range (TVθ 1 to WOT shown in the graph of FIG. 11) over which the throttle opening can be adjusted during the drive condition (enriched drive condition) in which the engine is operated with the supply of the enriched combustible mixture is so narrow that, under the engine operating condition in which the throttle opening is greater than the value TVθ 1 , an abrupt increase in torque tends to occur with an increase in the degree of throttle opening. Because of this, when the throttle opening attains the value TVθ 1 , the torque produced by the engine undergoes an abrupt change as indicated by the point P in the graph of FIG. 11 and torque shocks occur to such an extent that the automobile driver is made uncomfortable.
In order to substantially eliminate the possible occurrence of the torque shocks, a method has been contemplated in which a shift from the lower air/fuel mixing ratio to the higher air/fuel mixing ratio is slowed. However, since, as shown in the graph of FIG. 12, the NOx emission tends to be at a maximum when the air/fuel mixing ratio is within the range of 15 to 16, the slowing of the shift from the lower air/fuel mixing ratio (L 1 ) to the higher air/fuel mixing ratio (L 2 ), when the throttle opening is within the range of, for example, TVθ 1 to TVθ 2 , may result the supply of the combustible mixture having an air/fuel mixing ratio within the range of 15 to 16 continuing for a substantial length of time. This means that during such a substantial length of time, the maximum NOx emission takes place, as indicated by a portion R in the curve G in FIG. 11.
SUMMARY OF THE INVENTION
Accordingly, the present invention has been devised to substantially eliminate the above-discussed problems inherent in the prior art air/fuel control systems for automotive vehicles and has as its essential object to provide an improved air/fuel control system wherein, when a relatively low engine power output is required while the engine is in the practical driving condition, a substantial reduction in the fuel consumption and in the NOx emission can be accomplished and, on the other hand, during an engine operating condition in which a relatively high engine power output is required, a required amount of power output can be attained without any torque shock occuring and without incurring any increase in the fuel consumption and in the NOx emission.
To this end, an air/fuel control system herein provided comprises a supercharger for supercharging air to be supplied to the engine, a detecting means for detecting a plurality of parameters representative of an engine operating condition, an air/fuel ratio regulating means for regulating the air/fuel mixing ratio to an arbitrarily chosen predetermined value, and a control means for controlling the air/fuel ratio regulating means. The control means is designed to cause the air/fuel ratio regulating means to adjust the air/fuel mixing ratio to a predetermined value higher than the stoichiometric value when the detecting means indicates that the engine is in a normal operating condition while the supercharger is operated, and also to adjust the air/fuel mixing ratio to a predetermined value lower than the stoichiometric value when the detecting means indicates that the engine is in an operating condition in which a relatively high engine power output is required.
According to the present invention, when the detecting means for detecting the parameters representative of an operating condition indicates that a relatively low engine power output is required while the engine is in the practical driving condition and the throttle is open to a degree not greater than a predetermined degree of throttle opening, the control means causes the supercharger to be inoperative and also causes the air/fuel ratio regulating means to adjust the air/fuel mixing ratio to the predetermined value higher than the stoichiometric mixing ratio 14.7. Accordingly, as is the case with the prior art lean-burn engine, a reduction in the fuel consumption and in the NOx emission can be accomplished.
On the other hand, when the detecting means indicates that a relatively high engine power output is required during the practical driving condition with the throttle open to a degree not smaller than the predetermined value, the control means causes the supercharger to operate and also causes the air/fuel ratio regulating means to adjust the air/fuel mixing ratio to the predetermined value higher than the stoichiometric mixing ratio. Accordingly, the supercharging of the air being supplied to the engine ensures that the high engine power output is generated during the practical driving mode even though the engine is supplied with the lean combustible mixture to which minimized fuel consumption and minimized NOx emission can be attributed.
It is to be noted that, since during the practical driving condition the engine is supplied with the leaned combustible mixture, torque shock, which often occurs in the prior art lean-burn engine, will not substantially occur. Moreover, since, during a high load operating condition in which a higher load is imposed on the engine than that during the practical driving condition, the adjustment of the air/fuel ratio is effected, simultaneously with the supercharging of the air, to be lower than the stoichiometric value and therefore a powerful engine output can be obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
This and other objects and features of the present invention will become clear from the following description taken in conjunction with preferred embodiments thereof with reference to the accompanying drawings, in which:
FIG. 1 is a schematic sectional view of an automotive power plant acording to one preferred embodiment of the present invention, in which an engine-driven supercharger is employed;
FIG. 2 is a schematic sectional view of the automotive power plant according to another preferred embodiment of the present invention, in which an exhaustdriven supercharger, that is, a turbocharger is employed;
FIG. 3 is a graph illustrating the relationship between the average effective pressure and the suction pressure;
FIG. 4 is a graph illustrating the relationship between the average effective pressure and the air/fuel mixing ratio;
FIG. 5(a) is a graph illustrating the throttle opening relative to the suction pressure;
FIG. 5(b) is a graph illustrating the ignition timing relative to the suction pressure;
FIG. 5(c) is a graph illustrating the average effective pressure relative to the suction pressure;
FIG. 6(a) is a graph showing the the fuel consumption relative to the air/fuel mixing ratio;
FIG. 6(b) is a graph showing the maximum allowed ignition timing determined for avoiding the occurrence of engine knocking relative to the air/fuel mixing ratio;
FIG. 6(c) is a graph showing the average effective pressure relative to the air/fuel mixing ratio.
FIG. 7 is a flowchart showing one preferred sequence of control steps performed by a control means used in any one of the embodiments of the present invention;
FIG. 8(a) is a graph showing the change in the air/fuel mixing ratio with a change in suction pressure;
FIG. 8(b) is a graph showing the relationship between the suction pressure and the throttle opening, both controlled according to the flowchart of FIG. 7;
FIG. 8(c) is a graph showing the relationship between the air/fuel mixing ratio and the throttle opening, both controlled according to the flowchart of FIG. 7;
FIG. 9 is a flowchart showing another preferred sequence of control steps performed by the control means;
FIG. 10(a) is a characteristic curve showing the relationship between the speed correcting coefficient and the engine speed;
FIG. 10(b) is a characteristic curve showing the relationship between the throttle opening correcting coefficient and the suction pressure;
FIG. 10(c) is a characteristic curve showing the relationship between the suction pressure and the throttle opening;
FIG. 11 is a graph showing the change in torque relative to the throttle opening exhibited by the prior art lean-burn engine; and
FIG. 12 is a graph showing the change in NOx emission relative to the air/fuel mixing ratio.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Before the description of the present invention proceeds, it is to be noted that like parts are designated by like reference numerals throughout the accompanying drawings.
(First Embodiment)
Referring first to FIG. 1, there is shown an automotive power plant which comprises an internal combustion engine 1 having a combustion chamber 4. The combustion chamber 4 has a piston 5 movable up and down within the combustion chamber 4, the movement of the piston 5 being transmitted to a crankshaft (not shown) through a connecting rod 11 for transmitting the linear movement of the piston 5 into rotary motion of the crankshaft. This combustion chamber 4 communicates with a source of combustible air/fuel mixture through an intake port 3 adapted to be selectively closed and opened by an intake valve 2 synchronized with the movement of the piston 5, and also communicates with an exhaust passage 9 through an exhaust port 8 adapted to be selectively opened and closed by an exhaust valve 7 operated generally in a manner opposite to the intake valve 2. The engine 1 has an ignition plug 6 for igniting the combustible mixture, which has been charged into the combustion chamber 4 through the intake port 3 during the opening of the intake valve 2 and has subsequently been compressed by the piston 5. The resultant exhaust gases are subsequently discharged to the exhaust passage 9 through the exhaust port 8 during the opening of the exhaust valve 7. As is well known, the illustrated engine 1 undergoes four strokes facilitating fuel intake, compression, ignition and exhaust during each cycle of operation thereof.
Since the engine 1 having structure so far described is well known, the details thereof will not be reiterated here for the sake of brevity.
The source of combustible mixture comprises a fuel intake system including an intake passage 12 extending between the intake port 2 and an air cleaner 13 open to the atmosphere, an engine-driven, vane-type supercharger 15, and a fuel injector 18 installed in the intake passage 12 in the vicinity of the intake port 3 for injecting into the intake passage 12 fuel which will be subsequently mixed with air to provide the combustible mixture. The intake passage 12 adjacent the air cleaner 13 has an air flowmeter 14 installed in one end thereof for measuring and generating an air flow signal indicative of the flow of air therethrough from time to time, a throttle valve 16 operatively linked with the accelerator pedal (not shown) and disposed inside the intake passage 12 for regulating the flow of air therethrough towards the combustion chamber 4, and an accumulator chamber 17 defined therein at a position between the injector 18 and the throttle valve 16.
The accumulator chamber 17 is designed so that, when a negative pulsating pressure wave developed inside the intake passage 12 in the vicinity of the intake port 3 generated upon the opening of the intake valve 2 flows backwards into the intake passage 12, the negative pulsating pressure wave can be converted into a positive pressure wave which is then transmitted to the combustion chamber 4 at about the end of the suction stroke thereby effecting pressurization of the combustible mixture utilizing an inertia effect.
The fuel intake system also includes a bypass passage 23 bypassing the supercharger 15 and having its opposite ends connected at 21 to a portion of the intake passage 12 between the supercharger 15 and the air flowmeter 14 and at 22 to a portion of the intake passage 12 between the supercharger 15 and the throttle valve 16. The bypass passage 12 has a control valve 24 disposed therein for selectively opening and closing the bypass passage 23, which control valve 24 may be a butterfly valve, e.g., having a structure similar to that of the well known throttle valve 16. This control valve 24 is operatively connected through a suitable linkage system 27 to an actuator 26 adapted to receive a command from a control unit 25 as will be described later.
The illustrated power plant makes use of various sensors including a throttle sensor 31 disposed on the intake passage 12 for detecting, and providing a throttle signal indicative of, the opening of the throttle valve 16, an oxygen sensor 32 disposed on the exhaust passage 9 for detecting, and providing a ratio signal indicative of, the amount of oxygen contained in the exhaust gases emitted from the engine 1, a suction pressure sensor 33 disposed on a portion of the intake passage 12 between the supercharger 15 and the junction 22 for detecting, and providing a suction pressure signal indicative of the pressure of the air being supplied to the engine 1, an engine speed sensor 51 for detecting and providing a speed signal indicative of the engine speed, and an atmospheric pressure sensor 52 for detecting and providing a pressure signal indicative of the atmospheric pressure prevailing in the environment in which the engine 1 is operated. It is to be noted that, as is well known to those skilled in the art, the detection of the amount of oxygen contained in the exhaust gases can provide an indication of the air/fuel mixing ratio of the combustible mixture which has been supplied into and has been burned in the combustion chamber 4.
The throttle signal from the throttle sensor 31, the ratio signal from the oxygen sensor 32, the suction pressure signal from the suction pressure sensor 33, the speed signal from the engine speed sensor 51 and the pressure signal from the atmospheric pressure sensor 52 are all inputted to the control unit 25. The control unit 25 is designed to process these input signals to provide various commands necessary to control the engine speed, the air/fuel mixing ratio and the supercharged pressure in a manner which will now be described.
The supercharged pressure and the air/fuel mixing ratio are both controlled by the control unit 25 to ensure a reduction in fuel consumption and also in NOx emission, and the necessary engine power output depends on the operating condition of the engine characteristics of the suction pressure P (or the supercharged suction pressure when the supercharger 15 is operated) and of the air/fuel mixing ratio A/F relative to an average effective pressure Pe (i.e., the engine power output) of the engine 1 which provide the basis for the control performed by the control unit 25 are illustrated in FIGS. 3 and 4, respectively.
Referring to FIG. 3, if the air/fuel mixing ratio is any one of the constant ratios shown therein, the average effective pressure Pe increases as a linear function of the suction pressure P and the gradient of the linear function is substantially the same for all of the illustrated ratios. This gradient is, when the air/fuel mixing ratio is 18, expressed as follows.
δPe/δP=1.17 (kg/cm.sup.2)/100 (mmHg).
On the other hand, if the suction pressure is fixed, the average effective pressure Pe abruptly decreases with the leanness of the combustible mixture, that is, with an increase of the air/fuel mixing ratio, as shown in the graph of FIG. 4.
A control program according to which the control unit 25 can perform its control function is prepared in consideration of such characteristics as shown in and discussed with reference to FIGS. 3 and 4.
The relationship between the throttle opening and the suction pressure, which is exhibited when the supercharged suction pressure and the air/fuel mixing ratio are to be controlled by the control circuit 25 is represented by a line C 1 in FIG. 5(a). It should be noted that the higher the suction pressure, the more frequent the engine knocking, and therefore the ignition timing is retarded with an increase of the suction pressure as shown by a line C 2 in FIG. 5(c) to prevent such knocking.
When the throttle is opened to a degree not greater than a predetermined value TVθo, no relatively high engine power output is required and, therefore, the supercharger 15 is not operated. At this time, the control valve 24 in the bypass passage 23 is held in a full open position thereby permitting the air entering the intake passage 12 through the air cleaner 13 to flow through the bypass passage 23 while bypassing the supercharger 15. During such a non-supercharged operating condition, the air/fuel mixing ratio is adjusted to a value of, for example, 18 which is higher than the stoichiometric value of 14.7 for reducing fuel consumption. Characteristics of the fuel consumption relative to the air/fuel mixing ratio are such that, as shown by a line G 1 in the graph of FIG. 6(a), for example, at WOT (during supercharging) the fuel consumption decreases with an increase in the air/fuel mixing ratio. Also, characteristics of the combustion temperature relative to the air/fuel mixing ratio are such that, as shown by the bent line G 2 in the graph of FIG. 6(a), the combustion temperature tends to be lowered considerably with an increase in the air/fuel mixing ratio and, therefore, the NOx emission can be considerbly reduced.
The control of the air/fuel mixing ratio can be accomplished by varying the pulse width of fuel injection pulses, applied to the injector 18 from the control unit 25, in dependence on the amount of air detected by the air flowmeter 14. In this way, during a period in the practical driving when the supercharger 15 is not operated, the lean combustible mixture is supplied to the engine, thereby contributing to a reduction in fuel consumption and to a reduction in NOx emission as in the prior art lean-burn engine.
On the other hand, when the throttle opening exceeds the predetermined value TVθo, during the practical driving condition, a relatively high engine power output is required. Under this condition, therefore, the supercharger 15 is operated to supercharge the suction air. Simultaneously therewith, the control valve 24 is controlled by the control unit 25 by way of the actuator 26 to regulate the recirculating flow of the supercharged suction air from the junction 22 to the junction 21 through the bypass passage 23 so that the supercharged suction air actually supplied to the engine 1 can attain a target value. In other words, the supercharged air is subjected to a so-called feedback control. The target value to which the supercharged air is regulated under the feedback scheme described above is so selected as to increase with an increase in the degree of throttle opening; however, the target value is adjusted to even a higher value during the acceleration of the engine as will be described later.
When the supercharging of the suction air is effected while the degree of throttle opening has exceeded the predetermined value TVθo, and under an engine operating condition in which the suction pressure during supercharging is not higher than a predetermined value P 1 shown in the graph of FIG. 5(c), the air/fuel mixing ratio is controlled to a high value as is the case during the non-supercharging period. Since the suction pressure is not higher than the predetermined value P 1 under the practical driving condition and no higher engine output is therefore required, the engine is operated with the supply of the lean combustion mixture while the suction air is supercharged by the supercharger 15. By doing so, the reduction in the fuel consumption and in the NOx emission can be attained while the necessary engine power output is secured.
However, a relatively high engine power output may be required even though the engine is operated with the lean combustible mixture simultaneously with the supercharged suction air, that is, while the supercharger 15 is in operation. This occurs when the engine is accelerated, during which occasion the air/fuel mixing ratio is adjusted based on the acceleration of the engine. More specifically, when the engine is moderately accelerated while operated with supercharged suction air and the lean combustible mixture, the air/fuel mixing ratio is maintained, but the suction pressure is increased for a predetermined length of time thereby increasing the engine power output. On the other hand, when the engine is normally accelerated, the air/fuel mixing ratio of the combustible mixture is adjusted to the stoichiometric value without the suction pressure being changed. When the engine is rapidly accelerated, however, the suction pressure is increased and, at the same time, the air/fuel mixing ratio is decreased to a value lower than the stoichiometric value.
It is to be noted that, although knocking tends to occur easily during supercharging, characteristics of the ignition timing, required to avoid the occurrence of engine knocking, and the average effective pressure relative to the air/fuel mixing ratio can be established as illustrated in FIGS. 6(b) and 6(c), respectively.
As shown in the graphs of FIGS. 6(b) and 6(c), the average effective pressure at the knocking limit decreases with an increase of the air/fuel mixing ratio, and therefore, it is desirable that countermeasures for preventing engine knocking be taken such as, for example, the use of a cooling system for cooling the suction air being supplied to the engine 1.
High engine power output such as that required during the rapid acceleration of the engine is also required when the automotive vehicle is driven up an incline. If during such acceleration or ascent the lean combustible mixture were to be supplied to the engine 1, the required high engine power output could not be obtained, and, therefore, the air/fuel mixing ratio should be increased to a value higher than the stoichiometric value in dependence on the suction pressure. By way of example, referring to the graph of FIG. 5(c), the target value to which the air/fuel mixing ratio is controlled is so selected that, when the suction pressure P attains a predetermined value P 2 which is higher than the value P 1 , the air/fuel mixing ratio is adjusted to the stoichiometric value of 14.7, but when the suction pressure P attains the maximum suction pressure Pmax, the air/fuel mixing ratio is adjusted to 13.
When the control is carried out in the manner hereinbefore described, the average effective pressure Pe (the engine power output) relative to the suction pressure corresponds to a bent line C 3 in the graph of FIG. 5(c). Since the throttle opening TVθ and the suction pressure have a linear relationship as shown by the C 1 in the graph of FIG. 5(a), characteristics of the engine power output relative to the throttle opening will be similar to those represented by the bent line C 3 in the graph of FIG. 6(c).
(Second Embodiment)
In describing the previous embodiment of the present invention, reference has been made to the use of an engine-operated, vane-type supercharger. However, in the embodiment which will now be described with reference to FIG. 2, a turbocharger, that is, a supercharger driven by the exhaust gases flowing through the exhaust passage 9 is employed as generally identified by 40.
The turbocharger 40 comprises a turbine 40a, disposed in the exhaust passage 9 and adapted to be driven by the flow of the exhaust gases, and a compressor or blower 40b coupled with the turbine 40a through a connecting shaft 40c.
As shown in FIG. 2, the exhaust passage 9 has a bypass passage 42 bypassing the turbine 40a and having a waste gate valve 43 disposed inside the bypass passage 42 for regulating the flow of the exhaust gases bypassing the turbine 40a. This waste gate valve 43 is adapted to be controlled through any suitable linkage by an actuator 44 which may be a diaphragm valve. The actuator 44 is in turn controlled by an electromagnetic valve 45 operable to regulate the actuator 44 with a portion of the pressure prevailing inside a portion of the suction passage 12 between the blower 40b and the junction 22, the opening of said electromagnetic valve 45 being controlled in response to a command issued from the control unit 25. For this purpose, a positive pressure introducing passage 46 extends between the electromagnetic valve 45 and the portion of the suction passage 12 between the blower 40b and the junction 22. Thus, it will readily be seen that the opening of the waste gate valve 43 can be controlled by the pressure inside that portion of the suction passage 12 in response to the command issued from the control unit 25.
Instead of the control valve 24 shown in FIG. 1 and described as disposed inside the bypass passage 23, and its associated actuator 26, a pivotally supported gate valve 41 is disposed at the junction 22, which gate valve 41 is controlled by a command from the control unit 25 so as to assume one of a first position, at which the bypass passage 23 is closed as shown by the solid line, and a second position at which the bypass passage 23 is open and the flow of the supercharged air into the portion of the suction passage 12 between the junction 22 and the engine 1 is blocked as shown by the phantom line. Specifically, the gate valve 41 is in the second position, shown by the phantom line, when the turbocharger 40 is inoperative, allowing the air to be supplied through the bypass passage 23 to that portion of the suction passage 12 between the junction 22 and the engine 1.
The automobile power plant shown in and described with reference to FIG. 2 operates in a manner similar to that shown in and described with reference to FIGS. 1 to 6, and accordingly, the details thereof will not be reiterated for the sake of brevity.
Hereinafter, some of the control programs according to which the control unit 25 is programmed to operate will be described with reference to FIGS. 7 to 10.
(Program I)
A first preferred form of the control program is shown in FIG. 7 and will be described on a step-by-step basis.
Step S1: Subsequent to the start of the program, the suction pressure signal from the suction pressure sensor 33 and the throttle signal from the throttle sensor 31 are inputted to the control unit 25 to determine the suction pressure P.
Step S2: A decision is made to determine if the suction pressure P is higher than a predetermined value of -50 mmHg.
Step S3: If the suction pressure is higher than the predetermined value as determined at Step S2, Step S3 takes place, in which a flag is set to FLG1=1 indicates that supercharging should be carried out.
Step S4: If the suction pressure is lower than the predetermined value as determined at Step S2, Step S4 takes place. In other words, when the suction pressure is lower than the predetermined value, and is clearly so as a result of Step S5 at which a time delay is generated before another determination is made that the suction pressure is not greater than the predetermined value at Step S2, the next control Step S7 is executed.
Step S5: Only when t is greater than 2 to 3, that is, after a delay of about 2 to 3 seconds, will the program proceed from Step S5 to Step S8.
Step S6: The setting of FLG2=0 at Step S6 occurs when the suction pressure is greater than the predetermined value and supercharging is to be effected.
Step S7: The setting of FLG2=0 at Step S7 occurs when the suction pressure is not yet greater than the predetermined value and supercharging has yet to have been set in the program to be carried out.
Step S8: The setting of FLG2=1 at Step S8 causes the control program to proceed to Step S9 after the delay generated at Step S5 and P is ensuredly not greater than -50 mmHg.
Step S9: A decision is made to determine if the change in throttle opening δTV0 is higher than a first predetermined value of 50 degrees per second.
Step S10: A decision is made to determine if the throttle opening TV0 is greater than a predetermined value of 80 degrees.
Step S11: If the change in throttle opening δTV0 is higher than the predetermined value as determined at Step S9, FLG1=1 is set to indicate that supercharging is to be effected.
Step S12: A decision is made to determine if the change in throttle opening δTV0 is higher than a second predetermined value of 100 degrees per second.
Step S13: If the change in throttle opening δTV0 as determined either at Step S9 or at Step S12 is lower than the respective predetermined values, or if the throttle opening TV0 as determined at Step S10 is smaller than the predetermined value, this step takes place to adjust the air/fuel mixing ratio to a value based on the current suction pressure P as shown in the graph of FIG. 8(a).
Step S14: If the change in throttle opening δTV0 as determined at Step S12 is higher than the predetermined value, or if the throttle opening TV0 as determined at Step S10 is greater than the predetermined value, this step takes place to adjust the air/fuel mixing ratio to a value of 13.
Step S15: A decisionis made to determine if supercharging should be carried out after the suction pressure has been adjusted.
Step S16: Either subsequent to Step S14 or if FLG1=1 is confirmed at Step S15, this step takes place to bring the supercharger 15 into operation.
Step S17: Either subsequent to the start of operation of the supercharger 15 effected at Step S16 or if FLG1=1 is not confirmed at Step S15, this step takes place and the program flow returns.
As a result of the foregoing program flow, the suction pressure P and the air/fuel mixing ratio A/F can be controlled in the manner shown in FIGS. 8(b) and 8(c), respectively. In FIGS. 8(b) and 8(c), point A represents the start of the supercharging of the suction air, point B represents a kick down region, and point C represents a region in which no supercharging is effected.
The program flow shown in and described with reference to FIG. 7 is featured in that, the supercharging region exclusive of the kick-down region (i.e., when TV0 is greater than 80 degrees) represents when the lean combustible mixture is supplied to the engine while the supercharger 15 is operated so that an air/fuel mixing ratio having a high value is supplied under the occurrence of supercharged suction pressure and, on the other hand, the non-supercharging region represents when the lean combustible mixture is supplied to the engine during moderate acceleration while the supercharger 15 is operated, or the enriched combustible mixture is supplied to the engine during rapid acceleration while the supercharger 15 is operated.
(Program II)
A second preferred form of the control program is shown in FIG. 9 will be described on a step-by-step basis.
Step N1: Subsequent to the start of the program, the throttle signal from the throttle sensor 31, the speed signal from the engine speed sensor 33 and the pressure signal from the atmospheric pressure sensor 52 are inputted to the control unit 25.
Step N2: An equation TVθ=TVθi×K N ×K H is calculated to determine the value of the throttle opening TV0 at which supercharging is to be initiated. In this equation, TVθi represents the throttle opening during idling of the engine, K N represents a correction coefficient for the throttle opening which is determined with reference to the engine speed as shown in FIG. 10(a), and K H represents a correction coefficient for the atmospheric pressure determined with reference to the pressure P h as shown in FIG. 10(b).
Step N3: A decision is made to determine if the throttle opening TV0 is greater than the throttle opening TVθ.
Step N4: If the throttle opening TV0 is not greater than the throttle opening TVθ as determined at Step N3, this step takes place to determine if an appropriate delay at Step N5 has occurred.
Step N5: Only when t is greater than 2 to 3, that is, after a delay of about 2 to 3 seconds, will the program proceed from Step N5 to Step S8.
Step N6: If the throttle opening TV0 is greater than the throttle opening TVθ as determined at Step N3, this step takes place. FLG1=1 is set to indicate that the supercharging should be carried out.
Step N7: FLG2=0 is set when the throttle valve opening is greater than TVθ and supercharging is to be carried out.
Step N8: FLG2=1 is set after the delay generated at Step N5 which causes the program to proceed to Step N10 when it is assured that TV0 is not greater than TVθ.
Step N9: FLG2=0 is set when TV0 is appropriately greater than the value TVθ and supercharging is to be carried out.
Step N10: A decision is made to determine if the change in throttle opening δTV0 is higher than a first predetermined value of 50 degrees per second.
Step N11: FLG=1 is set to indicate that supercharging should be effected.
Step N12: A decision is made to determine if the throttle opening TV0 is greater than a predetermined value of 80 degrees.
Step N13: A decision is made to determine if the change in throttle opening δTV0 is higher than a second predetermined value of 100 degrees per second.
Step N14: If the change in throttle opening δTV0 as determined at Step N13 is higher than the second predetermined value, or if the throttle opening TV0 as determined at Step N12 is greater than the predetermined value, this step takes place to adjust the air/fuel mixing ratio to a value of 13.
Step N15: If the charge in throttle opening δTV0 as determined either at Step N10 or at Step N13 is lower than the respective predetermined values, or if the throttle opening TV0 as determined at Step N12 is smaller than the predetermined value, this step takes place to adjust the air/fuel mixing ratio to a value based on the current suction pressure P as shown in the graph of FIG. 8(a).
Step N16: A decision is made to determine if the program has indicated that the supercharger should be operated.
Step N17: Either subsequent to Step N14 or if the decision made at Step N16 had indicated that the supercharger 15 should be operated, this step takes place to initiate the operation of the supercharger 15.
Step N18: The target supercharger pressure P T is inputted according to the characteristic curve shown in FIG. 10(c) showing the relationship between the pressure P T and the throttle opening TVθ.
Step N19: the suction pressure P is inputted.
Step N20: The feedback control is carried out to bring the supercharged suction pressure to the target value.
Step N21: Either subsequent to Step N20 or if FLG1=1 is not confirmed at Step N16, this step takes place and the program flow returns.
Although as a result of the foregoing program flow, the suction pressure P and the air/fuel mixing ratio A/F can be controlled in the manner shown in FIGS. 8(b) and 8(c), respectively, the program flow shown in FIG. 9 is featured in that the supercharged suction pressure can be controlled in dependence on the throttle opening.
Although the present invention has fully been described in connection with the preferred embodiments thereof with reference to the accompanying drawings, it is to be noted that various changes and modifications will become apparent to those skilled in the art. Such changes and modifications are, unless they depart from the scope of the present invention as defined by the appended claims, to be understood as included therein.
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An air/fuel control system for a supercharged automotive engine includes a supercharger for supercharging air to be supplied to the engine, a detecting device for detecting a plurality of parameters representative of an engine operating condition, an air/fuel ratio regulating unit for adjusting the air/fuel mixing ratio to an arbitrarily chosen predetermined value, and a control unit for controlling the air/fuel ratio regulating unit. The control unit is designed to cause the air/fuel ratio regulating unit to adjust the air/fuel mixing ratio to a predetermined value higher than the stoichiometric value when the detecting device indicates that the engine is in a normal operating condition while the supercharger is operated, and also to adjust the air/fuel mixing ratio to a predetermined value lower than the stoichiometric value when the detecting device indicates that the engine is under an operating condition in which a relatively high engine power output is required.
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FIELD OF THE INVENTION
[0001] The present invention generally relates to a system for the rental or sale of advertising and promotional space in buildings or facilities frequented by large numbers of the general public and, more particularly, to a method and system for the rental or sale of advertising and promotional space in shopping malls.
BACKGROUND OF THE INVENTION
[0002] The past decade has seen continued growth in the number of new shopping malls being opened around the world, especially in Europe and the United States. This continued growth is allied to the fact that in many countries shopping is currently the fastest growing leisure pursuit. Thus, advertisers and brand managers have to come to recognize that buildings and facilities frequented by large numbers of the general public and, in particular, shopping malls are excellent places in which to demonstrate and promote products.
[0003] This type of advertising benefits both the advertiser and the shopping mall in question. For the owner of the mall, such promotional advertising generates income from previously unused retail space while also adding to the vitality and overall attraction of the mall to the public. On the advertiser's part, this type of promotion allows mass marketing whilst also permitting the customer to feel, see and hear products as they are demonstrated directly, as opposed to two-dimensional advertising in publications or on billboards. Furthermore, the rental of advertising and promotional space is far cheaper than advertising using conventional media such as the aforementioned publications or billboards. A yet further benefit to the advertiser of advertising in an environment such as a shopping mall is that customers are already in a purchasing mindset as demonstrated by their presence at the mall in the first place.
[0004] Despite the aforementioned benefits to both mall owner and advertiser, there is currently no national profile or advertising campaign in existence using the shopping mall as an advertising medium. If a mall is used as an advertising medium, it is invariably as part of a one-off, localized promotion. Due to this one-off format, there is no benchmarking to validate mall data and costs, and in many instances of one-off promotions unnecessary middlemen inflate costs as a result. For the advertiser, finding and booking space in a mall is currently a laborious, time-consuming process. This is not aided by the fact that the quality of information provided by each mall varies widely and is generally poor and unsubstantiated. In addition, most mall owners do not appreciate the functionality or potential of their malls with respect to promotional advertising of this nature.
[0005] In the light of the above, it is therefore an aim of the present invention to provide a system which will bring together advertisers and facility owners. This system will allow facility owners to successfully exploit unused space while also allowing advertisers to introduce their products to willing buyers. The system will be an interactive system whereby comprehensive information on available promotional space in major public facilities (e.g. shopping malls) throughout the advertiser's target country or region will be provided in order that advertisers can determine the most suitable sites and rent or buy advertising space at those sites.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Reference is now made more particularly to the drawings which illustrate the best presently known mode of carrying out the invention and wherein similar reference characters indicate the same parts throughout the views.
[0007] [0007]FIG. 1 is a schematic block diagram illustrating the pre-booking steps undertaken via the system of the present invention; and
[0008] [0008]FIG. 2 is a schematic block diagram of the post-booking process undertaken via the system.
DETAILED DESCRIPTION
[0009] It is anticipated that the system of the present invention will be presented to customers via an interactive Internet website and telephone support center. The system comprises a central server which includes a random access memory, read-only memory and a central processing unit (CPU). The CPU may be a single commercially available processor or else may be a number of such processors operating in parallel.
[0010] Although the following description will refer to advertising in shopping malls only, it is to be understood that the system of the invention may be used to store details of any building or facility used by large numbers of the public, such as movie theatres or airports for example.
[0011] As stated above, the system is intended for use by advertisers who subscribe or register to use the system, along with facility owners whose facilities are listed thereon. The advertisers may be individual companies, advertising or PR agencies, or the like. A facility owner may either be an individual or else. a corporation or the like which owns a particular facility or a number of facilities.
[0012] As shown at step 1 of FIG. 1, customers initially may use the site to browse for suitable malls or other facilities. The system has a database which contains information on a variety of different aspects to the mall, such as geographical location (where in the country or region the mall is located), exclusions (whether there are any products which the mall owner will not allow to be promoted in the facility), and pricing structure (how the cost of renting the available space is calculated) Further aspects may also be included relating to the mall customers, such as footfall statistics (the number of customers using the mall at given times) and customer demographics (statistics on mall customers such as age, employment, number in family, etc.). In addition aspects relating to the mall may be viewed, such as technical data relating to the mall, promotional site dimensions in the mall, who the key retail occupants of the mall are, and site availability.
[0013] Once the customer has identified the malls that may be of interest, they are invited to register various details on the system in order to proceed further, as shown at step 2 . These details may include personal details about the person and their position within their company, their contact details, information concerning the company whose products are to be advertised, and such like. Each customer will then be given personal registration data—most preferably a username and password—which they should use when revisiting the site.
[0014] Once their information is registered (or, in the case where the user has previously used the site, their username and password have been corroborated by the system) the customer may proceed to step 3 and select the sites where they wish to proceed and rent advertising space in. Should the client have any queries at any time during the use of the system, they may call the telephone support center for assistance and clarification, as illustrated at step 3 a . Once the client has selected the sites where they wish to advertise, then the system will proceed to step 4 , where the client may either book advertising space on-line or via the telephone center if they prefer.
[0015] The website can also offer a fully interactive search facility whereby customers may input particular requirements for the advertising space that they require in a particular geographical area (e.g. footfall, size of retail space, pricing, etc.) and the search engine will list suitable malls in that area. This provides a quick alternative to the client browsing through the different pages for each mall, as at step 1 of FIG. 1. The procedure following the client's booking will now be described, with reference to FIG. 2. Once the client has made the booking at step 4 , whether online or via the telephone center, a response e-mail is sent to the client at step 5 confirming the booking. At the same time, the call center confirms the booking with the mall at step 6 , again by email. Each mall owner who subscribes to the system will be provided with access at any time to a secure intranet so that they may check any aspect of any booking, illustrated here at step 7 . The intranet will enable the owner to log on to the system at anytime to check bookings at their facility or facilities, but as it is secure it will not be accessible by owners of other facilities, thereby preventing unauthorized access to by unscrupulous owners to their competitors' booking information.
[0016] Once the booking has been confirmed to both the client and the mall by the telephone center by way of steps 5 and 6 , the client and mall then deal directly with each other. At the next step, step 8 , the mall sends their invoice and terms and conditions of rental to the client directly for payment. Once the client receives the invoice at step 9 , they pay the invoice directly to the mall at step 10 . At step 11 , the mall receives payment and the client can then proceed with advertising in the space provided in the mall at the agreed time.
[0017] With the addition of a telephone help center, it is possible for both the customer and mall owner to discuss any aspect of a booking with an assistant in the center, if anything is unclear. In addition, where a customer does not wish to use the Internet in order to book advertising space, they can arrange bookings directly with a telephone center assistant if desired. The telephone center may also be used to bring prospective customers to the attention of mall owners. The center is manned by a number of staff during business hours so that users or owners may obtain assistance.
[0018] The main advantage of the system in accordance with the present invention is that customer and mall owner are brought together via one site, putting buyers in touch with sellers, rather than a customer having to deal individually with each mall. However, the system provides further advantages for both customer and mall owner alike. For the mall owner, the system provides professional presentation of the mall that might otherwise be of poor quality, whilst also providing a national or international profile for the mall.
[0019] In addition, mall staff deal with a large number of different tasks during each working day, which may perhaps reduce their effectiveness when it comes to dealing with retail advertising and advertising customers. In contrast, the system of the present invention is dedicated solely to the providing of advertising space in facilities, and as such the customers and mall owners have a dedicated website and telephone center staff trained solely for the purpose of helping customers rent or buy advertising space. Furthermore, the system will significantly reduce the administration workload of mall staff, providing an excellent time saving opportunity.
[0020] The system also allows the mall owner to retain complete control of bookings, so that they may determine who advertises at their mall. Mall owners and customers may also negotiate prices directly with each other if desired.
[0021] For advertisers, the system provides a one-stop site that allows them to determine the availability of mall advertising space for their products. Information on all malls and facilities is instantly available so that advertisers can determine which sites are of interest in their campaign strategy. Furthermore, the information provided by the system is standardized so that clear comparisons can be made between sites.
[0022] It is to be understood that the above description is of only one preferred embodiment and that modifications and improvements can be incorporated without departing from the scope of the invention. For example, the system described may further have a capability whereby a reminder is sent to the mall owner via electronic mail prior to the arranged date of advertisement to check that the mall owner has received payment from the advertiser. Furthermore, an invoicing and terms and conditions tool may be provided so that the mall owner may undertake step 8 of the procedure with assistance from the system. A forecasting tool can also be provided to allow the mall owner to understand the income potential of providing advertising space to advertisers. Additionally, the system can be adapted to notify customers of advertising space which becomes available at the last minute, either by electronic mail or other means. Also, individual mall pages or sites within the system can be adapted to provide hyperlinks to other sites or opportunities related to the respective malls.
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A system and method for the rental of advertising space in buildings are disclosed for allowing advertisers to conveniently view information on a number of buildings where space is available for advertising and promotional activities. The system contains a database containing a variety of information on each building so that advertisers may browse to determine the most suitable building for their promotion. The system may also contain a search facility whereby advertisers can request the system to select a shortlist of suitable buildings based upon the requirements of the advertiser. Once the building or buildings have been selected, the system also provides a centralized booking facility whereby advertisers may book the desired space.
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STATEMEMT OF GOVERNMENTAL INTEREST
The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefore.
BACKGROUND OF THE INVENTION
This invention relates to solar heating apparatus, and more particularly to such apparatus and system that concentrates the solar energy, and automatically tracks the sun throughout its daylight path to achieve a high temperature heat transfer, and for controlling and maintaining the desired temperature of the stored liquid medium.
Solar water heaters have been employed for many years throughout the world. They can be classified generally in two categories, namely panel solar heaters, and concentrator solar heaters, depending on the temperature requirements of the particular installation. The concentrator type of solar heater, of which the present invention is an example, employs a parabolic or cylindrical heat collector to concentrate and focus the reflected solar energy for producing temperatures above 212° F to be suitable for use in steam heating applications, air conditioning, refrigeration systems, power generation, as well as other suitable heating applications up to 500° F.
In order to fully utilize a concentrator type of solar heater, it is desirable to track the sun, and accordingly, it is conventional to mount the reflecting surface for rotation about one or more axes. Examples of such construction is illustrated by U.S. Pat. Nos. 2,182,222 and 820,127.
However, neither of these patents nor the others in the art, disclose a suitable control means to enable the heat collector to be continuously and automatically guided and oriented in the most advantageous position with respect to the sun throughout its daylight travel. Nor does the art disclose the novel techniques for sensing and controlling the temperature of the stored liquid medium throughout the day.
SUMMARY OF THE INVENTION
The solar heater is provided with an improved solar heat concentrator having a network of preheating coils positioned in the mouth of a parabolic reflector, which coils are connected to a main heating tube positioned at the focal axis of the parabolic reflecting surface. This arrangement of coils enables the temperature of the circulating fluid medium to be preheated initially to above 150° F before passing through the main heating tube.
An automatic tracking circuit includes photocells and a collimator to follow the sun, and to control the heat collector driving means to maximize the heat transfer throughout the daylight hours.
The solar heater preferably employs a unique heat closed loop exchanger that transfers the solar heat absorbed by the working fluid mediums to a hot water storage loop.
A temperature sensing circuit and modulating valve device compares the temperatures at the heat concentrator and the storage facility to maintain optimum heat replenishment therebetween.
STATEMENT OF THE OBJECTS OF THE INVENTION
It is a principal object of this invention to provide a more efficient solar heater by having a movable heat collector, or concentrator, capable of automatically tracking the sun during daylight hours.
Another important object is to provide a solar concentrator having an arrangement of pipes to preheat the circulating working liquid to be heated.
Still further objects are to provide a solar heater with an improved heat exchanger; and a modulated fluid flow control system that adjusts the rate of flow for optimum heating conditions.
Other objects and many of the attendant advantages of this invention will be readily appreciated as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a general arrangement of the components of the novel solar heater apparatus, with the concentrator shown in isometric view.
FIGS. 2 and 3 are sectional views of the novel concentrator taken along lines II--II and III--III of FIG. 1 showing the piping arrangement and other details.
FIGS. 4 and 5 are side and top views, respectively, of a collimator housing photocells to sense the position of the sun.
FIG. 6 is a tracking circuit utilizing the collimator of FIGS. 4 and 5 for controlling the movement of the solar concentrator.
FIG. 7 is an enlarged longitudinal sectional view of a vacuum insulator heat exchanger.
FIG. 8 is a temperature sensing and modulating circuit.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings where like reference numerals refer to similar parts throughout the figures there is shown in FIG. 1 a general arrangement of the basic components of the novel solar heater 10 as may be utilized preferably for steam generation. It should be understood that this basic solar heater can be incorporated in many different applications, such as forced air heating systems, air conditioning systems, steam or electric power generation, etc.
The illustrated solar heater 10 comprises at least one heat concentrator assembly 12; a solar collimator tracking apparatus 14 for the concentrator assembly; a heat exchanger 16 connected by piping between the concentrator assembly 12 and a hot water storage tank 18; and a temperature valve sensing system 20 electrically connected to concentrator 12 and to tank 18.
As shown in FIG. 2, concentrator assembly 12 includes an inner reflector panel 22 having a mirrored outer surface 24, the panel being configured in cylindrical parabolic shape by an aluminum rectangular frame 26. A layer of foil surfaced, fiberglass insulation 28 is positioned between frame ribs 29 and sandwiched between inner panel 22 and outer aluminum panel 30. Panel 30 has a white enamelled finish to reduce solar heat loss. Concentrator assembly 12 is provided with flat end walls 32, which have a similar sandwiched fabrication as the parabolic section.
The edges of the combined sandwich panel assembly are supported together by channelled side frame members 34, which are also channelled to support one temperatured glass cover 36 for protecting the reflecting surface 24 from dirt and moisture, and for reducing heat losses from the wind.
As is best illustrated in FIGS. 2 and 3, concentrator assembly 12 houses a unique piping system 38 made of copper or the like through which liquids can be circulated by a pump 39 (FIG. 1) in a simple direct hot water system; but preferably a working fluid, such as "Dowtherm, " in a closed loop system using heat exchanger 16, as illustrated in FIG. 1, but which can be incorporated in tank 18.
Piping system 38 includes a circuitous arrangement of spaced, parallel pipe sections traversely aligned centrally the concentrator assembly, preferably oriented normal to the reflecting surface and with the rotational axis of the collector. An uppermost superheat pipe 40 is positioned along the focal axis 41 of the parabolic panel 22 so as to be in the path of the directly reflected solar light rays 42, (FIG. 2) the remaining preheat pipes 44-50 being suspended inwardly therefrom and subject to random reflected solar light rays. The path of the working liquid passing through these pipes is indicated by broken arrow 52 (FIGS. 1 and 3) entering concentrator 12 at inlet pipe 54 and passing through preheat pipes 44-50 and finally through main heater pipe 40 which superheats the liquid prior to discharge at outlet pipe 56. Outlet pipe 56 is located nearest to heat exchanger 16, or storage tank 18 when no heat exchanger is utilized, and is suitably insulated. Superheat pipe 40 may be enclosed within an evacuated glass tube 58 for insulation purposes. In systems that may utilize more than one reflector module, only the module located at the cold end of the liquid exchange system need be provided with the preheater tubes.
Concentrator panel 22 and its supporting frame 24 are rotatably mounted at each end around axis 41 through tubular roller bearings 60 secured in triangular side supports 62. Glass tube 58, which encloses superheat pipe 40, laterally terminates at a vacuum seal, not shown, where the preheat pipe section connects to pipe 40 near inlet 54 to enable preheat pipe 50 to extend through and remain fixed within bearings 60. Thus, the entire piping system 38 remains stationary while concentrator assembly 12 pivots thereabout, an arrangement which simplifies construction and reduces the weight of the reflector assembly to be driven by motor 64 through gear reduction 65 worm 66.
Concentrator assembly 12 oF FIGS. 1-3 is designed to be movable about a single axis 41, i.e., north/south orientation and at a given inclination, so as to be able to pivot from east to west tracking the sun from sunrise to sunset. Since optimum heating is obtained when the axis is parallel to the local latitude, or even 10° more, it may be desirable to raise the north end of the assembly to compensate for the sun's inclination. A suitable roof location or other support may provide the required inclination. The precise angle of concentrator assembly 12 facing the south will depend on the seasonal inclination. Optimum heating the year around is achieved by a fixed tilt angle (as shown in FIG. 1) from 33° at the San Diego area to 48° at the northern U.S. Border; 10° more will benefit winter heating. The sun inclination is plus and minus 23° from this equinox angles. Providing concentrator 12 with a fixed tilted arrangement is the most simple and adequate for most contemplated applications. However, if greater heat transfer efficiency is desired by also following the north/south inclination of the sun throughout the year, reflector assembly 12 can be pivotally mounted to be tilted manually or power driven in a manner similar to that described for the tracking mode.
One of the unique features of this invention is to minimize heat loss in the early morning and late afternoon by providing concentrator drive motor 64 with an automatic tracking control circuit 67 to track the east-to-west path of the sun throughout the day. As shown broadly in FIG. 1, and detailed in FIGS. 4-6, tracking circuit 67 includes collimator 14 supported on the front of reflector frame 24 at the centerline of the concentrator. Collimator 14 comprises a cylindrical housing 68 having an open end 70, and a closed end 72 fixedly mounted to frame 24 providing a perpendicular orientation with respect to concentrator frame 24. At least two photocells, or the like, 74 and 76 are mounted to housing end 72, being spaced apart and oriented in an east-west alignment on each side of concentrator centerline 41. Housing 68 is separated into two longitudinal compartments 78 and 80 by a wall 82 forming a light barrier between the two photocells. The upper end of wall 82 supports a barrier plate 84 which provides a shadow to overlap photocells 74 and 76 when the sun is substantially aligned with the longitudinal axis of the collimator 14. In this position the collector is properly oriented with respect to the sun to achieve maximum heat transfer efficiency. Whenever the collimator, and the concentrator, become misaligned in any E-W position with respect to the sun because of interrupting clouds, etc., the respective photocell will be illuminated thereafter by the sun and heat concentrator 12 will be driven to cover said photocell, and restore the aligned condition without requiring a continuous current.
As shown in FIG. 6, tracking circuit 67 incorporates photocells 74 and 76 in a simplified version of the apparatus, suitable for small heating systems such as may be operable on a plus and minus 12-volt D.C. power source, connected across concentrator drive motor 64, which in this application is a reversible 24-volt D.C. motor. For larger installations, an A.C. motor with reversible relays, or thyristor control, can be employed.
Photocell 74 is provided with a motor circuit including transistors Q1, Q3, Q6, current limiting resistor R1, and bias limiting resistors R3 and R5. Photocell 76 is provided with a motor circuit including transistors Q2, Q4, and Q5, current limiting resistor R2, and bias limiting resistors R4 and R6.
Operation of the tracking circuit is obvious from FIG. 6. For example, if photocell 74 is illuminated by the sun current flows through Q1, Q3, motor 64, and Q6, driving the concentrator 12 in a direction to uncover photocell 76. When the sun strikes photocell 76, the current flows through its respective motor circuit to drive concentrator 12 in the opposite direction. As long as both photocells are shielded from the sun, no power is consumed and the concentrator is properly aligned with the sun in its optimum position.
As previously stated, if desired, concentrator 12 can be provided with a tilt drive mechanism and a tilt circuit identical to tracking circuit 67. Tracking could also be done at a steady rate, with corrections being made by the above tracking circuit.
Another important feature of the invention resides in the construction of heat exchanger 16, shown in detail in FIG. 7, hydraulically connected between concentrator heater 12 and hot water storage tank 18. The use of the heat exchanger is necessary when a special working fluid 52 is used instead of water; and it is highly desirable to use a working fluid in place of water in a heat collector system to reduce undesirable deposits, to prevent freezing, to prevent corrosion and electrolysis, and to avoid the high steam pressures in high temperature systems with water. As shown in FIG. 1, the heat exchanger is separated from tank 18, but the same basic heat exchanger can be located within the tank and provide the same advantages to the storage system.
Exchanger 16 comprises two concentric tubes 86 and 88 having optimum dimensions, depending on the volume required for the specific application. Outer tube 86 provides a circuit for the working fluid 52 and is connected at its top to concentrator outlet 56, and at its bottom to concentrator inlet 54. Inner tube 88 provides a circuit for the hot water 89, and at the bottom is connected via inlet pipe 90 and T-joint 92 (FIG. 1) from the colder, bottom of storage tank 18; and from the water supply line via valve 101 and line 102. The upper end of tube 88 is connected by outlet pipe 94 to the upper end of tank 18 through T-joint 96. Hot water may be drawn either from the exchanger 16 directly or from the top of tank 18 via outlet pipe 98, as long as the steam pressure does not exceed the water supply pressure. A drain 103 is provided on the bottom of the exchanger 16 to facilitate removal of any sediment in the water supply. Vanes 104 and 106 are inserted into the inlets, near 56 and 103 respectively, to provide a rotary flow to the liquids so that cold water will travel to the outside and warm water toward the center of each tube to enhance the heat transfer therebetween. Heat exchanger 16 is provided with an evacuated outer insulating jacket 108, within which is mounted a concentric, cylindrical foil radiation barrier 109. Similar insulating means is recommended for storage tank 18 and the hot water piping.
Temperature sensing system 20, shown generally in FIG. 1, and in detail in FIG. 8, functions to prevent cooling of the stored hot water in tank 18 by colder water from the heat concentrator system 12, which may occur during night time, or long periods of interrupted sunlight.
Sensing circuit 20 is a simple comparison electrical circuit, which may also be powered by plus and minus 12-volt D.C. batteries, and includes two identical thermistors R8 and R9. Thermistor R8 is located in heat concentrator outlet pipe 56 and senses the temperature of the heated working fluid leaving the concentrator, while thermistor R9 is located in upper portion of hot water storage tank 18 and senses the temperature therein. Thermistor R8 is connected across NPN transistor Q7, while thermistor R9 is across PNP transistor Q8. The outputs of the transistors control a reversible 12-volt D.C. motor M ganged to a butterfly valve V located in concentrator inlet pipe 54 and to a rheostat R10.
In operation, as the temperature of the working fluid in the concentrator rises, the resistance of R8 decreases which raises the voltage at condenser C and at the base NPN transistor Q7, and positive current flows through Q7 to drive motor M in the positive direction. This movement starts the opening of valve V and moves rheostat R10 to compensate for the resistance lost by R8 as it is heated. At a certain point, the sum of R8 and R10 will equal the value of R9, the voltage at C returning to zero and the motor will stop as will valve V. If the working fluid temperature rises higher, the process will be repeated to again balance the system.
Should a cloud shade concentrator 12 from the sun, or at sunset, the resistance of R8 will increase, lowering the voltage at C and to the base of Q8. This drives negative current through PNP transistor Q8 and motor M, thereby reversing the motor and starts closing valve V; and R10 again balances the systems to stop motor M. This not only starts and stops the working liquid flow from the collector, it also modulates the rate of working liquid flow through the one or more collectors to maintain the optimum rate of flow for the conditions at any given time. If sunlight is plentiful, valve V will be opened wide, but any condition that reduces the insolation will reduce the rate of working fluid flow until the heating condition improves. Whenever the temperature in the tank at R9 is higher than the working fluid temperature at R8, valve V will be closed until heating is again favorable.
The novel solar heat exchanger system described above provides a more efficient and inexpensive manner of utilizing solar energy.
Obviously many modifications and variations of the present invention are possible in the 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.
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A solar apparatus is provided for heating liquids such as water, to a high temperature by utilizing a movable parabolic heat collector to concentrate the sun's rays associated with a special piping arrangement to obtain progressive liquid pre-heating; a collector tracking device including photocells and a collimating system for controlling the movement of the collector to maintain alignment with the sun; a device for modulating the flow of the heat transfer liquid between the collector and the storage to maintain optimum heat replenishment therebetween; and also a vacuum insulated heat exchanger to isolate the heat transfer liquid from the water being heated.
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FIELD OF THE INVENTION
The present relates to the field of airflow management and in particular to cooling systems that may be suitable for electronic equipment.
BACKGROUND
Modern day electronic equipment often includes multiple subsystems mounted within a relatively small cabinet for protection and for the convenience of the user. However, such arrangements tend to concentrate large amounts of heat within a constrained area. This heat must be removed for system reliability and safety reasons from the cabinet. Often, the extreme density of electronics within the cabinet necessitates a high airflow rate and relatively high pressure to accomplish the heat removal. In addition, to provide for redundancy and high reliability of the electronic systems, it may be preferred to provide for a heat removal and cooling system that is not totally dependent on a single air mover.
Centrifugal blade blowers may provide for high pressure and high volume air movement that may be suitable for electronic cooling. However, because of the construction of the impeller typically provided on the blower, it is very difficult and inefficient to provide for redundant blowers for a single cabinet. One difficulty in providing redundant centrifugal blowers is based on the typical construction of the blowers. The centrifugal blowers have impellers that typically have a solid base structure that prevents air from flowing in a direction other than transverse to the inlet. This may dictate that blowers may have to be mounted side by side if redundancy is desired. A side by side mounting may not be desirable due to changes in airflow patterns if an individual blower fails and other reasons
Therefore, what is needed is an airflow method and apparatus that provides redundancy while sustaining the required total airflow and maintaining the same airflow patterns within a cabinet and other advantages.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may be best understood by referring to the following description and accompanied drawings that are used to illustrate embodiments of the invention. In the drawings:
FIG. 1 illustrates stacked centrifugal blower according to embodiments of the present invention;
FIG. 2 illustrates stacked centrifugal blowers wherein one blower is operational;
FIG. 3 illustrates a centrifugal blower mounting system according to embodiments of the present invention; and
FIG. 4 illustrates a centrifugal blower having a flow gate coupled to the impeller according to embodiments of the present invention.
DETAILED DESCRIPTION
Referring now to FIG. 1, two centrifugal blowers 101 and 103 are stacked such that the centrifugal blower 103 is mounted above the centrifugal blower 101 . The centrifugal blower 101 has an inlet area 105 and a first exhaust area 107 . Additionally, centrifugal blower 101 has a pass through air passage 109 .
In like manner, the centrifugal blower 103 has an inlet area 111 and an exhaust area 113 . Also, each of the centrifugal blowers 101 and 103 include an airflow gate 115 and 117 respectively.
In operation, air is drawn from the inlet 105 of centrifugal blower 101 and exhausted by centrifugal blower 101 through exhaust area 107 . In addition, centrifugal blower 103 draws air through the pass through area 109 in centrifugal blower 101 and into the inlet area 111 of blower 103 . Centrifugal blower 103 then exhausts the air from inlet 111 through exhaust area 113 .
Exhaust areas 107 and 113 exhaust air into a plenum area indicated generally by 119 . With both centrifugal blowers 103 and 101 operational, the air exhaust gates 115 and 117 are held in an open position by the airflow pressure provided by the centrifugal blowers 101 and 103 respectively.
As illustrated, airflow as illustrated by arrows 121 , air flows from a bottom area 123 up through the centrifugal blowers and into the plenum area 119 .
Referring now to FIG. 2, centrifugal blower 101 may have a reduced or zero airflow while centrifugal blower 103 is operational. In this case, air, as illustrated by airflow lines 201 , is pulled by centrifugal blower 103 from area 123 and exhausted into the plenum area 119 . As centrifugal blower 101 has reduced or no airflow, exhaust gates 115 are in a more closed position thereby reducing pressure losses from the plenum area 119 through the centrifugal blower 101 . The exhaust gates 115 may be forced into a more closed position by airflow pressure in the plenum area 119 acting on the outside of the exhaust gate and thereby pushing it toward centrifugal blower 101 . However, other mechanisms are possible also. As an additional example, a spring loaded exhaust gate may be utilized to bias the exhaust gate closed should centrifugal blower 101 have a reduced air flow. It is also possible to attach the exhaust gates to the impeller plate. The gates would then be opened by centrifugal force. Their closure would then be achieved by the weight of the gates pulling the gates down. In other embodiments, the gates may be biased toward a closed position by springs, air pressure or by other force.
Each of the exhaust gates may also be responsive to open based, in part, on the flow rate of the associated blower. For example, exhaust gates 115 may open, in part or fully, based on the air flow from the centrifugal blower 101 .
In like manner, centrifugal blower 103 incorporates exhaust gates 117 which may also become in a more closed position should centrifugal blower 103 have reduced or no airflow.
Exhaust gates 115 and 117 may include a hinge area 203 . This hinge may be incorporated into the exhaust gate. As illustrated, hinge area 203 has a reduced cross section which may tend to create a bendable, or flexible, area. However, other hinge arrangements are also possible. For example, a metal hinge, a fabric hinge, an elastomeric hinge or other hinge may be utilized to achieve the advantageous results.
Referring now to FIG. 3, an external frame 301 includes spokes 303 and a hub 305 . Additionally, frame 301 includes airflow pass through areas 109 . A centrifugal impellor 309 may be suspended from a motor such a motors 125 and 127 (not shown) by spokes 311 .
Impellor 309 may be representative of impellers 107 and 113 respectively. The frame 310 may be mounted to an exhaust gates such as exhaust gates 115 and 117 thereby suspending the motor and the attached impellor 309 below the frame. The air pass through areas 109 permit air to pass from the inlet area such as area 105 associated with centrifugal blower 101 to pass axially through the center of the centrifugal blower to a centrifugal blower stacked above it such as the arrangement illustrated in FIGS. 1 and 2 with respect to blowers 101 and 103 .
Upon the failure or a reduced operating capability of a single centrifugal blower in a stacked arrangement, the operational centrifugal blower may provide the required airflow for cooling or other purposes. Additionally, the speed of an operational centrifugal blower may be adjusted to provide a suitable airflow upon the failure of one or more other centrifugal blowers. Also, while the present method and apparatus is described for providing airflow and pressure, the same system may be utilized to provide for other fluid flow and fluid pressures for the same or other applications.
Referring now to FIG. 4, blowers 401 and 403 each include an impellers 405 and 407 respectively. Each of the impellers 405 and 407 includes a flow gate 409 and 411 respectively. The flow gates may be coupled to the impellor by an integrated hinge or other attachment. As the impellor spins, the flow gates open allowing air or other flow to occur. The flow gates 409 and 411 may be forced open by centrifugal force, force from the air or other flow, or other force applied to the flow gates. As discussed above, should one of the blowers have reduced air or other flow, the gate may close fully or partially.
While the present invention has been described with respect to a limited number of embodiments, those skilled in the art will appreciate numerous modifications and variations there from. For example, while two stacked blowers have been illustrated and described, the use of three or more stacked blowers may be utilized. In addition, the air flow of one or both of the blowers may be adjusted individually or collectively to provide for a desired air flow or air pressure for cooling or other purposes. Still additionally, while each blower has been illustrated and described as having a single impeller, other variations may be possible. For example, one or more of the blowers may utilize multiple impellers or impellers and stators. Also, while the blowers have been illustrated and described has only having two exhausts, the one or more of the blowers may be constructed with from one exhaust area to a substantially continuous exhaust area substantially surrounding the impeller(s).
Therefore, it is intended that the appended claims cover all such modifications and variations that fall within the true spirit and scope of the present invention.
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A fluid moving system is disclosed wherein a plurality of stacked blowers may provide for the redundant supply of cooling fluid such as air. This system may be advantageously utilized to cool electronic equipment or other uses. One or more of the blowers may utilize an impellor design that allows for the axial flow of fluid through the blower in addition to a transverse fluid outlet. In addition, the blowers may incorporate a flow gate operative to reduce back flow should a particular blower have a reduced fluid flow.
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REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of copending U.S. patent application Ser. No. 14/203,200, filed Mar. 10, 2014 by the inventor, which claims the benefit of U.S. Provisional Patent Application Ser. No. 61/780,157, filed Mar. 13, 2013 by the same inventor, both of which are incorporated herein by reference in their respective entireties.
BACKGROUND OF THE INVENTION
[0002] Technical Field
[0003] The present invention relates to the field of cleaning aqueous fluid streams, and more specifically, provides a processing unit for aqueous fluid streams which improves the flocculation and separation of contaminants by increasing the amount and size of the floc, which provides for much improved separation and removal of contaminants from the aqueous fluid stream.
[0004] Background
[0005] Electro-(coagulation precipitation or flocculation) entered into commercial application with Cottrell's smoke stack dust precipitator in the late 1800's. One of the best representations of the art as applied to fluids is the Liggett patent, U.S. Pat. No. 4,293,400. All others are some variation of the basic concept. Some of the best documentation of the results of Electroflocculation was presented in U.S. Pat. No. 4,872,959 titled “Electrolytic Treatment of Liquids” as presented by Robert J. Herbst and Russell R. Renk with their patent of the “tube within a tube” configuration. However, the time consuming maintenance required by this configuration, cost of special parts fabrication, difficulty locating close tolerance tubing and maintaining proper clearance between the inner and outer tubes necessitated that a better solution be found. In U.S. Pat. Nos. 4,293,400, 4,378,276 and 4,872,959 there are described devices for applying an electric field to a liquid flowing through the devices. These devices employ the tube within a tube configuration. In U.S. Pat. No. 5,043,050, which is by Robert J. Herbst, all of the many, noted problems of cost, material acquisition and difficulties of maintenance of the tube within a tube device are quite well covered.
[0006] There have been many methods put forward for the removal of contaminants from aqueous fluid streams. There exist many forms and shapes of electrocoagulators. Most electrocoagulation (Electroflocculation) units are quite difficult to maintain and clean out. This must be accomplished on a regular basis if the units are to perform correctly. As a solution to this, some have advocated using chemicals while others have added a fluidized bed of conductive particles to aid in eliminating this problem. This usually just introduces a new problem.
[0007] U.S. Pat. Nos. 4,053,378, 4,094,755 and 4,329,111 describe using flat plates and fluidized beds. The flat plate device patents discuss the need for caution due to maintenance problems encountered caused by buildup of solids from the fluid stream on the carbon granules used in the fluidized bed. All of these devices are single technology treatment units.
SUMMARY OF THE INVENTION
[0008] The present invention is a processing unit for the electrolytic treatment of aqueous fluid streams employing the effects of at least three technologies, electrornagnetics, oxidation and electrolytics taking place in the proper order in a single processing unit fabricated of materials which are chemically inert. The inventive processing unit treats aqueous solutions in the correct order specific to the contaminant to be removed, and if required for specific contaminants, additional filter utilizing nanotechnology can be attached to the processing unit to further filter the aqueous stream as it exits the unit.
[0009] The present invention not only helps to solve the flow problems present in the prior art but also greatly increases the overall contaminant removal rate. The electromagnetic ionic realignment improves flocculation and reduces scaling depositions on the charged treatment plates. The microscopically bubbled ozone aids in the turbulence and the rapid formation of hydroxyl radicals as a result of oxidation, which accelerates flocculation and chemical reduction of the contaminants. The physical design of the inventive processing unit is such that visual inspection, maintenance and occasional plate replacement is quite easy and rapid.
[0010] The present invention has been designed with the following principal advantages: improvement of processing, reduction of fouling, facilitation of visual inspection, and simplification of maintenance by the utilization of the synergistic effects of the technologies of electrornagnetics, oxidation and electrolysis, while allowing more flexibility in processing different types of aqueous fluid streams by employing multiple types of interchangeable treatment plates depending on the type of aqueous fluid stream being processed. The physical design of the flow through horizontal maze processing unit is such that maintenance and occasional plate replacement is quite easy and rapid. The maze is designed to take full advantage of physical laws and physicochemical reactions by utilizing a series of horizontal maze flow channels constructed with a vertical descent to each succeeding flow channel to fully utilize the effect of the fluid flow against the natural rise of the extremely fine venturi injected Ozone/Oxygen bubbles as required for a particular contaminant.
[0011] By utilizing a strong electromagnetic field along with saturating the fluid stream with microscopic ozone/oxygen bubbles, combined with automatic and systematic polarity reversal of the treatment plates, it has been possible to dramatically reduce the major buildup problems. In addition, the ozone bubbles are in constant agitation of the fluid stream exposing more of the fluids to the treatment plates. The ozone also enhances the formation of the hydroxyl radicals and hydroperoxides, which accelerate and aid in the formation of floc and oxidation of almost all contaminants. All of this is accomplished by the synergistic interactions and reaction of the three technologies being applied simultaneously within the processing unit.
[0012] It is important to supply an adequate power source to meet the demands of the fluid stream. What will control the required current and voltage supplied to these plates is as follows: Voltage will have to be set at a sufficient level to drive the required current through the fluid stream. This is a function of the distance between the treatment plates. The current demand is the amount of current required to properly remove all contaminants from the fluid stream. This is a function of the conductivity of the contaminated stream itself, which is in turn the function of conductivity of the combination of types of contaminants (suspended and dissolved solids in the fluid stream) and the quantity of the contaminants (concentrations). This will indicate the electron charge requirements to either change state or cause flocculation and sedimentation of the dissolved and suspended solids, which make up the contaminants of a particular fluid stream. In most cases the fluid stream will, due to its conductivity, draw the current required for proper processing.
[0013] The removal of contaminants is quite often directly affected or controlled by the pH of the stream. Before the contaminated stream is sent to the processing unit the pH, if need be, can be adjusted as required for the best removal by any of the commonly known methods of pH adjustment.
[0014] Actual physical dimensions of the processing unit will be dependent on the desired treatment flow as well as the number of treatment plates used in the unit. The plate thickness, width and length as well as space between plates, may be varied to meet specific removal requirements. The processing unit is designed with horizontal flow maze channels with a vertical descent between each succeeding maze flow channel, thus taking full physical advantage of the downward fluid flow against the natural rise of the venturi-injected minute ozone bubbles to attain maximum ozone contact time within the unit. When used for a specific and constant fluid stream, the unit can be specifically designed to be more efficient at removal of very specifically targeted contaminants.
[0015] The processing unit itself is constructed of non-conductive material that is resistant to acids, caustics, organic and inorganic chemicals and contaminants, solvents, chlorinated hydrocarbons and oxidation by ozone. The sidewalls are grooved, while the ends of the treatment plates engage the grooves and a highly conductive metal contact to hold the treatment plates in place. Every other channel and plate will nest in one end and stop short of other end, while the alternate plate and channel will nest in the other end and stop short of the other end to create the horizontal maze flow in the unit.
[0016] The aqueous fluid stream is introduced into the top of the processing unit through an inlet conduit which communicates with the interior of the processing unit and allows flow through of the aqueous fluid stream to a horizontal maze of treatment plates. A number of flow channels exist in the horizontal maze and flow proceeds from channel to channel falling vertically to the outflow point on bottom where an output conduit has been attached to receive the outflow. Attached to the output conduit is a U-shaped pipe which extends from tank side and rises to the top of the treatment area top level, and in an inverted configuration, descends to connect just beyond where the bottom drain cut-off valve is attached. This allows the free flow output after the treatment unit is full and as fluid continues to enter the unit. When input fluid flow stops the drain cut-off valve opens to allow the treatment unit to drain completely through the treatment outflow point. On the end of the entry pipe, a venturi injector is mounted to the unit entry to inject ozone/oxygen directly into the fluid flow as it enters into the process unit. Connected directly to the venturi injector, so as to accomplish ionic alignment before blending the ozone, is an electromagnet sized to system flow. An electromagnet is utilized as it has proven to be more effective at ionic alignment than a permanent type magnet. Liquid flow pressure is monitored by pressure gauges.
[0017] The treatment plate maze arrangement is as follows: An aqueous fluid stream enters the processing unit at its top. The maze is so arranged that the flow is lengthwise of the unit. Flowing from one end to the other end around the end of each treatment plate and downward into the next horizontal maze flow channel. This continues in a downward manner until the last flow channel is reached. The fluid stream then exits out of an output pipe. The various flow channels are bordered by plates of opposite polarity, one plate being an anode and the other a cathode. In the center of each flow channel, frames containing membranes can be installed as may be required for treatment of specific fluid streams. These may be “doped” (chemically impregnated or other type of treatment but not limited to nanofiltration, nanoparticles or enhanced nanomagnetic particles) screens or other forms.
[0018] The method of plate installation allows the use of many types of anode and cathode plates. It is possible to use multiple treatment plate configurations to meet the removal parameters of the contaminants being treated.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is an exterior side view of the inventive processing unit comprising the invention.
[0020] FIG. 2 is a perspective view of the inventive processing unit comprising the invention shown with its access lid removed so as to provide a full view of the maze unit.
[0021] FIG. 3 is a plan view of the inventive processing unit shown with the access lid removed and looking downward at the various plates comprising the maze unit.
[0022] FIG. 4 is a perspective view of an electrical contact which is part of the invention.
[0023] FIG. 5 is an exterior side view of the inventive processing unit.
[0024] FIG. 6 is a plan view of an anode plate, a cathode plate and a membrane attached between the anode and cathode plates which are attached to various wiring and ammeter shunts as used in the best presently known embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0025] The present invention is a flow through processing unit apparatus which incorporates the following technologies: electromagnetics, oxidation and electrolytics arranged in such a manner to take full advantage of the synergistic physicochemical actions and reactions when these technologies are applied simultaneously in a confined environment in a specially designed processing unit.
[0026] Referring generally, to FIG. 1 , a processing unit 10 includes a rectangular housing 12 made of non-conductive material resistant to acids, caustics, organic and inorganic chemicals and contaminants, solvents, chlorinated hydrocarbons 20 and ozone oxidation. The housing 12 is preferably capable of handling pressures of at least 60 psi. The exact ideal dimensions of the housing is dependent upon the use to which it is applied and can be ascertained with minimal experimentation and experience. The housing dimensions can be modified for a specific non-variable contaminant and flow rate at a permanent site without being at variance to this patent. Other internal dimensions and exact number of plates for a particular application may vary. As shown in FIGS. 2 and 3 the housing 12 has sidewalls 14 , 16 which are grooved on their inner face where half of the grooves 24 contain treatment plates 68 which run from the inner face of a first sidewall 14 to within about a half-inch of and opposite second sidewall 16 . The other half of the grooves 25 will contain plates 69 which run from the inner face 22 of the second sidewall 16 to within about a half inch of the first sidewall 14 . These grooves 24 , 25 are staggered so that when treatment plates 68 , 69 are inserted into the grooves 24 , 25 a horizontal maze unit 28 is formed.
[0027] As depicted in FIG. 2 and FIG. 3 the housing 12 with associated plates 68 , 69 is shown with its access lid (not shown) removed so that the plates 68 , 69 can be seen in their horizontal orientation to form a horizontal maze unit 28 . The horizontal maze unit 28 shown in FIG. 2 also shows aqueous fluid stream (fluid stream flow indicated by arrows) entering at the inlet 29 at the top side 31 of the housing 12 , cycling across the various plates 68 , 69 via gravity feed until the fluid reaches the outlet 30 located at the bottom side 27 of the housing 12 .
[0028] Inlet 29 communicates with an input conduit 32 , as shown in FIG. 1 . Along the input conduit 32 , processing apparatus can be included to act upon the aqueous fluid stream prior to its entry into the maze unit 28 . One such apparatus is an electromagnet 34 , as shown in FIG. 1 . Another is a venturi injector 36 as shown in FIG. 1 through which oxidizing agents can be added to act upon the fluid stream. One such oxidizing agent would be ozone 33 which would be introduced at the venturi injector 36 . Just after the venturi injector 36 is the inlet 29 to the processing unit 10 , through which the fluid stream is introduced to the horizontal maze unit 28 of treatment plates 68 , 69 as shown in FIG. 2 .
[0029] Still referring to the FIG. 1 and FIG. 2 , the processing unit has an outlet 30 with a drain valve 40 on the bottom. An output conduit 46 extends from outlet 30 , which in turn connects to an inverted pipe configuration 44 . The inverted pipe configuration 44 keeps water filled to the top of the water level in the housing 12 to prevent the processing unit 10 from shorting out. Drain valve 40 is located on output conduit 46 . At the bottom 27 there is an outflow arrangement. This will generally include a flat offset spacer block 48 to which the output conduit 46 is attached. The output conduit 46 is sized to the unit's maximum flow rate. The output conduit 46 extends to connect to a “T” junction 52 which is connected to riser 54 off of the top of the “T” junction 52 which rises to the top fluid level 56 of a full treatment unit. Pipe configuration 44 also allows an extension 58 for the installation of other equipment if necessary for further reduction of contaminants beyond acceptable levels. For example, as shown in FIG. 1 , the free flow output can then connect to a filtration system 62 including but not limited to nanoparticles, enhanced nanomagnetic particles, biologically activated granulated charcoal, or the like. Flow will be outward from the outlet 30 from the last horizontal flow channel 78 of the unit as shown in FIG. 2 .
[0030] Referring to FIG. 2 and FIG. 3 , the staggered arrangement of the treatment plates 68 , 69 , which comprise the horizontal maze unit 28 , is shown. Between each pair of treatment plates 68 , 69 is a channel 64 through which flows the fluid stream (arrows). Each channel 64 is bordered by two treatment plates 68 , 69 , one plate being an anode 68 and the other a cathode 69 . The sidewalls 14 , 16 of the housing 12 , as shown in FIG. 1 , have a slot (not shown) for highly conductive metal contacts 71 , as shown in FIG. 4 . These also help to hold the anode and cathode treatment plates 68 , 69 in place. A plate 68 nests in a first sidewall groove 24 at the plate's first end 74 and stops short of an opposing second sidewall 16 at the second end 76 of the plate 68 , while the first end 74 of an alternate plate 69 nests in a groove 25 in the opposing second sidewall 16 and where the second end 76 of the alternate plate 69 stops short of the first sidewall 14 . This alternating plate arrangement combines in a plurality of alternating plates 68 , 69 to create the horizontal maze unit 28 . The fluid stream travels through the flow channels 64 and flows in a vertical manner through each flow channel from inlet 29 to outlet 30 . The plates are preferably at least one half (½) inch shorter than the distance between sidewalls 14 , 16 plus an allowance for insertion of contacts 71 . The material of the plates will and can be selected from among those materials known (or to be determined in the future) to attract any particular contaminants that are to be removed, and they can be mixed or matched as needed. The material of the plates is not a necessary aspect of the invention, and any generally highly conductive material will suffice. The exact dimensions of the plates and the number of plates will be dependent on the flow rate and the process time required. The aqueous fluid stream, upon reaching the final channel 78 , will leave the unit by the outlet 30 and the output conduit 46 as shown in FIG. 1 . The number of treatment plates, and therefore the number of flow channels in the maze unit, can be modified depending on the type of aqueous fluid stream being treated. For example, a particular contaminant may require the fluid stream to remain in the maze for a certain time “x” before it is adequately treated. This time “x” is called the residence time. The number of plates and flow channels can be increased or decreased to achieve the appropriate residence time for a particular fluid stream.
[0031] Referring to FIG. 3 , the grooves 24 , 25 imparted into the interior sidewalls 14 , 16 of the housing 12 for mounting the treatment plates 68 , 69 are shown. Grooves 24 are cut into the 2inner face 21 of a first sidewall 14 and grooves 25 are cut into the inner face 22 of a second sidewall 16 . A first subset of anode plates 68 are inserted into the first sidewall grooves 24 and a second subset of cathode plates 69 are inserted into the second sidewall grooves 25 . When the entire plurality of treatment plates 68 , 69 are inserted into their respective first and second sidewall grooves, the plates 68 , 69 comprise the maze unit 28 as shown in FIG. 2 and are positioned in a staggered relation. Both sidewalls 14 , 16 are provided with two holes (not shown) at each groove 24 , 25 for the mounting and securing of the contacts 71 as shown in FIG. 4 , which are then connected to a power source 92 as shown in FIG. 6 to cause a plate to be, respectively, an anode plate 68 or a cathode plate 69 .
[0032] Referring to FIG. 4 , the contacts 71 are shown. Each contact 71 has a slot 108 into which is inserted a treatment plate 68 or 69 . Contacts 71 are inserted into slots (not shown) located in sidewalls 14 , 16 . Stud bolts 110 protrude outward from contacts 71 and extend through sidewalls 14 , 16 . As depicted in FIG. 5 , stud bolts 110 are protruding through sidewall 14 . The ends 74 of cathode plates 68 reside in grooves 24 and in slot 108 of contact 71 . Cables 72 as shown in FIG. 5 are attached to stud bolts 110 and to power source 92 (See FIG. 6 ).
[0033] As shown in FIG. 5 and FIG. 6 the protruding portion of the stud bolts 110 on the outside of the side walls 14 , 16 will be the power connection points. At the positive sidewall 14 ammeter shunts 112 will connect to the stud bolts 110 and then the other end of the ammeter shunt 112 will connect to a power bus 106 . At the negative sidewall 16 the stud bolt 110 will connect directly to the other power bus 106 . The end of an anode plate 69 has all connections for one polarity while the other end has the cathode plate 68 connections. The shunts 112 are then connected to display ammeters 114 on the control panel 117 adjacent to the power unit's voltage control 115 and current limit 116 control. As there are two stud bolts 110 , one for each side, and due to close proximity of the plates, the shunts are connected alternately to one stud or the other to avoid close proximity problems with the shunt mounting. These shunts provide the ability to monitor the amperage drawn by each set of plates to determine efficiency of the process and will also indicate the status and condition of each set of plates.
[0034] The sidewall grooves 24 , 25 , as shown in FIG. 3 , are cut to a sufficient depth to hold the cathode and anode plates in place with approximately ⅜ inch spacing between plates. The sidewalls 14 , 16 are of non-conductive material. Also, while FIG. 2 and FIG. 3 show a side removed so that access to the plates 68 , 69 can be gained, the housing 12 is entirely closed during operation and an access lid (not shown) is placed over the plates 68 , 69 and held in a fluid tight manner with a gasket and bolts. As shown in FIG. 2 and FIG. 3 , the plates 68 , 69 are removable when the cover is removed, thus allowing them to be serviced and inspected as necessary.
[0035] As shown in FIG. 6 , the processing unit 10 preferably allows for the insertion of membranes 94 between the anode and cathode plates 68 , 69 of each flow channel 64 in the horizontal maze unit 28 . The membranes can be comprised of different materials as may be required for treatment of specific fluid streams and potential contaminants. These may be “doped” membranes 94 (chemically impregnated or other types including but not limited to nanofilters and or nanoparticle or nanomagnetic impregnated filters).
[0036] There are pressure sensor gauges 102 as shown in FIG. 1 on the unit. One will be on the input conduit 32 and the other on output conduit 46 . These will give an indication of the pressure drop across the maze unit 28 and thus will be indicative of the unit flow status.
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A method and apparatus for the removal of both suspended and dissolved contaminants in a fluid stream, including but not limited to heavy metals, organics, inorganics, hydrocarbons and others. The method combines passing an aqueous fluid stream through an electromagnetic field, an ozone/oxygen venturi injector for oxidation and through a horizontal flow and vertical fall within a horizontal plate maze unit of alternately electrically charged plates. The plates are charged alternately to be cathodes and anodes, respectively. A framework to mount and support membranes, dividers or separators, as may be required to enhance special treatment of the fluid stream, is optionally provided.
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BACKGROUND OF THE INVENTION
The present invention relates generally to a method and a system for creating and delivering electronic postcards.
Electronic communication has provided new ways to communicate greetings and short messages that typically are sent on cards such as greeting cards and postcards. In order to send a card, one must find a place to purchase the card, a postage stamp to affix to the card and a post office at which to mail the card. When one is travelling in an unfamiliar location, the steps associated with sending a card are particularly difficult.
Currently, a number of vendors maintain web sites that enable a person to create and send an electronic “greeting card” via e-mail. Such web sites provide a plurality of “cards” each having graphics and an associated message to which the sender can add a typed personal message. Typically, there are available a relatively small selection of “standard cards” and a larger selection of “premium cards” available to registered “members”. The sender provides an e-mail address for the addressee and the vendor associated with the web site transmits the “greeting card”. The vendor may send a confirmation (delivery or non-delivery) to an e-mail address provided by the sender. However, such systems require the sender have access to and operate an Internet connected computer, and the sender must provide personal information and a credit card number to access the “premium cards”.
The U.S. Pat. No. 5,343,386 shows an apparatus housed in a booth for producing printed postcards incorporating a self-portrait of the sender with a selected one of several standard pictorial backgrounds. A cash-receiving device, a video camera, a monitor and background selection buttons are connected to a computer that controls the operation of the apparatus.
The U.S. Pat. No. 5,587,740 shows a kiosk equipped with a digital camera for taking a photograph of a user in front of a scenic attraction. The kiosk also includes a computer, a credit card reader, a telephone connection and a color printer.
The U.S. Pat. No. 6,018,774 shows a system for creating an electronic postcard incorporating a user supplied image and optional text, such as a handwritten message, and sending a notification with an identifier to a recipient. The recipient must access a server with the identifier to view and print the postcard.
The U.S. Pat. No. 6,161,131 and the related U.S. Pat. No. 6,370,568 show an apparatus for creating a digital postcard and sending the postcard to a recipient via the Internet. The apparatus includes a digital camera for generating an image that is combined with a selected postcard template including geographical information overlaid on the image.
SUMMARY OF THE INVENTION
The present invention concerns a method and an apparatus for communicating with electronic postcards including: providing a server for processing electronic postcards; selecting at least one input site remote from the server; establishing a verified communication link between the at least one input site and the server; providing a sender input device at the at least one input site for receiving input information from a sender, the request including an addressee e-mail address; inputting sender information to the input device; generating an electronic postcard from the sender information; and transmitting the electronic postcard from the at least one input site to the server and from the server to the addressee e-mail address.
DESCRIPTION OF THE DRAWINGS
The above, as well as other advantages of the present invention, will become readily apparent to those skilled in the art from the following detailed description of a preferred embodiment when considered in the light of the accompanying drawings in which:
FIG. 1 is a flow diagram of a method of establishing “electronic postcard” communication according to the present invention;
FIG. 2 is a block diagram of a terminal for creating an electronic postcard in accordance with the present invention;
FIG. 3 is schematic view of the electronic postcard layout and content as created by the terminal shown in FIG. 2 ; and
FIG. 4 is a block diagram of a communication system incorporating the terminal shown in FIG. 2 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
A person desiring to send a postcard (a “sender”) from a travel location must first find a postcard sales location, then correctly address the card to the addressee, purchase and affix the proper postage and find a post office at which to mail the card. All of these steps take time and effort, and a failure to complete any one step frustrates the objective of informing the addressee that the sender was thinking about him or her. The method according to the present invention simplifies or eliminates each of the above-described steps so that “postcards” are easier to send and thus more likely to be sent.
As shown in FIG. 1 , the method according to the present invention begins at a step 11 of establishing a web site to enable a sender to create and address an electronic postcard that is delivered to an addressee. As discussed below, the web site is implemented with a server that can be connected to the Internet or a similar communications network. Although a web site is utilized in this example, a server type computer having communication capabilities can be utilized to communicate with the input site. In a next step 12 , potential input sites are identified at which the transaction of inputting the sender information and payment for the service will take place. For example, likely input sites are gift shops in hotels, airports and tourist attractions, front desks at hotels and motels, theme parks and other sites all of which typically sell printed postcards and are exposed to significant business traveler and/or tourist traffic. Once an identified input site is selected for participation in the method according to the present invention, verified communication is established between the input site and the web site in a step 13 . Verified communication requires the web site to authenticate that an incoming request for an electronic postcard is originating from a particular one of the selected input sites. In a step 14 , an input device is provided at each of the selected input sites. The input device can be any suitable means for communicating with the web site such as a dedicated terminal or a personal computer running software necessary to communicate with the web site.
Now the method according to the present invention is ready to create and send electronic postcards. In a step 15 , a sender provides input information to the input device located at one of the selected input sites including an e-mail address for the addressee and a selection of a local scene. As one alternative, the sender inserts required information, including a handwritten message if desired, onto a preprinted form. The completed form is presented to an operator along with payment for the service and the sender has completed all of the work required of him or her. The operator uses the input device to create the electronic postcard from the information placed on the form by the sender. In some instances, the person receiving the form from the sender may be at a location that has a relatively low volume of transactions such as the reception desk at hotel. In those instances, the input site may include the pickup site of the person, e.g. a reception clerk, receiving the forms and a separate transmission site for the operator and the input device. Forms could be collected at various pickup sites and delivered to the transmission site.
In another alternative, the sender inputs the required information, including a handwritten message if desired, directly into the input device. In a step 16 , the input device transmits the completed electronic postcard to the web site and the web site verifies the identity of the input site. The web site then affixes to the electronic postcard a postmark associated with the identified input site in a step 17 . Now the web site sends the electronic postcard to the addressee at the associated e-mail address in a step 18 . As an alternative, the input site can include the postmark which would be verified by the web site before transmitting the electronic postcard to the addressee.
There is shown in FIG. 2 a terminal 20 according to the present invention for use as the input device to create an electronic postcard according to the method of the present invention. A central processing unit CPU 21 controls the operation of the terminal 20 and has ports connected to several peripheral devices. One port of the CPU 21 is connected to an output of a payment device 22 that can operate to accept one or more modes of payment from the user. For example, the payment device 22 can include one or more of a conventional credit card reader, a conventional coin and bill acceptor and a conventional token acceptor. The payment device 22 also could be a keypad for entering a payment code obtained from a separate payment device as typically used at a gas station with a non-attended car wash. Furthermore, the payment device 22 can be any type of control actuated by a human operator to activate the terminal 20 in response to receipt of payment in any selected form.
A handwriting device 23 is connected to a port of the CPU 21 for converting a handwritten message into digital form to be incorporated in the electronic postcard. The message is converted in such a manner that the original handwriting can be displayed to an addressee.
A keyboard 24 is connected to a port of the CPU 21 for user input of information such as a message (instead of a handwritten message) and an addressee name and address. The address can be an e-mail address for electronic delivery, a mailing address for a hard copy delivery, or both.
A display 25 is connected to a port of the CPU 21 for generating images to aid the user in the creation of the electronic postcard. The display 25 can include a touch screen that performs a portion or all of the functions of the payment device 22 and the keyboard 24 . For example, the payment code and the user message can be input through the display 25 rather than through the payment device 22 and the keyboard 24 respectively. The display 25 also can be used to prompt the user to perform required tasks, verify inputted information and display scene images as described below.
A printer 26 can be connected to a port of the CPU 21 for generating a payment receipt and/or verification of the addressee information and/or a hard copy of the electronic postcard.
A modem 27 is connected to a port of the CPU 21 for two-way communication whereby the electronic postcard is transmitted on a communication line 28 connected to the modem. As discussed below, the terminal 20 is configured to operate as a component of an electronic postcard delivery system.
A memory or data storage device 29 is connected to a port of the CPU 21 and stores a plurality of digital images typically related to scenes found in the area around the location of the terminal 20 . The CPU 21 can cause these stored scenes to be reproduced on the display 25 for viewing and selection by the user. The selection can be made using any suitable device such as the keyboard 24 or a touch screen of the display 25 . The scene selection, message and addressee information can be accumulated and stored in the memory 29 until the electronic postcard is complete and ready to be sent through the modem 12 onto the communication line 28 .
Referring to FIG. 3 , there is shown a graphic representation of an electronic postcard 30 . Although the electronic postcard 30 is depicted using the layout of a typical paper postcard, any suitable arrangement of the information can be used for an electronic display and/or a hard copy. The postcard 30 includes a scene “side” 31 and a message “side” 32 . Associated with the scene side 31 is a scene information area 33 representing a selected one of a plurality of available images stored in the memory 29 of the terminal 20 shown in FIG. 1 . The message “side” 32 is divided into a message information area 34 , including a scene description 35 and a user generated message 36 , a postmark information area 37 and an address information area 38 . The scene description 35 typically is a short identification of the scene information in the area 33 . The message information 36 is the handwritten or typed message entered into the terminal 20 by the user. The postmark 37 can include a location identification such as the business (hotel gift shop), the city and the country where the electronic postcard 30 was generated. If authenticity is important, a verification code can be generated by the terminal 30 and included in the postmark 37 . The address 38 can be an e-mail address and/or a postal address for use as described below. The layout of the postcard 30 shown in FIG. 2 is simply illustrative of how the information can be displayed on a computer screen or printed out.
There is shown in FIG. 4 , an electronic postcard system 39 according to the present invention. The system includes a plurality of the input device terminals 20 available at the selected input sites throughout the world. Such locations might be, for example, businesses that traditionally sell preprinted postcards. The terminals 20 are connected by the communication line 28 to a communication network 40 such as a telephone network, a cable television network and/or the Internet. Also connected to the network 40 is a central server 41 located at the web site that processes the electronic postcards from the plurality of terminals 20 . The central server 41 can either verify the postmark 37 as having come from a corresponding one of the terminals 20 or add the postmark to the postcard 30 . The central server 41 also stores the postcard 30 for reference should an addressee request verification of the postmark. Then the central server sends the postcard 30 to the e-mail address of the addressee through the network 40 . If a postal address is provided in addition to or instead of the e-mail address, the central server 41 can generate a hard copy of the postcard 30 that can be mailed by the operator of the central server.
A local server 42 can be connected to the network 40 . The local server 42 represents, for example, an association with a geographical area such as a country where it is more efficient to process the postcards directed to addressees in that country through the local server than through the central server 41 . However, the local server 42 would also communicate all postcards to the central server 41 . The central server 41 can then accumulate operating data from the system 39 such as the volume of postcards generated by each of the terminals 20 , and payments collected and fees owed by the local operators of the terminals.
The central server 41 and/or the local server 42 also can maintain account information for a frequent user of the system. The account information can include, for example, credit card charge authorization data, a list of postcards sent and/or an address book of e-mail addresses (postal addresses, telephone numbers, etc.) to make it more convenient to send an electronic postcard and make less likely that the user will forget to send a postcard to someone.
In accordance with the provisions of the patent statutes, the present invention has been described in what is considered to represent its preferred embodiment. However, it should be noted that the invention can be practiced otherwise than as specifically illustrated and described without departing from its spirit or scope.
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A method and an apparatus for communicating with electronic postcards include a server for processing electronic postcards. Input sites remote from the server are selected based upon exposure to significant numbers of business travelers and tourists and provided with input devices. A verified communication link is established between the input devices and the server. A sender generated postcard request received at one of the input devices including an addressee e-mail address ( 38 ), a sender message ( 36 ) and a scene selection ( 33 ) transmits an electronic postcard ( 30 ) to the addressee.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a digital-to-analog (D/A) converter, and more particularly to a current cell matrix type of D/A converter for calibrating the current value of a current source cell.
[0003] 2. Description of the Background Art
[0004] Conventionally, there is a type of digital-to-analog (D/A) converter having a plurality of current source cells arranged in a matrix to receive digital data to be converted to analog data through a row decoder and a column decoder. This type of D/A converter is able to convert the current value, differential-outputted from each current source cell, to an output voltage by output end resistors to deliver the resultant output voltage as an analog output.
[0005] The current source cells operate as current sources to generate cell currents in proportion to a preset bias voltage and to differential-output the resultant cell currents in response to the input codes derived from digital data. Each current source cell includes a transistor, operating as a current source, and two current source switches, respectively controlling the positive and negative outputs of the cell current. These switches are actuated in accordance with the input codes.
[0006] Thus, the amount of current flowing through the output end resistors of the D/A converter is varied by the current source switch of each current source cell.
[0007] The transistors for each current source cell may involve unevenness caused by variation in manufacturing process to generate the current value involving an error. Such an error of the current should be corrected. For example, Hsin-Hung Chen, et al., “A 14-b 150MS/s CMOS DAC with Digital Background Calibration” 2006 Symposium on VLSI Circuits Digest of Technical Papers, proposes a digital background self-calibration scheme of the CMOS DAC (Complementary Metal-Oxide Semiconductor Digital-to-Analog Converter). In this scheme, a current source for correction, such as a dummy current source cell (CAL_DAC), is provided in a current source cell, such as a digital background calibrating current source cell, to adjust the cell current.
[0008] In this scheme, the D/A converter carries out calibration for determining the correction value of the current source for correction. During the process of the calibration, each current source cell generates current to output the resultant current via a calibration switch provided on the correction path. In the D/A converter, the current value in each current source cell is converted to a corresponding analog voltage value by a resistive current-to-voltage converter. The analog voltage value is converted to corresponding digital data by a ΔΣ modulator and a digital counter. On the basis of the result of the digital-conversion, a calibration decision circuit calculates a digital value to be delivered to the current source for correction, i.e. the correction value, and causes the calculated correction value to be stored in a memory.
[0009] A D/A converter disclosed by Japanese patent laid-open publication No. 289450/1997 operates in accordance with a segment system in which D/A converted outputs of upper bit segments equalized in current value are summed to D/A converted outputs of lower bit segments weighted in current to produce an resultant analog output. To the upper bit segments, a least one segment is added, the voltage value for switching which and the region for outputting the lower bits are controlled to correct an error in that segment.
[0010] Such conventional D/A converters use the calibration technique for ameliorating its accuracy to correct the current value of the current source cells. However, the effect brought by the connections for calibration, i.e. circuit paths for correction, is not taken into account.
[0011] For example, in the constitution for calibration as disclosed by the above Hsin-Hung Chen, et al., the CMOS DAC is provided with two switches for current source outputting and one switch for calibration for a transistor operating as a current source. However, the switches thus connected in the CMOS DAC cause the capacitance additive in a node of the switch for the current source to be increased. For example, when the switch for calibration is turned on in operation for calibration and off in regular operation, the parasitic capacitance by the switch for calibration is additively caused in the course of regular operation.
[0012] Thus, in a current source cell, when large parasitic capacitance is caused additively on the node of the switch for the current source, the effect of capacitance mismatch between the cells increases to deteriorate alternating current characteristics of the D/A converter.
[0013] If the number of switches in the current source cell is increased in order to prevent deterioration of the alternating current characteristics of the D/A converter, then the circuit is increased in size.
SUMMARY OF THE INVENTION
[0014] It is an object of the present invention to provide a digital-to-analog converter which Is capable of correcting the current generated in current source cells arrayed in matrix configuration without deteriorating its alternating current characteristics.
[0015] In accordance with the present invention, there is provided a digital-to-analog (D/A) converter including a plurality of current source cells, arranged in a matrix configuration. The D/A converter of the present invention comprises an output current oath section or digital-to-analog conversion in the regular operation and a correcting current path section for the calibration operation, as a current path for conducting a cell current generated in the current source cells. Each current source cell includes a first transistor serving as a current source that generates the cell current for a predetermined bias voltage applied thereto. In the current source cell, the first transistor is connected during the regular operation to the output current path section in cascade to flow the cell current through the output current path section and during the calibration operation to the correcting current path section in cascade to flow the cell current through the correcting current path section. The D/A converter also comprises a current corrector operative in response to a correction value obtained on the correcting current path section for generating the correction current that is used for correcting the cell current.
[0016] According to the digital-to-analog (D/A) converter of the present invention, each current source cell comprises two current source transistors functioning as current sources so that, during the regular operation, the two transistors are connected in cascode to provide an output current path section. The transistors then conduct the cell current to flow on the output current path section. When the current source cell operates for calibration, one of the current source transistors and a transistor for calibration are connected in cascade, that is, the transistor for calibration is used in place of the other current source transistor, to provide a correcting current path section. Then, the current source transistor and the calibration transistor conduct the cell current to flow on the correcting current path section.
[0017] Thus, each current source cell in the D/A converter carries out the operation for calibration to determine a correction value. The correction value is used to correct current value of each current source cell. It is therefore possible to correct differences in the current values ascribable to process variations.
[0018] Moreover, with the D/A converter, the current path for calibration is not connected to a node connected to a switch for the current source, but is connected to a junction point between the current source transistors connected in cascode to each other. It is therefore possible to prevent the parasitic capacitance from being additively caused on the node of the switch for the current source.
[0019] Additionally, with the D/A converter, if there is an error caused by the process variations between-the current source transistors used for the regular operation and the calibration transistors used for the operation for calibration, these transistors are arranged in proximity from each other so that the adverse effect caused by the process variations can be reduced extensively.
[0020] Furthermore, the D/A converter may comprise a single current corrector for correcting the cell current generated in the plurality of current source cells, the single current corrector being shared with those current source cells, thereby reducing the circuit size.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] The objects and features of the present invention will become more apparent from consideration of the following detailed description taken in conjunction with the accompanying drawings in which:
[0022] FIG. 1 is a schematic block diagram showing a preferred embodiment of a digital-to-analog (D/A) converter according to the present invention;
[0023] FIG. 2 is a schematic block diagram showing an array of current source cells in the D/A converter of the embodiment shown in FIG. 1 ; and
[0024] FIG. 3 is a schematic block diagram showing part of an alternative embodiment in which the calibration transistor is disposed outside the current source cells of the D/A converter.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0025] With reference to the accompanying drawings, a preferred embodiment of a digital-to-analog (D/A) converter according to the present invention will be described in detail. As shown in FIG. 1 , a D/A converter 10 converts digital data to analog data by a plurality of current source cells 12 arranged in a matrix configuration to output the resultant current values to output end resistors 14 and 16 , thereby obtaining the analog data. For that aim, the D/A converter 10 includes a reference current source 18 , transistors 20 and 22 , a current comparator 24 and a logic circuit 26 , which are interconnected as illustrated to calibrate the current values obtained by each current source cell 12 . It is noted that parts or elements not directly relevant to understanding the present invention will neither be described nor shown for avoiding redundancy.
[0026] Referring to FIG. 2 , the D/A converter 10 may be formed by a matrix array of current source cells 12 , to which digital data for D/A conversion are fed as input by a row decoder 70 and a column decoder 72 . Although a multiplicity of current source cells may actually be arranged in the D/A converter 10 , only a smaller number of current source cells 12 are shown in FIGS. 1 and 2 for simplicity.
[0027] The D/A converter 10 is adapted to receive the currents differentially outputted from the current source cells 12 on output lines 28 and 30 , which are in turn connected to output end resistors 14 and 16 , respectively, and thence to a reference voltage, e.g. power supply voltage VDD. On these output lines 28 and 30 , output terminals 32 and 34 are provided between the current source cells 12 and the output end resistors 14 and 16 , respectively.
[0028] In accordance with the currents flowing from the current source cells 12 , the voltages applied to the output end resistors 14 and 16 are varied, that is, the voltages outputted from the output terminals or contact pads 32 and 34 are varied. The digital input is converted in this manner to a corresponding analog output.
[0029] The current source cell 12 includes current source transistors 36 and 38 functioning as current sources, one 36 of which is connected in cascode to the other 38 . The one transistor 36 has its source electrode connected to another reference voltage, e.g. grounded, while the other transistor 38 has its drain electrode connected via switches 40 and 42 to the output lines 28 and 30 , respectively. The circuitry consisted of the transistors 36 and 38 and the switches 40 and 42 is referred to hereinbelow as a current source block 51 .
[0030] The current source block 51 runs, for instance, to supply the bias voltage to the current source transistors 36 and 38 . The current source block 51 controls the switches 40 and 42 in accordance with the digital data for D/A conversion, i.e. input codes obtained from the row decoder 70 and the column decoder 72 , so as to switch the ON and OFF conduction states between the drain electrode of the transistor 38 and the output lines 28 and 30 , respectively.
[0031] The current source cell 12 also includes a current corrector 50 adapted to calibrate the differential current values delivered from the current source block 51 , to which the current corrector 50 is electrically connected. The current corrector 50 includes a plurality of correction transistors 52 and 54 serving as current sources for calibration correction, and a plurality of switching transistors 56 and 58 serving as switches for switching the ON and OFF conduction states between the correction transistors 52 and 54 , respectively, and the current source block 51 .
[0032] In the current source cell 12 of the illustrative embodiment, particularly, a calibration transistor 60 is connected in cascode to the current source transistor 36 , which is connected via the transistor 60 to the current comparator 24 . The current source cell 12 also includes a switch 62 for switching its ON and OFF states of the connection to the current comparator 24 , and the calibration transistor 60 connected to the current comparator 24 via the switch 62 .
[0033] The current source cell 12 may preferably have a path for use in calibration operation of the calibration transistor 60 connected to a junction point between the current source transistors 36 and 38 . That causes in calibration operation the current source transistor 36 and the calibration transistor 60 to function as a couple of transistors operating as a current source. That is, the transistor 60 is used in place of the current source transistor 38 . In the illustrative embodiment, the same bias voltage is supplied to the transistors 38 and 60 .
[0034] In the current source cell 12 , if the switch 40 or 42 is in its ON state the transistor 38 allows a cell current 102 to flow therethrough, while if the switch 62 is in its ON state the transistor 60 allows the cell current to flow therethrough.
[0035] The reference current source 18 generates a reference current 104 . With the illustrative embodiment, this current 104 is set beforehand.
[0036] The D/A converter 10 further includes transistors 20 and 22 respectively positioned on the side of the reference current source 18 and the side of the current source cell 12 to form a current mirror circuit 23 together. In the illustrative embodiment, the transistor 20 is connected simply to the reference current source 18 , while the other transistor 22 is connected to, in particular, the calibration transistor 60 of the current source cell 12 and also to the current comparator 24 .
[0037] The current mirror circuit 23 including the transistors 20 and 22 generates the current in proportion to the size ratio between the side of the reference current source 18 and the side of the current source cell 12 . In the illustrative embodiment, the current substantially equal to the reference current 104 is generated on the side of the current source cell 12 .
[0038] In the illustrative embodiment, the switch 62 on the side of the current source cell 12 is connected to the calibration transistor 60 and the current comparator 24 . Thus, according to the current mirror circuit 23 , if an error caused by the mirror circuit 23 is not taken into account, the sum of a cell current 102 flowing through the calibration transistor 60 and the current 106 supplied to the comparator 24 is substantially equalized to the reference current 104 .
[0039] More specifically, by the current mirror circuit 23 , the input current 106 substantially equal to the difference between the reference current 104 and the cell current 102 is supplied to the current comparator 24 . When the reference current 104 is larger than the cell current 102 , the current 106 becomes of a positive value to flow into the comparator 24 . When the reference current 104 is smaller than the cell current 102 , the current 106 becomes of a negative value to flow out from the comparator 24 .
[0040] The current comparator 24 is adapted to compare the input current 106 to, for example, a predetermined threshold value. Specifically, the comparator 24 determines which is larger of the reference current 104 and the cell current 102 and outputs a decision result 108 to the logic circuit 26 .
[0041] The logic circuit 26 is adapted for deciding a code directing the quantity of the current 112 , i.e. a correction value 110 , conducted through the current corrector 50 . In the illustrative embodiment, the correction value 110 for the current quantity 112 to be used during the regular operation is determined in accordance with the decision result 108 by the current comparator 24 in the course of calibration operation. Preferably, the logic circuit 26 may have, e.g. a memory, not shown, adapted for storing the correction value 110 .
[0042] The D/A converter 10 of the illustrative embodiment carries out the respective calibration operation on the plurality of current source cells 12 . That is, the current comparator 24 finds a decision result 108 from each current source cell 12 and the logic circuit 26 determines the code 110 from that current source cell 12 .
[0043] Preferably, when the D/A converter 10 carries out the calibration operation, the current corrector 50 of the current source cell 12 controls the correction current value 112 to be varied little by little. In addition, the current corrector 50 preferably causes the correction current value 112 at a transition point of the sign of the input current 106 of the current comparator 24 to be stored in, e.g. a memory.
[0044] Now, the operation of the D/A converter 10 of the illustrative embodiment will be described directed to an example of regular operation for D/A conversion.
[0045] In the D/A converter 10 , the bias voltage and the input code corresponding to digital data for conversion are supplied to each current source cell 12 . In the current source cell 12 , a cell current 103 is generated between the node 44 of the current source block 51 and the predetermined reference voltage, i.e. ground (GND) in the embodiment.
[0046] During the regular operation, the switch 62 is in its OFF state initially. However, when the input codes corresponding to the digital data are supplied to the switches 40 and 42 of the current source cell 12 , the switches 40 and 42 are changed over in response to the digital data.
[0047] If the switch 40 and/or the switch 42 are in the ON state thereof, then the cell current 103 flows through the current source transistor 38 in-to the output lines 28 and/or 30 . On these output lines 28 and 30 , the cell current 103 is converted by the output end resistors 14 and 16 to a corresponding output voltage, which is in turn delivered as an output via the output terminals 32 and 34 .
[0048] In addition, if the switch 56 and/or the switch 58 of the current corrector 50 are in the ON state thereof during the regular operation, the cell current 103 may be expressed as the sum of a current 114 flowing through the current source transistor 36 and a current 112 flowing through the transistors 52 and/or 54 of the correction current source of the current corrector 50 . The cell current 112 thus serves as a current source for correcting an error caused by current mismatch of the current 114 of the current source transistor 36 . Although the illustrative embodiment configures the current corrector 50 by four transistors 52 , 54 , 56 and 58 , the block 50 may consist of more transistors than this embodiment.
[0049] Next, the operation of the D/A converter 10 of the illustrative embodiment will be described in terms of an example of operation for calibration.
[0050] In the D/A converter 10 , as with the regular operation, the bias voltage and the input codes corresponding to digital data for conversion are supplied to the respective current source cells 12 .
[0051] During the operation for calibration, the switch 62 is in its ON state, while the switches 40 and 42 are not in the ON state thereof. The cell current 102 therefore flows through the calibration transistor 60 and the switch 62 .
[0052] In addition, during the operation for calibration, the current mirror circuit 23 including the transistors 20 and 22 equalizes the current flowing through the current source cell 12 to the reference current 104 . The sum of the cell current 102 and the current 106 flowing into the current comparator 24 is therefore equal to the reference current 104 . That renders the current substantially equivalent to the difference between the reference current 104 and the cell current 102 flow into the current comparator 24 .
[0053] The current comparator 24 compares the input current 106 to the predetermined threshold value. The comparator 24 determines which is larger of the reference current 104 and the cell current 102 and outputs the decision result 108 to the logic circuit 26 .
[0054] The logic circuit 26 determines, in response to the decision result 108 of the current comparator 24 , the correction value 110 which directs the current quantity 112 for the current corrector 50 during the regular operation.
[0055] The D/A converter 10 of the illustrative embodiment carries out the above-described operation for calibration for each of the plurality of current source cells 12 . Thus, if the currents developed by the current source cells 12 are different between the cells due to a variation in manufacturing process, the D/A converter 10 may efficiently correct the currents in terms of the difference.
[0056] In an alternative embodiment, the D/A converter 10 may include, as shown in FIG. 3 , a sole calibration transistor 60 on the outside of the current source cells 12 so as to be shared with the plurality of current source cells 12 , each of which includes a switch 62 which is arranged to be controlled to change over its conductive state to the common calibration transistor 60 .
[0057] Moreover, with the D/A converter 10 of the illustrative embodiment, it is possible to provide with a sole current corrector 50 on the outer side of the current source cell 12 to correct the cell current 102 in the current source block 51 of the current source cell 12 . In this case, the current corrector 50 may be used to be shared with the plurality of current source cells 12 .
[0058] According to the illustrative embodiment, the D/A converter 10 can correct the cell current 103 ( 102 ) flowing in the current source block 51 of the current source cell 12 without using the current comparator 24 . For example, the D/A converter 10 may be configured so as to calibrate by converting the cell current to a corresponding voltage, further converting the voltage to a digital data by A/D conversion and determining the digital-converted result in comparison.
[0059] In addition, the D/A converter 10 of the embodiments is able to execute the calibration no matter whether the respective cell current quantities of the plurality of current source cells 12 are equal to or different from each other. For example, there is a type of current source cells which can execute weighting correction, to which the calibration transistor 60 of the present invention may be applied without influencing the weighting correction.
[0060] In the D/A converter 10 of the embodiments, the current source in the current source block 51 of the current source cells 12 may be constructed by applying a gain boost cascode connection. Alternatively, the current source may be constructed to include two cascode connections. The transistors in the current source of the current source cell 12 may be an NMOS or a PMOS transistor.
[0061] The entire disclosure of Japanese patent application No. 2007-181972 filed on Jul. 11, 2007, including the specification, claims, accompanying drawings and abstract of the disclosure is incorporated herein by reference in its entirety.
[0062] While the present invention has been described with reference to the particular illustrative embodiments, it is not to be restricted by the embodiments. It is to be appreciated that those skilled in the art can change or modify the embodiments without departing from the scope and spirit of the present invention.
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A current cell matrix type of digital-to-analog (D/A) converter to prevent deterioration of a.c. characteristics on a current path for digital-to-analog conversion includes a array of current source cells arranged in a matrix configuration. Each current source cell includes a current source transistor to generate the cell current. During the regular operation, the cell current is flowed on output lines via a first transistor connected in cascode to the current source transistor. During the calibration operation, the cell current is flowed into a current comparator via a second transistor connected in cascode to the current source transistor. This prevents parasitic capacitance from being additively caused in switches for the first transistor and in another switch for the second transistor to prevent deterioration of a.c. characteristics on the current path.
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[0001] This application claims of the benefit of Application No. 61/760,688, filed on Feb. 5, 2013. The disclosure of Application No. 61/760,688 is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] Polyurea coatings are known in the industry for fast curing, ability to cure at wide temperature/humidity range and excellent performance properties. Polyurea coatings are very versatile and have wide-ranging applications as commercial and industrial protective coatings, and some aliphatic polyureas are used as decorative coatings on walls, floors and other surfaces. Most polyurea coatings are two component thermoset systems that can be applied as a thick coating in one pass if a high solids formulation is used, but usually the applied finish tends to be high in reflectivity or gloss. It is very difficult to reduce or downgloss high solids polyurea coating even with high loadings of gloss reducing agents because such coatings tend to have high viscosity and cure very quickly.
[0003] There are applications where a low gloss finish is required for functional or decorative purposes because they are aesthetically preferred. In general, low gloss industrial or commercial coating formulations tend to be low solids, water or solventborne systems and usually contain high loadings of gloss reducing agents such as inorganic silica. To attain low gloss in clear coats, coating compositions are loaded with an excess amount of gloss reducing agent, typically more than 10 weight percent based on the total weight of the composition of the gloss reducing agent. Unfortunately, the gloss reducing agent in these excessively loaded coating compositions tends to coagulate. As a result, the conventional low gloss coatings resulting therefrom can have visually unacceptable cloudy or seedy appearance. Furthermore, the presence of the excessive amount of these gloss reducing agents in a coating composition tends to make the resultant coatings more brittle than conventional coating compositions. Another limitation of the current low gloss waterborne or solventborne coatings are their ability to achieve a thick coating in one pass or application at wide temperature/humidity range because of the high water or solvent content in the formulations. Thus, a need exists in this art for durable low gloss coatings that can be applied in one pass and having a desirable appearance.
BRIEF SUMMARY OF THE INVENTION
[0004] The instant invention can solve problems with conventional coatings by providing a high solids polyurea coating having a low gloss value. By “low gloss value” it is meant a gloss value of less than about 50 when measured in accordance with ASTM D-523 and using a glossmeter at an angle of 60° to a coated surface (e.g., a gloss of less than about 50 including about 45 to about 25; and about 40 to 25). By “high solids” it is meant greater than about 70% by weight solids including about 75 to about 95; and about 80 to about 90.
[0005] One aspect of the invention relates to a low gloss, high solids polyurea coating that maintains the handling and performance of typical polyureas coatings such as rapid return to service, ability to cure at a wide temperature/humidity range and excellent physical properties. In addition, the inventive low gloss coating can be applied at up to about 30 mils dry film thickness at one pass by using conventional application methods such as a roller, brush or spray and still maintain the gloss value of less than 45 (at 60° angle) when the coating is applied and cured at 5° C. to 35° C. temperature and from 10% to 90% relative humidity.
[0006] One aspect of the invention relates to a non-aqueous coating composition comprising:
A. An isocyanate reactive agent comprising at least one secondary diamine wherein the secondary diamine comprises the reaction product of at least one diamine and alkyl esters of 2-butendioic acid; B. optionally at least one polyisocyanate resin; C. optionally at least one gloss reducing agent; and D. At least one viscosity modifier; wherein C) and D) comprise less than about 35% by weight of the total coating composition. By “non-aqueous” it is meant that the coating composition comprises less than about 1 weight percent water and typically about 0 weight percent water.
[0011] Another aspect of the invention relates to a composition comprising: a reaction product of at least one diamine and alkyl esters of 2-butendioic acid; and at least one solvent.
[0012] A further aspect of the invention relates to a coating composition comprising at least one isocyanate reactive agent, at least one organic polymer, at least one gloss reducing agent and at least one solvent.
[0013] Another aspect of the invention relates to a composition comprising at least one viscosity modifier, and the reaction product of bis(4-aminocyclohexyl)methane and an ethyl ester of 2-butendioic acid.
[0014] A further aspect of the invention relates to a composition comprising at least one viscosity modifier, and the reaction product of bis(4-amino-3-methylcycohexyl)methane and an ethyl ester of 2-butendioic acid.
[0015] The various aspects of the invention can be used alone or in combinations with each other.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The instant invention relates to coating compositions and coatings that can be advantageously used to provide protection such as resistance to abrasion, impact, chemical, stain and UV, to a variety of substrates and/or can be used for decorative purposes to enhance the appearance of a certain surface.
[0017] The term “coating composition” refers to an uncured fluid composition that is sprayable or that can be brushed/rolled onto a substrate, or into which the substrate can be dipped. The term coating refers to a layer that is derived from the coating composition and is substantially free from water and/or solvent and that has undergone curing in an amount effective to form a thermoset film. The phrase “substantially free from water” means a coating composition comprising less than about 1 weight percent water and typically about 0 weight percent or non-aqueous. A protective coating as defined as one that is disposed directly or indirectly upon the substrate and can comprise one or more layers, one of which is derived from the coating composition. The term “disposed indirectly” refers to a coating that is separated from the substrate by other layers, while the term “disposed directly” refers to layers that in intimate physical contact with the substrate. While any suitable substrate can be coated, examples of such substrates including at least one of concrete, wood, metal, plastic, composites, among other suitable substrates.
[0018] Organic polymers that can be used in the coating composition as well as in the coating comprise at least one member selected from the group consisting of thermoplastic polymers, thermosetting polymers, or blends and copolymers of thermoplastic polymers with thermosetting polymers. Examples of suitable organic polymers are dendrimers, elastomers, ionic polymers, copolymers such as block copolymers, graft copolymers, random copolymers, star block copolymers, or the like. Exemplary organic polymers are thermosets. An exemplary thermoset comprises a polyurea.
[0019] The organic polymers can comprise at least one member selected from the group consisting of polyacetals, polyureas, polyurethanes, polyolefins, polyacrylics, polycarbonates, polyalkyds, polystyrenes, polyesters, polyamides, polyaramides, polyamideimides, polyarylates, polyarylsulfones, polyethersulfones, polyphenylene sulfides, polysulfones, polyimides, polyetherimides, polytetrafluoroethylenes, polyetherketones, polyether etherketones, polyether ketone ketones, polybenzoxazoles, polyoxadiazoles, polybenzothiazinophenothiazines, polybenzothiazoles, polypyrazinoquinoxalines, polypyromellitimides, polyquinoxalines, polybenzimidazoles, polyoxindoles, polyoxoisoindolines, polydioxoisoindolines, polytriazines, polypyridazines, polypiperazines, polypyridines, polypiperidines, polytriazoles, polypyrazoles, polycarboranes, polyoxabicyclononanes, polydibenzofurans, polyphthalides, polyacetals, polyanhydrides, polyvinyl ethers, polyvinyl thioethers, polyvinyl alcohols, polyvinyl ketones, polyvinyl halides, polyvinyl nitriles, polyvinyl esters, polysulfonates, polysulfides, polythioesters, polysulfones, polysulfonamides, polyureas, polyphosphazenes, polysilazanes, polyolefins, polysiloxanes, fluoropolymers, polybutadienes, polyisoprenes, or a combination comprising at least one of the foregoing organic polymers. Exemplary organic polymers are polyureas. It is desirable for the polyurea to be a thermoset. The aforementioned organic polymers listed above can be blended and/or copolymerized with the polyurea if desired. The amount of organic polymer typically ranges from about 70% to about 95% by weight of the coating composition.
[0020] The coating composition also comprises at least one isocyanate reactive agent comprising at least one secondary diamine formed by reaction of diamines with alkyl esters of 2-butendioic acid. The secondary diamine product has the general formula (I):
[0000] R 1 O 2 CCH 2 CH(CO 2 R 2 )NH—X—NHCH(CO 2 R 3 )CH 2 CO 2 R 4 (I)
[0000] wherein R 1 , R 2 , R 3 , and R 4 are the same or different and each are alkyl groups having an amount of about 1 to about 12 carbon atoms.
[0021] In one embodiment, the alkyl groups of the secondary diamine product have an amount of 1 to about 4 carbon atoms. An exemplary alkyl group is an ethyl group. R 5 can be aliphatic, alicyclic, or aromatic. X− represents a divalent hydrocarbon group obtained by the removal of the amino groups from at least one of 1,4-diaminobutane, 1,6-diaminohexane, 2,2,4- and/or 2,4,4-trimethyl-1,6-diaminohexane, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcycohexyl)methane, ethylene diamine, 1,2-diaminopropane, 1,4-diaminobutane, 2,5-diamino-2,5-dimthylhexane, 1,11-diaminoundecane, 1,12-diaminododecane, 2,4 ‘and’ or 2,6-hexahydrotoluyene diamine, 2,4- and/or 2,6-diaminotoluene and 2,4- and/or 4,4′ diaminodiphenyl methane, and polyetherdiamines. The amount of the isocyanate reactive agent typically ranges from about 20 to about 70 wt %; including about 25 to about 65 wt %; and about 30 to about 60 wt % of the coating composition. The amine equivalent weight can range from about 100 to about 500 including about 150 to about 450; and about 200 to about 400.
[0022] The coating composition can also comprise at least one polyisocyanate that comprises of an isocyanate functional compound having the general formula:
[0000] R(NCO) i, (II)
[0000] wherein R is an organic radical having the valence of i, wherein i is greater than or equal to about 2. R can be a substituted or unsubstituted hydrocarbon group (e.g., a methylene group or an arylene group).
[0023] The isocyanates can be aromatic or aliphatic. Useful aromatic diisocyanates can comprise, for example, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (each generally referred to as TDI); mixtures of the two TDI isomers; 4,4′-diisocyanatodiphenylmethane (MDI); p-phenylene diisocyanate (PPDI); diphenyl-4,4′-diisocyanate; dibenzyl-4,4′-diisocyanate; stilbene-4,4′-diisocyanate; benzophenone-4,4′-diisocyanate; 1,3- and 1,4-xylene diisocyanates; or the like, or a combination comprising at least one of the foregoing aromatic isocyanates. Exemplary aromatic diisocyanates for the preparation of polyurethane prepolymers include TDI, MDI, and PPDI.
[0024] Useful aliphatic diisocyanates can comprise, for example, 1,6-hexamethylene diisocyanate (HDI); 1,3-cyclohexyl diisocyanate; 1,4-cyclohexyl diisocyanate (CHDI); the saturated diphenylmethane diisocyanate known as H(12)MDI; (also known commercially as bis{4-isocyanatocyclohexyl}methane, 4,4′-methylene dicyclohexyl diisocyanate, 4,4-methylene bis(dicyclohexyl)diisocyanate, methylene dicyclohexyl diisocyanate, methylene bis(4-cyclohexylene isocyanate), saturated methylene diphenyl diisocyanate, and saturated methyl diphenyl diisocyanate), isophorone diisocyanate (IPDI); or the like; or a combination comprising at least one of the foregoing isocyanates. An exemplary aliphatic diisocyanate is H(12)MDI.
[0025] Other exemplary polyisocyanates include hexamethylene diisocyanate (HDI), 2,2,4- and/or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4′- and/or 4,4′-diisocyanato-dicyclohexyl methane, 2,4- and/or 4,4′-diisocyanato-diphenyl methane and mixtures of these isomers with their higher homologues which are obtained by the phosgenation of aniline/formaldehyde condensates, 2,4- and/or 2,6-diisocyanatotoluene and any mixtures of these compounds. Higher functional hexamethylenediisocyanate (HDI) polyisocyanates such as biurets, trimers, and dimers, was found to be particularly useful for purposes of the present invention. The amount of polyisocyanate typically ranges from about 10 to about 60 wt % including about 25 to about 55 wt %; and about 20 to about 50 wt % of the coating composition.
[0026] In one aspect of the invention, R in the formula (II) can also represent a polyurethane radical having a valence of i, in which case R(NCO)i is a composition known as an isocyanate-terminated polyurethane prepolymer or semi-prepolymer. Prepolymers or semi-prepolymers are formed when an excess of organic diisocyanate monomer is reacted with an active hydrogen containing component.
[0027] The inventive composition can comprise at least one gloss reducing agent. Examples of suitable gloss reducing agents comprise fine particle powders of organic and inorganic materials, urea-formaldehydes, silicas such as, for example, precipitated silica and fumed silica, polymeric beads, talc, alumina, calcium carbonate, or the like, or a combination comprising at least one of the foregoing gloss reducing agents. An exemplary gloss reducing agent is silica. An example of an exemplary gloss reducing agent is a fine-grained, organic treated precipitated silica. The gloss reducing agent typically have a particle size, d50 of about 0.5 μm to about 20 μm, about 1 μm to about 10 μm and in some cases about 3 μm to about 7 μm. The amount of gloss reducing agent typically ranges from about 1 to about 25 wt % including about 3 to about 20 wt %; and about 5 to about 15 wt % of the coating composition.
[0028] The coating composition can also comprise of at least one viscosity modifier. A viscosity modifier can comprise at least one of polar or nonpolar solvents or non-reacting diluents. Examples of solvent comprise at least one member selected from the group consisting of hexane, heptane, xylene, toluene, cyclohexane; ester type one such as methyl acetate, ethyl acetate, t-butyl acetate, acetic acid ethylene glycol monomethyl ether, acetic acid diethylene glycol monomethyl ether, dibasic ester; ether type one such as isopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether; ketone type such as methyl isobutyl ketone, methyl ethyl ketone, isophorone, acetophenone; carbonate type such as propylene carbonate, dimethyl carbonate; Pyrollidone type such as n-methylpyrollidone, n-ethyl pyrollidone; halogenated solvent type such as parachlorobenzotrifluoride, 1,1,2,2-Tetrachloroethane, 1,1-Dichloroethane and any other protic or aprotic solvent that are inert towards amines or polyisocyanates. Examples of non-reacting diluents comprise at least one member selected from the group consisting of phthalate type such as bis(2-ethylhexyl) phthalate, diisononyl phthalate, butyl benzyl phthalate; ester type such as dioctyl adipate, dibutyl sebacate, 1,2-Cyclohexane dicarboxylic acid diisononyl ester, 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate, alkyl sulphonic acid phenyl ester; citrate types such as acetyl triethyl citrate, triethyl citrate; trimellitate type such as trimethyl trimellitate, tri-(2-ethylhexyl)trimellitate and other class of non-reacting diluents such as benzoates, sulfonamides, epoxidized vegetable oils, organophosphates, glycols, polyethers, polybutene and combinations thereof. The amount of viscosity modifier typically ranges from about 2 to about 30 wt % including about 5 to about 25 wt %; and about 10 to about 20 wt % of the coating composition.
[0029] Other additives useful in the coating compositions include leveling agents, defoamers, air release agents, antioxidants, UV stabilizers, rheology modifier, pigments, dispersants, plasticizers, diluents, fillers or combinations thereof. The amount of these additives typically ranges from about 0 to about 10% including about 1 to about 5 wt %; and about 2 to about 5 wt % of the coating composition.
[0030] The components of the inventive coating composition can be combined by using any suitable conventional equipment and methods. Examples of the foregoing include a blender, agitation with impellar blade, hand mixing with stirring stick, among other conventional equipment.
[0031] The components of the coating composition are typically combined in the following order: 1) Isocyanate reactive agent(s), 2) viscosity modifier(s), 3) additive(s), 4) gloss reducing agent (mixed until solution is homogeneous); and 5) polyisocyanate.
[0032] The various aspects of this invention can be used alone or in combination. Certain aspects of the invention are illustrated by the following Examples. These Examples shall not limit the scope of the appended claims.
EXAMPLES
[0033] In the following examples, the gloss reducing agent was added to the secondary diamine product and dispersed in using a Flacktek Speedmixer™. The isocyanate reactive agent containing the gloss reducing agent and the polyisocyanate resin were then hand mixed together and applied directly to a Leneta chart by a drawdown bar. Unless specified, the films were dried at ambient conditions around 22° C., 50% relative humidity. The thickness of the film was about 2 to 25 mils. The gloss measurements were conducted after letting the coated film cure for at least 24 hours. The gloss measurements were conducted using ASTM D-523 test with glossmeter supplied by Byk-Gardner.
[0034] The following ingredients used in the formulations are shown in Table 1:
[0000]
TABLE 1
Ingredients
Details
Secondary diamine A
A reaction product of bis(4-aminocyclohexyl)
methane and ethyl ester of 2-butendioic acid
Secondary diamine B
A reaction product of bis(4-amino-3-
methylcycohexyl) methane and ethyl ester of 2-
butendioic acid
Flexisolv ™
Dibasic ester solvent mixtures from Invista
DBE Solvent
Gloss reducer A
Wax treated precipitated silica such as Acematt ®
OK-607
Gloss reducer B
Polymer treated precipitated silica such as
Acematt ® 3600
Gloss reducer C
Organic treated silica gel such as Gasil ® UV70C
from PQ Corporation
Viscosity reducer A
Propanoic acid, 2-methyl-,1,1′-[2,2-dimethyl-1-(1-
methylethyl)-1,3-propanediyl] ester
Viscosity reducer B
Alkyl sulfonic acid ester diluent
Aromatic 100
Light aromatic Naptha solvent consisting of
C9-10 dialkyl and trialkylbenzenes
Sylosiv ® A3
3 angstroms molecular sieve powder from Grace
Example 1
[0035] The first example shows coating compositions comprising secondary diamine product blended with solvents (i.e., dibasic esters, propylene carbonate, n-methyl pyrollidone or butyl diglyme). The gloss reducing agent is dispersed into the amine blend using a Speedmixer to form a homogeneous mixture. Then the polyisocyanate, hexamethylene diisocyanate trimer is added to the isocyanate reactive mixture at a stoichiometric ratio of 1.05 NCO to amine and hand mixed together before applying it onto a Leneta chart with a drawdown bar at two different thicknesses. The coating is cured for at least 24 hours at ambient conditions before measuring gloss with a glossmeter in accordance with ASTM D523. The data shows that all of the films had 60° gloss of less than 45.
[0000]
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
1A
1B
1C
1D
1E
1F
1G
1H
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
Secondary Diamine A
35.1
36.1
36.1
36.1
36.1
32.8
32.8
32.8
Secondary Diamine B
28.7
29.5
29.5
29.5
29.5
32.8
32.8
32.8
Dibasic ester solvent:
Diethyl malonate
21.2
Diethyl succinate
21.9
Flexisolv DBE-LVP
21.9
Flexisolv DBE-5
21.9
Flexisolv DBE-9
21.9
N-methyl pyrollidone
21.9
Butyl diglyme
21.9
Propylene carbonate
21.9
Gloss reducer A
15
12.5
12.5
12.5
12.5
12.5
12.5
12.5
Amine eq. wt
441
430
430
430
430
430
430
430
60° Gloss Measurement of cured coating
Dry Film
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Thickness (mil)
1A
1B
1C
1D
1E
1F
1G
1H
5
25
38
30
29
35
No data
No data
No data
10
No data
38
32
33
38
38
42
41
Example 2
[0036] Example 2 shows isocyanate reactive agent compositions comprising the secondary diamine blend, a commercial dibasic ester solvent mixture, another additive such as a non-reacting diluent, co-solvent and/or a molecular sieve and the gloss reducing agent. The low gloss coating was formed and applied using similar procedure as Example 1.
[0000]
Sample
Sample
Sample
Sample
Sample
Sample
Sample
2A
2B
2C
2D
2E
2F
2G
wt %
wt %
wt %
wt %
wt %
wt %
wt %
Secondary Diamine A
32.5
32.4
32.4
33.7
33.7
36
32.5
Secondary Diamine B
26.6
26.6
26.6
27.6
27.6
29
26.6
Flexisolv DBE-5
8.7
4.4
4.4
8.7
8.7
9
Other Additives:
Viscosity reducer A
13.8
13.8
13.8
17.5
17.5
4.5
13.8
Viscosity reducer B
5.9
5.9
5.9
5.9
Propylene carbonate
9
dimethyl carbonate
4.4
Parachlorobenzotrifluoride
4.4
Xylene
8.7
Sylosiv A3
0.5
Gloss reducer A
12.5
12.5
12.5
12.5
12
Gloss reducer B
12.5
Gloss reducer C
12.5
Amine eq. wt
475
475
475
430
430
430
430
60° Gloss Measurement of cured coating
Dry Film
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Thickness (mil)
2A
2B
2C
2D
2E
2F
2G
10
34
34
39
39
36
41
42
Example 3
[0037] Example 3 shows an isocyanate reactive agent compositions comprising the secondary diamine blend, various solvents and a gloss reducing agent. The coating was formed and applied using similar procedure as Example 1. While these solvents used in this example are effective at producing a useful coating, this Example shows that these solvents do not provide a coating having a gloss of less than 45.
[0000]
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
3A
3B
3C
3D
3E
3F
3G
3H
3I
3J
3K
3L
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
Secondary Diamine A
48
36.1
36.1
36.1
36.1
36.1
36.1
36.1
36.1
36.1
36.1
36.1
Secondary Diamine B
39.5
29.5
29.5
29.5
29.5
29.5
29.5
29.5
29.5
29.5
29.5
29.5
Solvent:
Propylene glycol
21.9
diacetate
Dipropylene glycol
21.9
methyl ether acetate
Ethylene glycol
21.9
mononbutylether acetate
Propylene glycol
21.9
monoethyl ether acetate
Aromatic 100
21.9
Methyl amyl ketone
21.9
Dipropylene glycol
21.9
dimethyl ether
Parachlorobenzotrifluoride
21.9
Dimethyl carbonate
21.9
t-butyl acetate
21.9
Xylene
21.9
Gloss reducer A
12.5
12.5
12.5
12.5
12.5
12.5
12.5
12.5
12.5
12.5
12.5
12.5
Amine eq. wt
320
430
430
430
430
430
430
430
430
430
430
430
60° Gloss Measurement of cured coating
Dry Film
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Thickness (mil)
3A
3B
3C
3D
3E
3F
3G
3H
3I
3J
3I
3m
10
92
83
68
80
88
89
84
71
81
85
83
79
Example 4
[0038] Example 4 shows one particular isocyanate reactive agent composition comprising secondary diamine blend, Flexisolv DBE-5, Viscosity reducer A and the Gloss reducer A fumed silica. This isocyanate reactive agent containing the gloss reducing agent was mixed with the polyisocyanate, hexamethylene diisocyanate trimer at 1.05 NCO to amine ratio and applied on a Leneta chart at 2, 10 and 25 dry film thicknesses. The process was repeated two more times and each of the Leneta chart was cured at three different conditions; Ambient (22° C., 50% relative humidity); Low temperature (5° C.) and high temperature/humidity (35° C., 80%). The results show that a low gloss polyureas coating can be achieved when applied at wide temperature/humidity conditions and at wide thickness ranges.
[0000]
Sample 4A
wt %
Secondary Diamine A
32.9
Secondary Diamine B
26.9
Flexisolv DBE-5
8.5
Viscosity reducer A
17.1
Gloss reducer A
14.6
Amine eq. wt
430
60° Gloss Measurement of cured coating
Dry Film Thickness (mil)
Sample 4A
22° C., 50% Relative Humidity
2
24
10
31
25
38
5° C.
2
30
10
34
25
39
35° C., 80% Relative Humidity
2
34
10
38
25
35
[0039] The present invention is not to be limited in scope by the specific aspects or embodiments disclosed in the examples which are intended as illustrations of a few aspects of the invention and any embodiments that are functionally equivalent are within the scope of this invention. Various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art and are intended to fall within the scope of the appended claims.
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A method of forming a low gloss, high solids polyurea coating containing very low volatile organic compounds (VOC) in the coating composition. The low volatile content not only makes the coating environmentally friendly but allows it to be applied at variable thickness levels and over a wide variety of environmental conditions. The coating composition is comprised of an isocyanate reactive agent containing a secondary diamine, a polyisocyanate, a gloss reducing agent and a viscosity modifier. The gloss reducing agent is generally pre-mixed into an isocyanate reactive agent containing a secondary diamine and/or polyisocyanate containing the viscosity modifier before mixing the two components together to form a low gloss polyurea coating.
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[0001] In 1995, the American Lung Association (ALA) estimated that between 15-16 million Americans suffered from COPD. The ALA estimated that COPD was the fourth-ranking cause of death in the U.S. The ALA estimates that the rates of emphysema is 7.6 per thousand population, and the rate for chronic bronchitis is 55.7 per thousand population.
[0002] Those inflicted with COPD face disabilities due to the limited pulmonary functions. Usually, individuals afflicted by COPD also face loss in muscle strength and an inability to perform common daily activities. Often, those patients desiring treatment for COPD seek a physician at a point where the disease is advanced. Since the damage to the lungs is irreversible, there is little hope of recovery. Most times, the physician cannot reverse the effects of the disease but can only offer treatment and advice to halt the progression of the disease.
[0003] To understand the detrimental effects of COPD, the workings of the lungs requires a cursory discussion. The primary function of the lungs is to permit the exchange of two gasses by removing carbon dioxide from venous blood and replacing it with oxygen. Thus, to facilitate this exchange, the lungs provide a blood gas interface. The oxygen and carbon dioxide move between the gas (air) and blood by diffusion. This diffusion is possible since the blood is delivered to one side of the blood-gas interface via small blood vessels (capillaries). The capillaries are wrapped around numerous air sacs called alveoli which function as the blood-gas interface. A typical human lung contains about 300 million alveoli.
[0004] The air is brought to the other side of this blood-gas interface by a natural respiratory airway, hereafter referred to as a natural airway or airway, consisting of branching tubes which become narrower, shorter, and more numerous as they penetrate deeper into the lung. Specifically, the airway begins with the trachea which branches into the left and right bronchi which divide into lobar, then segmental bronchi. Ultimately, the branching continues down to the terminal bronchioles which lead to the alveoli. Plates of cartilage may be found as part of the walls throughout most of the airway from the trachea to the bronchi. The cartilage plates become less prevalent as the airways branch. Eventually, in the last generations of the bronchi, the cartilage plates are found only at the branching points. The bronchi and bronchioles may be distinguished as the bronchi lie proximal to the last plate of cartilage found along the airway, while the bronchiole lies distal to the last plate of cartilage. The bronchioles are the smallest airways that do not contain alveoli. The function of the bronchi and bronchioles is to provide conducting air ways that lead inspired air to the gas-blood interface. However, these conducting airways do not take part in gas exchange because they do not contain alveoli. Rather, the gas exchange takes place in the alveoli which are found in the distal most end of the airways.
[0005] The mechanics of breathing include the lungs, the rib cage, the diaphragm and abdominal wall. During inspiration, inspiratory muscles contract increasing the volume of the chest cavity. As a result of the expansion of the chest cavity, the pleural pressure, the pressure within the chest cavity, becomes sub-atmospheric with respect to the pressure at the airway openings. Consequently, air flows into the lungs causing the lungs to expand. During unforced expiration, the expiratory muscles relax and the lungs begin to recoil and reduce in size. The lungs recoil because they contain elastic fibers that allow for expansion, as the lungs inflate, and relaxation, as the lungs deflate, with each breath. This characteristic is called elastic recoil. The recoil of the lungs causes alveolar pressure to exceed the pressure at airway openings causing air to flow out of the lungs and deflate the lungs. If the lungs' ability to recoil is damaged, the lungs cannot contract and reduce in size from their inflated state. As a result, the lungs cannot evacuate all of the inspired air.
[0006] Emphysema is characterized by irreversible damage to the alveolar walls. The air spaces distal to the terminal bronchiole become enlarged with destruction of their walls which deteriorate due to a biochemical breakdown. As discussed above, the lung is elastic, primarily due to elastic fibers and tissues called elastin found in the airways and air sacs. If these fibers and tissues become weak the elastic recoil ability of the lungs decreases. The loss of elastic recoil contributes to more air to entering the air sacs than can exit preventing the lungs from reducing in size from their inflated state. Also, the bio-chemical breakdown of the walls of the alveolar walls causes a loss of radial support for airways which results in a narrowing of the airways on expiration.
[0007] Chronic bronchitis is characterized by excessive mucus production in the bronchial tree. Usually there is a general increase in bulk (hypertrophy) of the large bronchi and chronic inflammatory changes in the small airways. Excessive amounts of mucus are found in the airways and semisolid plugs of this mucus may occlude some small bronchi. Also, the small airways are usually narrowed and show inflammatory changes.
[0008] In COPD, a reduction in airflow arises as a result of 1) partial airway occlusion by excess secretions, 2) airway narrowing secondary to smooth muscle contraction, bronchial wall edema and inflation of the airways, and 3) reduction in both lung elasticity and tethering forces exerted on the airways which maintain patency of the lumen. As a result of the COPD, the airways close prematurely at an abnormally high lung volume. As mentioned above, in an emphysematous lung there is a decrease of lung parenchyma as there are larger and fewer air sacs. Thus, there is a decrease in the amount of parenchymal tissue which radially supports the airways. This loss of radial traction allows the airway to collapse more easily. As lung recoil decreases and airway closure occur at higher lung volumes, the residual volume of gas in the lung increases. Consequently, this increased residual gas volume interferes with the ability of the lung to draw in additional gas during inspiration. As a result, a person with advanced COPD can only take short shallow breaths.
[0009] One aspect of an emphysematous lung is that the flow of air between neighboring air sacs, known as collateral ventilation, is much more prevalent as compared to a normal lung. Yet, while the resistance to collateral ventilation may be decreased in an emphysematous lung the decreased resistance does not assist the patient in breathing due to the inability of the gasses to enter and exit the lungs as a whole.
[0010] Currently, although there is no cure for COPD, treatment includes bronchodilator drugs, and lung reduction surgery. The bronchodilator drugs relax and widen the air passages thereby reducing the residual volume and increasing gas flow permitting more oxygen to enter the lungs. Yet, bronchodilator drugs are only effective for a short period of time and require repeated application. Moreover, the bronchodilator drugs are only effective in a certain percentage of the population of those diagnosed with COPD. In some cases, patients suffering from COPD are given supplemental oxygen to assist in breathing. Unfortunately, aside from the impracticalities of needing to maintain and transport a source of oxygen for everyday activities, the oxygen is only partially functional and does not eliminate the effects of the COPD. Moreover, patients requiring a supplemental source of oxygen are usually never able to return to functioning without the oxygen.
[0011] Lung volume reduction surgery is a procedure which removes portions of the lung that are over-inflated. The improvement to the patient occurs as a portion of the lung that remains has relatively better elastic recoil which allows for reduced airway obstruction. The reduced lung volume also improves the efficiency of the respiratory muscles. However, lung reduction surgery is an extremely traumatic procedure which involves opening the chest and thoracic cavity to remove a portion of the lung. As such, the procedure involves an extended recovery period. Hence, the long term benefits of this surgery are still being evaluated. In any case, it is thought that lung reduction surgery is sought in those cases of emphysema where only a portion of the lung is emphysematous as opposed to the case where the entire lung is emphysematous. In cases where the lung is only partially emphysematous, removal of a portion of emphysematous lung increases the cavity area in which the non-diseased parenchyma may expand and contract. If the entire lung were emphysematous, the parenchyma is less elastic and cannot expand to take advantage of an increased area within the lung cavity.
[0012] Both bronchodilator drugs and lung reduction surgery fail to capitalize on the increased collateral ventilation taking place in the diseased lung. There remains a need for a medical procedure that can alleviate some of the problems caused by COPD. There is also a need for a medical procedure that alleviates some of the problems caused by COPD irrespective of whether a portion of the lung, or the entire lung is emphysematous. The production and maintenance of collateral openings through an airway wall which allows expired air to pass directly out of the lung tissue responsible for gas exchange. These collateral openings ultimately decompress hyper inflated lungs and/or facilitate an exchange of oxygen into the blood.
SUMMARY OF THE INVENTION
[0013] This invention relates to devices and methods for altering gaseous flow in a diseased lung. In particular, the inventive method includes the act of improving gaseous flow within a diseased lung by the step of altering the gaseous flow within the lung. A variation of the inventive method includes the act of selecting a site for collateral ventilation of the diseased lung and.creating at least one collateral channel at the site. The term “channel” is intended to include an opening, cut, slit, tear, puncture, or any other conceivable artificially created opening. A further aspect of the invention is to locate a site within a portion of a natural airway of the respiratory system of the patient having the diseased lung. The portion of the natural airway selected for the creation of the collateral channels may be, for example, the bronchi, the upper lobe, the middle lobe, the lower lobe, segmental bronchi and the bronchioles.
[0014] A variation of the invention includes selecting a site for creating a collateral channel by visually examining areas of collateral ventilation. One variation includes visually examining the lung with a fiber optic line. Another example includes the use of non-invasive imaging such as x-ray, ultrasound, Doppler, acoustic, MRI, PET computed tomography (CT) scans or other imaging. The invention further includes methods and devices for determining the degree of collateral ventilation by forcing gas through an airway and into air sacs, reducing pressure in the airway, and determining the reduction in diameter of the airway resulting from the reduction in pressure. The invention further includes methods and devices for determining the degree of collateral ventilation by forcing a volume of gas within the lung near to the airway and measuring pressure, flow, or the return volume of gas within the airway. The invention also includes methods and devices for occluding a section the airway and determining the degree of collateral ventilation between the occluded section of the airway and the air sacs.
[0015] An important, but not necessarily critical, portion of the invention is the step of avoiding blood vessels or determining the location of blood vessels to avoid them. It is typically important to avoid intrapulmonary blood vessels during the creation of the collateral channels to prevent those vessels from rupturing. Thus, it is preferable to avoid intrapulmonary or bronchial blood vessels during the creation of the collateral channels. Such avoidance may be accomplished, for example by the use of non-invasive imaging such as radiography, computed tomography (CT) imaging, ultrasound imaging, Doppler imaging, acoustical detection of blood vessels, pulse oxymetry technology, or thermal detection or locating. The avoidance may also be accomplished using Doppler effect, for example transmission of a signal which travels through tissue and other bodily fluids and is reflected by changes in density that exist between different body tissue/fluids. If the signal is reflected from tissue/fluid that is moving relative to the sensor, then the reflected signal is phase shifted from the original signal thereby allowing for detection. The invention includes devices having at least one sensor for the above described imaging methods. In variations of the invention having multiple sensors, the sensors may be arranged in a linear pattern or in an array pattern. Also, the invention may have a mark to serve as a reference point while the device is remotely viewed.
[0016] The invention may include adding an agent to the lungs for improving the imaging. For example, a gas may be inserted into the lungs to provide contrast to identify hyperinflation of the lungs during an x-ray or other non-invasive imaging. For example, 133 Xe (Xenon 133) may be used as the agent. Also, a contrast agent may help in identifying blood vessels during CT scans. Another example includes inserting a fluid in the lungs to couple an ultrasound sensor to the wall of an airway.
[0017] Another variation of the act of looking for blood vessels includes insertion of a probe into a wall of the natural airway for the detection of a blood vessel. Such a probe may, for example, detect the presence of a blood vessel upon encountering blood such as when the probe is inserted into a vessel. The probe may also use ultrasonic detection to determine the location of a vessel. For example, ultrasound may be used to determine changes in composition of the tissue beyond the airway wall for determination of the location of a vessel. A probe may, for example, use low frequency radio energy to induce heat at a point and determine the presence of a vessel by measuring a change in temperature due to the conduction of heat by the blood flowing within the vessel. Another variation is that the probe could detect changes in impedance given a pre-arranged discharge of current through the bloodstream. It is also contemplated that the probe is used, for example, purposely to find the blood vessel, so that an alternative. site may be selected at a safe distance from the vessel.
[0018] Another variation of the invention is via the delamination of the blood vessel and the wall of an airway. This delamination may occur in many ways. For instance, the airway may be expanded until the vessel separates from the wall of the airway. Or, a vacuum may be applied within the interior of the airway using, for example, two occlusive balloons or the like to isolate a portion of the airway and apply a vacuum. The vacuum between the balloons constricts the diameter of the airway by collapsing the walls of the airway until the exterior walls separate from any blood vessel.
[0019] The invention may also include providing a remotely detectable signal to indicate the presence or absence of any blood vessels at the target site. The invention also includes methods and devices for marking a desired site for the creation of a collateral channel.
[0020] The invention also includes the act of creating one or more collateral channels within the respiratory system of the individual. The collateral channels may have a cross sectional area anywhere between 0.196 mm 2 to 254 mm 2 . Any subset of narrower ranges is also contemplated. The collateral channels may also extend anywhere from immediately beyond the epithelial layer of the natural airway to 10 cm or more beyond the epithelial layer. The channel or channels should be created such that the total area of the channel(s) created is sufficient to adequately decompress a hyperinflated lung. The channel may be, for example, in the shape of a hole, slit, skive, or cut flap. The channel may be formed by the removal of any portion of the airway wall; e.g., a circumferential or arc-shaped ring of material may be removed to form the channel. Such an excised periphery may be for example, perpendicular or at angled with respect to the axis of the airway.
[0021] Another variation of the invention involves creation of a collateral channel by creating an incision in a natural airway and using a blunt member to push the vessel away from the path of a collateral channel. Another variation of forming the collateral channel is, for example, by use of a mechanical process such as dilation, cutting, piercing, or bursting. For example, a balloon may be used to expand an incision made in the natural airway or the natural airway itself until a collateral channel is opened. Or, a mechanical cutter or piercing tool could be used to open and create the collateral channel. Another variation for creating a collateral channel includes making an incision in the natural airway and placing the wall of the airway in tension, then advancing a blunt instrument into the incision.
[0022] Also, it is anticipated that along with any method of creating a collateral channel any loose material or waste generated by the creation of the collateral channel is optionally removed from the airway.
[0023] Another variation for creating the collateral channel is the creation of the airway using electric energy, for example radio frequency. Or, for example, ultrasonic energy, a laser, microwave energy, chemicals, or cryo-ablative energy may be used to form a collateral channel as well. A feature of these methods often includes creation of a hemostasis in the event that any blood vessel is punctured. For example, use of RF energy provides a hemostasis given a puncture of a vessel by using heat to seal the vessel. Similarly, an ultrasonic scalpel also provides an area of hemostasis in ease the vessel is punctured. It is understood that any combination of different methods may be used for forming a single or multiple collateral channels. A variation of the invention includes a limiter for limiting the depth of a collateral channel.
[0024] A variation of the inventive device includes a device that detects motion within tissue using Doppler measurements. The device may include a flexible member having a transducer assembly that is adapted to generate a source signal and receive a reflected signal. The inventive device may also comprise a hole-making assembly that is adapted to making collateral channels within tissue. The transducer assembly may include an acoustic lens which enables the transmission and detection of a signal over a tip of the device. The hole-making assembly may be an RF device and use portions of the tip of the device as RF electrodes, or the hole-making assembly may use ultrasound energy to make the hole.
[0025] Another variation of the invention includes the act of inserting an implant or conduit within a collateral channel to maintain the patency of the channel over time during the expiration cycle of the lung. A conduit could, for example, have distal and proximal ends with a wall defining a lumen extending between the ends. The conduit could have, for example, a porous wall permitting the exchange of gasses through the wall. The conduit may, for example, be comprised of a material such as elastomers, polymers, metals, metal alloys, shape memory alloys, shape memory polymers, or any combination thereof. A variation of the invention includes an expandable conduit, either one that is self-expanding, or one that expands in diameter in relation to any applied radial, or axial force. For example, the conduit may be expanded into an opening of the natural airway upon the inflation of a balloon. A variation of the conduit may include the use of flanges or anchors to facilitate placement of the device within an airway. Another variation of the conduit includes placing a one-way valve within the conduit. Another variation includes using a self cleaning mechanism within the conduit to clear accumulating debris.
[0026] The inventive conduit may be, for example, removable or permanent. Also, another variation of the device includes a means for inserting the conduit within a collateral channel. The conduit may be constructed to allow for passage of gasses through its wall, for example, the conduit may have a wall consisting of a braid. A variation of the conduit may be located through an opening in a wall of an airway and engage both an inside and outside of the wall. Another variation of the conduit includes a distal end having a porous member and a proximal end having a grommet member which engages an opening in a wall of the natural airway. Yet another variation of the implant, for example, comprises an expandable conduit-like apparatus which could bridge an opening within a wall of a natural airway. Another variation includes the conduit-like apparatus having a cutting portion exterior to the device wherein expansion of the device pierces the wall of the natural airway and creates a collateral channel.
[0027] An aspect of the invention is that conduits of varying cross-sectional areas may be placed in various sections of the lung to optimize the effect of the collateral channels.
[0028] Another variation of the invention includes the application of a cyano-acrylate, fibrin or other bio-compatible adhesive to maintain the patency of a collateral channel. The adhesive may be used with or without the conduit described above. For example, the adhesive may be deposited within the collateral channel to maintain patency of the channel or to create a cast implant of the channel. The inventive act further includes the act of delivering medications such as steroids which have been shown to inhibit the healing process, bronchodilators, or other such drugs which aid in breathing, fighting infection, or recovery from the procedure. The steroids inhibit inflammation and then promote the stabilization of the created channel.
[0029] Another variation of the inventive process includes promoting the flow of gasses through under-utilized parenchymal inter-conduits, or bypassing restricted airways. It is also contemplated that the gaseous flow may be altered by, for example, making separate inspiratory and expiratory paths. Also, relieving pressure on the external wall of a natural airway may be accomplished to assist the natural airway by maintaining patency during the expiration cycle of the lung. Yet another variation includes creating collateral channels parallel to existing airflow paths, or the existing airflow paths may be increased in cross-sectional area.
[0030] The invention further includes a device for altering gaseous flow in a diseased lung comprising a locator for locating a site for collateral ventilation of the lung, and optionally, a creating means for opening at least one collateral channel at the site. It is contemplated that the device includes a means for locating a blood vessel as described above. Also, as stated above, the device may use a mechanical, electrical, laser, ultrasonic, microwave, or chemical process for creating a collateral channel.
[0031] Another variation of the device includes a means for coagulating blood upon the entry of the device into a blood vessel. Yet another variation of the device includes the means for locating and the means for creating are the same. The device may further include a means for simultaneously creating a plurality of collateral channels.
[0032] Another variation of the implant includes conduits constructed from materials that oppose the constriction of the natural airway over time during the expiration cycle of the lung. Yet another variation of the implant includes a device which expands as the pressure in the lung decreases during the expiration cycle.
[0033] The invention further includes a modified respiratory airway having an artificially created channel allowing gaseous communication between an exterior of the airway and an interior of the airway.
[0034] The invention may include an endoscope or a bronchoscope configured to select sites and create collateral channels at those sites. An endoscope or a bronchoscope may also be configured to deploy conduits within the collateral channels. Another variation of the invention includes sizing the device to fit within the working channel of a bronchoscope.
[0035] The invention also includes methods for evaluating an individual having a diseased lung for a procedure to create collateral channels within an airway of the individual. The invention further includes the method of determining the effectiveness of the procedure.
[0036] The invention further includes the act teaching any of the methods described above.
[0037] The invention further includes the method of sterilizing any of the devices or kits described above.
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] FIGS. 1 A- 1 C illustrates various states of the natural airways and the blood-gas interface.
[0039] FIGS. 1 D- 1 G illustrate devices and methods for determining the degree of collateral ventilation within a lung.
[0040] [0040]FIG. 2A illustrates a natural airway with a collateral channel in relation to a blood vessel.
[0041] FIGS. 2 B- 2 K illustrate methods of avoiding blood vessel prior to the creation of a collateral channel.
[0042] FIGS. 2 B- 2 E illustrate various methods for delaminating an airway from a blood vessel.
[0043] [0043]FIG. 2F illustrates the use of a probe to determine a site for creating a collateral channel.
[0044] FIGS. 2 G- 2 K illustrate the use of sensors to determine a site for creating a collateral channel.
[0045] FIGS. 3 A- 3 I illustrate methods of and devices for creating a collateral opening within a natural airway.
[0046] FIGS. 3 J- 3 K illustrate a method of folding epithelial tissue through a collateral channel.
[0047] [0047]FIG. 4 illustrates a device and method for simultaneously creating numerous collateral channels or deployment of numerous probes.
[0048] FIGS. 5 A- 5 W illustrate various configuration of implantable conduits.
[0049] FIGS. 6 A- 6 D illustrate devices for detecting blood vessels within tissue.
[0050] FIGS. 6 E- 6 O illustrates various devices for detecting blood vessels within tissue where the devices also include hole-making assemblies.
[0051] FIGS. 6 P- 6 V illustrate various electrode configurations for the hole-making assemblies of the device.
[0052] FIGS. 7 A- 7 B illustrate devices and methods for creating a collateral channel with a device having a hole-making assembly and also preserving the tissue surrounding the collateral channel.
[0053] FIGS. 7 C- 7 D illustrate additional electrode configurations for use with a device of the present invention where the structure of the electrodes limits the possible depth of a collateral channel formed by the electrode.
[0054] FIGS. 8 A- 8 U illustrate variations of conduits of the present invention.
[0055] FIGS. 9 A- 9 I illustrate variations of methods and devices for deployment of conduits of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0056] Prior to considering the invention, simplified illustrations of various states of a natural airway and a blood gas interface found at a distal end of those airways are provided in FIGS. 1 A- 1 C. FIG. 1A shows a natural airway 100 which eventually branches to a blood gas interface 102 . FIG. 1B illustrates an airway 100 and blood gas interface 102 in an individual having COPD. The obstructions 104 impair the passage of gas between the airways 100 and the interface 102 . FIG. 1C illustrates a portion of an emphysematous lung where the blood gas interface 102 expands due to the loss of the interface walls 106 which have deteriorated due to a biochemical breakdown of the walls 106 . Also depicted is a constriction 108 of the airway 100 . It is generally understood that there is usually a combination of the phenomena depicted in FIGS. 1 A- 1 C. More usually, the states of the lung depicted in FIGS. 1B and 1C are often found in the same lung.
[0057] The following illustrations are examples of the invention described herein. It is contemplated that combinations of aspects of specific embodiments or combinations of the specific embodiments themselves are within the scope of this disclosure.
[0058] As will be explained in greater detail below, central to this invention in all of its aspects is the production and maintenance of collateral openings or channels through the airway wall so that expired air is able to pass directly out of the lung tissue and into the airways to ultimately facilitate exchange of oxygen into the blood and/or decompress hyper inflated lungs. The term ‘lung tissue’ is intended to include the tissue involved with gas exchange, including but not limited to, gas exchange membranes, alveolar walls, parenchyma and/or other such tissue. To accomplish the exchange of oxygen, the collateral channels allow fluid communication between an airway and lung tissue. Therefore, gaseous flow is improved within the lung by altering or redirecting the gaseous flow within the lung, or entirely within the lung. FIG. 1D illustrate a schematic of a lung 118 to demonstrate a principle of the invention described herein. As shown, a collateral channel 112 places lung tissue 116 in fluid communication with airways 100 allowing expired air to directly pass out of the airways 100 . As shown, constricted airways 108 may ordinarily prevent air from exiting the lung tissue 116 . In the example illustrated in FIG. 1D, conduits 200 may be placed in the collateral channels 112 to assist in maintaining the patency of the collateral channels 112 . Therefore, it is not necessary to pierce the pleura to improve gaseous flow within the lungs. While the invention is not limited to the number of collateral channels which may be created, it is preferable that 1 or 2 channels are placed per lobe of the lung. For example, the preferred number of channels is 2-12 channels per individual patient.
[0059] Accordingly, since the invention is used to improve the function of the lungs, a variation of the inventive device may include an endoscope or a bronchoscope configured to locate a site for creating a collateral channel and create the collateral channel. Another variation includes sizing the inventive device to fit within a working channel of an endoscope or a bronchoscope. For the sake of brevity, hereafter, any reference made to an endoscope includes the term bronchoscope.
[0060] The invention includes assessing the degree of the collateral ventilation taking place in an area of a lung to select a site for creation of a collateral channel. The invention may include locating a site for creation of a collateral channel by visually examining an airway for dynamic collapse. One method of visual examination includes the use of a fiber optic line or camera which may be advanced into the lungs and through the airways. Other variations of visually examining the lung to determine the location of a site for the creation of the collateral channel using non-invasive imaging, including but not limited toradiography, computer tomography, ultrasound, Doppler, and acoustic imaging. Such imaging methods may also be used to determine the amount of collateral channels to be created.
[0061] Also contemplated in the invention is the addition of various agents to assist during imaging of the airways or lungs. One example includes the use of a non-harmful gas, such as Xenon, to enhance the visibility of hyperinflated portions of the lung during radiological imaging. Another example includes the use of inserting a fluid in the lungs to provide an improved sound transmission medium between the device and the tissue in variations of the invention using ultrasound, acoustic, or other imaging.
[0062] Another variation of the invention includes methods and devices for triggering a collapse of the airway to determine the degree of collateral ventilation in the lung. One example includes forcing a fluid, such as a gas, air, oxygen, etc., through the airway and into the air sacs. Next, to assess the patency of the airway, the pressure is reduced in the airway. One example of how pressure is reduced in the airway includes evacuating the air in a direction opposite to the air sacs. Constriction of the airway given a drop in pressure may be an indication of collateral ventilation of the lung in that region.
[0063] [0063]FIG. 1E, illustrates a method and device 212 for causing collapse of the airway wall 100 . The device 212 includes a fluid delivery member 214 located at a distal end of the device 212 . The fluid delivery member 214 is configured to deliver a volume of fluid through the airway 100 and into an air sac (not shown). The device 212 may also comprise a probe 216 configured to collect data within the lung. The probe 216 may also simply consist of a channel that transmits signals outside of the lung. Moreover, the fluid delivery member 214 and the probe 216 may not be separate channels. Also, the device 212 may, but does not necessarily, have an occlusion member 218 designed to isolate a section of the airway 100 between the occlusion member 218 and the air sacs (not shown). The occlusion member 218 , which forms a seal against the airway 100 walls, may provide a partially closed system allowing a more effective search for collateral ventilation between the air sacs (not shown.) The device delivers a burst of fluid, through the fluid delivery member 214 and subsequently uses the probe 216 to measure characteristics such as pressure, flow, or return volume to determine the degree of collateral ventilation. The term fluid is intended to include, air or a gas, such as oxygen, etc. For example, if the air sacs are diseased (as shown in FIG. 1C), the forced fluid will escape/disperse through another air sac due to the collateral ventilation of the air sacs. As a result, the probe 216 may fail to record any increase in pressure, volume, flow, or any other characteristic of the fluid at the site. Another variation of the invention includes using the fluid delivery member 214 to add or remove fluid distally to the occluded segment and using the probe 216 to monitor flow or pressure changes in the area. For example, if after adding/removing fluid the pressure in the occluded segment fails to build/drop, the assumption may be made that the gas is being collaterally vented through diseased air sacs.
[0064] [0064]FIG. 1F illustrates another variation of the invention. In this example, the device 220 comprises a separated probe 216 and gas delivery member 214 . In this variation, the fluid delivery member 214 is configured to pass through a wall of the airway 100 so that fluid may be directly forced into, or pulled out of an air sac 102 .
[0065] [0065]FIG. 1G illustrates yet another variation of the invention. In this variation, the device 222 may have at least one fluid exchange passageway 224 . The device 222 may force fluid into the airway 100 via the passageway 224 . Then, fluid can be pulled out via the passageway 224 , thus decreasing pressure distally to the device 222 . The decrease in pressure permits fluid to flow out of the airway 100 and away from the air sac (not shown). In this case, if the air sacs surrounding the airway 100 are diseased and collateral ventilation is taking place, then the airway 100 may collapse. A variation of the invention may include an expandable member 218 , such as a balloon, to create a seal against the airway 100 walls. Forming a seal may provide a partially closed system to search for collateral ventilation between air sacs (not shown.) As described above, observation of a collapsing airway 100 may indicate a desired site for creation of a collateral channel.
[0066] [0066]FIG. 2A illustrates a blood vessel 110 on an outer wall of an airway 100 . In this figure, the collateral channel 112 created using this invention is located away from the vessel wall 110 . Such a positioning of the collateral channel 112 eliminates the risk of rupturing the vessel 110 during formation of the collateral channel 112 . As mentioned above, the term channel is intended to include an opening, cut, slit, tear, puncture, or any other conceivable artificially created opening.
[0067] Of course, it is not the case that blood vessels are necessarily as conveniently located as is seen in FIG. 2A. Consequently, it may be desirable to move the vessels or to avoid them. FIG. 2B illustrates a first way of moving the nearby vessel. FIG. 2B shows the inflation of the airway 100 using a balloon 204 provided on a delivery device 202 . As shown in FIG. 2C, upon deflation of the balloon 204 , the airway 100 and the vessel 110 become delaminated thereby moving the vessel from the region just outside the exterior of the airway. Subsequent creation of a collateral channel using the inventive procedures will be less likely to hit the vessel.
[0068] [0068]FIG. 2D demonstrates another device 206 and method for delaminating an airway 100 from a vessel 110 . In this variation, the two balloons ( 204 & 205 ) occlude the airway 100 . As shown in FIG. 2E, upon application of a vacuum, the vessel 110 and the airway 100 delaminate as the airway 100 separates from the vessel 110 . It may be desirable to make a channel while the airway is contracted as shown in FIG. 2E.
[0069] [0069]FIG. 2F illustrates the insertion of a probe 210 into a wall of the airway 100 . Although, the probe 210 is illustrated to be a singular probe, the delivery device 208 may be adapted to have multiple probes. As described above, the probe 210 may detect the presence of blood such as when the probe is inserted into a vessel. For example, the probe 210 could be configured to puncture a wall of the airway 100 , and detect the presence of blood. Optionally, the probe 210 could pull a vacuum to facilitate entry of blood into the probe 210 . The probe 210 may also use ultrasonic detection to determine the location of a vessel. For example, ultrasound may be used to determine changes in composition of the tissue beyond the airway wall for determination of the location of a vessel. A probe 210 may, for example, use low frequency radio energy to induce heat at a point and determine the presence of a vessel by measuring a change in temperature due to the conduction away or removal of heat by the blood flowing within the vessel. Another variation is that the probe 210 could detect changes in impedance given a pre-arranged discharge of current through the bloodstream. If a probe 210 detects blood during its travel outside the airway, the user could select another spot for a collateral channel.
[0070] Another variation of the invention includes methods and devices for determining whether a blood vessel is in proximity to a potential site. Making this determination prior to creating the channel is advantageous as the risk of puncturing a blood vessel is minimized. As mentioned above, non-invasive imaging may be used to locate blood vessels or to confirm the absence of a vessel at a site. FIG. 2G illustrates an example of this variation of the device 226 having a single sensor 228 . The device may be, but is not necessarily, steerable and rotatable such that the sensor 228 can be placed in contact with any portion of the airway 100 wall. In non-steerable variations, the device may be located to a site by the use of an endoscope. The device 226 may also be stiff so that the sensor 228 may be placed in firm contact with a wall of the airway 100 . It is important that the device does not ‘wander’ causing the creation of a collateral channel at a distance from the area originally searched. Such an occurrence may compromise a blood vessel (e.g., puncture, rupture, or otherwise open the blood vessel) even though the step of detecting the location indicated the absence of a blood vessel. In those cases, a stiffer wall provides added benefits.
[0071] Another variation of the invention includes inserting a fluid into the airway to provide a medium for the sensor 228 couple to the wall of the airway 100 to detect blood vessels. In those cases where fluid is not inserted, the device may use mucus found within the airway to directly couple the sensor 228 to the wall of the airway 100 .
[0072] [0072]FIG. 2H illustrates another variation of the inventive device 230 having a plurality of sensors 228 arranged in an array pattern. Although not shown, the array could extend around the circumference of the device 230 . FIG. 2I illustrates yet another variation of the inventive device. In this example, the device 232 comprises a plurality of sensors 228 arranged in a linear pattern. Although not shown, the pattern may also wind helically or in other patterns around the perimeter of the device 232 .
[0073] [0073]FIG. 2J illustrates another variation of the invention. In this example, the device 234 comprises a sensor 228 encapsulated by an expandable member 236 e.g., a balloon. The expandable member 236 may be filled with a fluid or other substance that couples the sensor 228 to an outer surface of the expandable member 236 . The sensor 228 may be rotatable within the expandable member 236 , or the entire device 234 may be rotatable within the airway 100 . Another variation of the device 234 includes a mark 238 which provides a reference for orientation of the device 234 in the airway 100 . The mark 238 is preferably remotely detectable and may be positioned on the expandable member 236 .
[0074] Another variation of the invention includes a means for marking the site. This variation of the device allows marking of the site after it is located. Accordingly, once marked, a previously selected site can be located without the need to reexamine the surrounding area for collateral ventilation, or the presence or absence of a blood vessel. The marking may be accomplished by the deposit of a remotely detectable marker, dye, or ink. Or, the marking may comprise making a physical mark on the surface of the airway to designate the site. Preferably, the mark is detectable by such imaging methods as radiography, computer tomography (CT) imaging, ultrasound imaging, doppler imaging, acoustical detection, or thermal detection or locating. Also, the mark may be detectable by direct visualization such as the case when a fiber optic cable is used. FIG. 2K illustrates an example of the device 240 having a sensor 228 to locate a site and a marking lumen 242 which may deposit an ink, dye, or other marker (not shown) on the site once located.
[0075] Although not illustrated, the invention may include a user interface which provides feedback once an acceptable site is located. For example, once a site is located a visual or audible signal or image is transmitted to the user interface to alert the user of the location of a potential site. The signal could be triggered once a blood vessel is located so that the site is selected in another location. In another example, the signal may trigger so long as a blood vessel is not located.
[0076] FIGS. 3 A- 3 I depict various ways of providing openings in the airway wall which may be used as collateral air passageways.
[0077] [0077]FIG. 3A illustrates an airway 100 having a piercing member 300 and a dilation member 302 . In this example, the piercing member 300 makes an incision (not shown) in the airway 100 wall. Next, the piercing member 300 is advanced into the wall so that a dilation member 300 can expand the incision to thereby provide a collateral channel. In this example, the dilation member 300 is depicted as a balloon. One variation of the invention includes filling a balloon with a heated fluid as the balloon dilates the tissue to form the collateral channel. Use of a heated balloon allows the transfer of heat to the collateral channel for modifying the healing response. However, it is also contemplated that the dilation member may be an expanding wedge (not shown) or other similar device.
[0078] [0078]FIG. 3B shows a cutting device 304 and an airway 100 having an opening 306 cut from a wall. In this example, a flap 308 is cut from the wall and is attached to an outside or an inside wall of the airway 100 . As will be mentioned below, the flap may be glued, using for instance, fibrin-based or cyano-acrylate-based glues or stapled to that wall.
[0079] [0079]FIG. 3C illustrates a cutter 304 making an incision 310 in a wall of the airway 100 . FIG. 3D illustrates one example of placing the walls of the airway 100 in tension and inserting a blunt instrument 314 into the incision. In this example, the delivery device 312 is flexible and may be shaped to the contour of an airway 100 to provide support for the blunt instrument 314 so that the instrument 314 can advance into the incision. The delivery device 312 is also used to deliver a blunt instrument 314 which expands the original incision. The blunt instrument 314 may have a hooked configuration as needed.
[0080] [0080]FIG. 3E shows the use of a balloon 320 to dilate a previously formed collateral channel in the airway wall 100 . This procedure may be used variously with other mechanical, chemical, cryo-energy or RF based penetration systems to expand the size of that previously-formed opening.
[0081] [0081]FIG. 3F illustrates a variation of the device 322 having an RF electrode 324 . This variation of the invention uses RF energy to create a collateral channel. The device 322 may be mono-polar or bi-polar. The RF energy throughout this invention is similar to that of a typical RF cutting probe operating between the 300 KHz-600 KHz range.
[0082] FIGS. 3 G- 3 I illustrates additional variations of devices of the present invention used to create collateral channels. The devices may use RF energy, either monopolar or bipolar, or the devices may use light, infrared heat, or any of the other methods describe herein. In the variation of FIG. 3G, the device 328 has an electrode 324 located on a side of the device. This variation of the device 328 automatically limits the depth of the collateral channel as the body of the device 328 remains against an airway 100 wall while the electrode 324 creates a channel.
[0083] [0083]FIGS. 3H and 3I illustrates another variation of a device 330 of the present invention having an electrode 324 located on a front face of the device. FIG. 3I illustrates a perspective view of the device 330 with an electrode on the front face 324 . The device 330 may either have an electrode 324 disposed on a front surface of the device 330 or the device may comprise a conductive material with an insulating layer 332 covering the device 330 and leaving an electrode surface 324 exposed. In the variations illustrated in FIGS. 3 G- 3 I, the size of the electrode may be selected based upon the size of the desired collateral channel.
[0084] The device of the present invention may also be configured to limit the depth of the collateral channel. In one example, the invention may include a shoulder or stop 326 to limit the depth of the collateral channel. Another example includes graduated index markings on a proximal end of the device or on the distal end so long as they are remotely detectable. Also contemplated is the use of RF impedance measuring. In this example, the use of RF impedance may be used to determine when the device leaves the wall of the airway and enters the air sac or less dense lung tissue.
[0085] The invention also includes creating a collateral channel by making a single or a series of incisions in an airway wall then folding back the cut tissue through the collateral channel. This procedure allows the surface epithelium which was previously on the inside of the airway wall to cover the walls of the newly formed collateral channel. As discussed herein, promoting growth of the epithelium over the walls of the collateral channel provides a beneficial healing response. The incision may be created by the use of heat or a mechanical surface. For example, FIG. 3J illustrates a section of an airway 100 having several incisions 356 forming a number of sections 358 of airway wall tissue the airway 100 . FIG. 3K illustrates the sections or flaps 358 of the airway wall folded through the collateral channel 112 . Any number of incisions 358 may be made to form any number of sections 358 of airway wall tissue as desired. For example, a plus-shaped incision would result in four sections of tissue that may be folded through a channel. The sections 358 may be affixed with a suture material, an adhesive, or the sections 358 may simply be inserted into surrounding tissue to remain folded through the collateral channel 112 .
[0086] Another-variation of the device includes safety features such as probes to determine the presence of blood. If a probe indicates that a blood vessel is contacted or penetrated, a signal is sent which prevents the channel making device from causing further harm to the vessel. Such a feature minimizes the risk of inadvertently puncturing a blood vessel within the lungs.
[0087] Although the examples depict mechanically forming a collateral opening, the invention is not limited to such. Alternative methods of forming the opening are contemplated in the use of RF energy, bi-polar, or single pole electrosurgical cutters, ultrasonic energy, laser, microwave, cryo-energy or chemicals.
[0088] The present invention includes the use of a device which is able to detect the presence or absence of a blood vessel by placing a front portion of the device in contact with tissue. One variation of the invention includes the use of Doppler ultrasound to detect the presence of blood vessels within tissue. It is known that sound waves at ultrasonic frequencies travel through tissue and reflect off of objects where density gradients exist. In which case the reflected signal and the transmitted signal will have the same frequency. Alternatively, in the case where the signal is reflected from the blood cells moving through a blood vessel, the reflected signal will have a shift in frequency from the transmitted signal. This shift is known as a Doppler shift. Furthermore, the frequency of the signals may be changed from ultrasonic to a frequency that is detectable within the range of human hearing.
[0089] The ultrasound Doppler operates at any frequency in the ultrasound range but preferably between 2 Mhz-30 Mhz. It is generally known that higher frequencies provide better the resolution while lower frequencies offer better penetration of tissue. In the present invention, because location of blood vessels does not require actual imaging, there may be a balance obtained between the need for resolution and for penetration of tissue. Accordingly, an intermediate frequency may be used (e.g., around 8 Mhz).
[0090] [0090]FIG. 6A illustrates a variation of a device 600 adapted to determine the presence of blood vessels as previously mentioned. The device 600 includes a flexible elongate member 604 having a transducer assembly 606 , at least a portion of which is located adjacent to a distal end of the elongate member 604 . Although the elongate member 604 is illustrated as having a lumen, the elongate member 604 may also be selected to be solid, or the elongate member 604 may have a support member (not shown) such as a braid to increase the strength and/or maneuverability of the device. The transducer assembly 606 is adapted to generate a source signal and receive a reflected signal. It may use a single transducer or multiple transducers. For example, at least a first transducer may be used to generate a signal and at least a second transducer may be used to receive the signal.
[0091] The transducer or transducers use may comprise a piezo-ceramic crystal. In the current invention, a single-crystal piezo (SCP) is preferred, but the invention does not exclude the use of other types of ferroelectric material such as poly-crystalline ceramic piezos, polymer piezos, or polymer composites. The substrate, typically made from piezoelectric single crystals (SCP) or ceramics such as PZT, PLZT, PMN, PMN-PT Also, the crystal may be a multi layer composite of a ceramic piezoelectric material. Piezoelectric polymers such as PVDF may also be used. The transducer or transducers used may be ceramic pieces coated with a conductive coating, such as gold. Other conductive coatings include sputtered metal, metals, or alloys, such as a member of the Platinum Group of the Periodic Table (Ru, Rh, Pd, Re, Os, Ir, and Pt) or gold. Titanium (Ti) is also especially suitable. For example, the transducer may befurther coated with a biocompatible layer such as Parylene or Parylene C. The transducer is then bonded on the lens. A coupling such as a biocompatible epoxy may be used to bond the transducer to the lens. The transducer assembly 606 communicates with an analyzing device 602 adapted to recognize the reflected signal or measure the Doppler shift between the signals. As mentioned above, the source signal may be reflected by changes in density between tissue. In such a case, the reflected signal will have the same frequency as the transmitted signal. When the source signal is reflected from blood moving within the vessel, the reflected signal has a different frequency than that of the source signal. This Doppler effect permits determination of the presence or absence of a blood vessel within tissue. Although depicted as being external to the device 600 , it is contemplated that the analyzing device 602 may alternatively be incorporated into the device 600 . The transducer assembly of the invention is intended to include any transducer assembly that allows for the observation of Doppler effect, e.g., ultrasound, light, sound etc. The device 600 illustrated in FIG. 6A includes a transducer assembly 606 comprising an ultrasound transducer 608 and an acoustic lens 610 that is adapted to refract and disperse a source signal over an outer surface of the lens 610 . The lens 610 is designed such that it interferes and redirects the signals in a desired direction. The lens 610 may be comprised of materials such as dimethyl pentene (plastic-TPX), aluminum, carbon aerogel, polycarbonate (e.g., lexan), polystyrene, etc. It also may be desirable to place an epoxy between the lens 610 and the transducer 608 . Preferably, the epoxy is thin and applied without air gaps or pockets. Also, the density/hardness of the epoxy should provide for transmission of the signal while minimizing any effect or change to the source signal. The configuration of the transducer assembly 606 permits the lens 610 to disperse a signal over a substantial portion of the outer surface of the lens 610 . The lens 610 also is adapted to refract a reflected signal towards the transducer 608 . Accordingly, given the above described configuration, the device 600 of FIG. 6A will be able to detect vessels with any part of the lens 610 that contacts tissue (as illustrated by the line 612 - 612 .) Although the lens 610 is illustrated as being hemispherical, as described below, the lens 610 may have other shapes as well.
[0092] [0092]FIG. 6B illustrates another variation of the device 614 having a hemispherical shaped ultrasound transducer 618 affixed to an end of a flexible elongate member 616 . The transducer 618 communicates with an analyzing device (not shown) to measure the Doppler effect to determine the location of a blood vessel.
[0093] [0093]FIG. 6C illustrates another variation of the device 620 including a transducer assembly 622 , at least a portion of which is located adjacent to a distal end of the elongate member 628 . The transducer assembly 622 includes a flat ultrasound transducer 626 , and a cone or wedge-like acoustic mirror 624 . The mirror 624 is adapted to reflect the signal over an area 360° around the device. The angle α of the mirror may be varied to optimally direct the signal as needed.
[0094] [0094]FIG. 6D illustrates a variation of a device 630 of the present invention further comprising a joint 632 to articulate an end of the device either to make sufficient contact with an area of tissue to be inspected for the presence of a blood vessel, or to navigate within the body to access the area to be inspected.
[0095] The variations of the invention described herein may also be adapted to use ultrasound energy, for example, high energy ultrasound, to produce openings in or marks on tissue. In such a case, the transducer assembly and acoustic lens also functions as a hole-making or site marking device. In this case, use of ultrasound in a low power operation permits the detection of a blood vessel and location of a site for a collateral channel. Using the same device and switching the operation of the device to a high power ultrasound permits the use of the ultrasound to create a collateral channel.
[0096] [0096]FIG. 6E illustrates a variation of a device 632 comprising a transducer assembly 634 connected to a flexible elongate member 636 . In this example, the transducer assembly 634 comprises a first transducer 641 , a second transducer 642 , and an acoustic lens 640 . As mentioned above, in variations using alternate transducers 641 , 642 , one transducer may transmit a signal while the other receives a signal. Also, both transducers 641 , 642 may simultaneously transmit and receive signals. It is intended that any combination of using the transducers to send and receive signals is contemplated. The device 632 also includes a hole-making assembly 638 for creating a channel in tissue. FIG. 6E illustrates the hole-making assembly 638 as an RF wire-like member. As illustrated, the device 632 is connected an RF generator 644 as well as an analyzing device 646 which is adapted to measure the Doppler shift between the generated and reflected signals.
[0097] [0097]FIG. 6F illustrates the device 632 of FIG. 6E where the hole-making assembly 638 is retracted within the device 632 , in this case within the elongated member 636 .
[0098] [0098]FIG. 6G illustrates another variation of a device 648 where a hole-making assembly 650 is exterior to a transducer assembly 606 . The hole-making assembly 650 may be either an RF device or a mechanical device that simply cuts the tissue. For example, the hole making assembly 650 can be a hypotube placed over the transducer assembly 606 . In this variation of the device 648 , the transducer assembly 606 may be moveable within the hole-making assembly 650 , or the hole-making assembly 650 may be moveable over the transducer assembly 606 . In either case, the transducer assembly 606 may be advanced out of the hole-making assembly 650 to determine the presence of a blood vessel. If no blood vessel is found, the transducer assembly 606 may be withdrawn into the hole-making assembly 650 allowing the hole-making assembly 650 to create a channel in the tissue either by mechanically cutting the tissue, or by using RF energy to create the channel. FIG. 6H illustrates a view taken along the line 6 H in FIG. 6G.
[0099] [0099]FIG. 6I illustrates another version of a device 652 of the present invention wherein the device has a transducer assembly 654 with an opening 658 through which a hole-making assembly 656 may extend. FIG. 6J illustrates the hole-making assembly 656 extended through the transducer assembly 654 . The hole-making assembly 656 may comprise RF electrodes or needle-like members which puncture the tissue to create the channels.
[0100] [0100]FIG. 6K illustrates a variation of a device 666 of the present invention where a tip 660 of the device has a conductive portion allowing the tip to serve as both an acoustic lens and an RF electrode. In such a case, the tip 660 is connected to an RF generator 644 for creating channels within tissue and a transducer 662 is placed in communication with an analyzing device 646 that is adapted to measure the Doppler shift between generated and reflected signals. In this variation, the tip 660 is separated from the transducer 662 , but both the tip 660 and transducer 662 are in acoustic communication through the use of a separation medium 664 . The separation medium 664 transmits signals between the tip 660 and the transducer 662 . The spacing of the transducer 662 from the tip 660 serves to prevent heat or RF energy from damaging the transducer 662 . It is intended that the spacing between the transducer 662 and tip 662 shown in the figures is for illustration purposes only. Accordingly, the spacing may vary as needed. The separation medium must have acceptable ultrasound transmission properties and may also serve to provide additional thermal insulation as well. For example, an epoxy may be used for the separation medium.
[0101] [0101]FIG. 6L illustrates a variation of a device 680 of the present invention wherein the transducer assembly 670 comprises a tip 672 , an ultrasound coupling medium 674 , a transducer 676 , and an extension member 678 . In this variation of the invention, the tip 672 of the device serves as an acoustic lens and also has conductive areas (not shown) which serve as RF electrodes. As shown in FIG. 6M, the tip 672 may extend from the device 680 and separate from the transducer 676 . Separation of the tip 672 protects the transducer 676 from heat or RF energy as the tip 672 creates a channel in tissue. The extension member 678 may serve as a conductor to connect the tip 672 to an RF energy supply (not shown). When the tip 672 of the device 680 is being used in an ultrasound mode, the tip 672 may be coupled to the transducer 676 via the use of an ultrasound coupling medium 674 . Any standard type of ultrasound gel material may be used, also highly formable silicone may be used. It is desirable to use a fluid boundary layer (such as the gel) which may be permanent or temporary. In those cases where the boundary layer is temporary, subsequent applications of the boundary layer may be necessary.
[0102] [0102]FIG. 6N illustrates another variation of a device 682 of the present invention having a tip 684 and transducer 686 that are separable from each other. Again, the tip 684 may include conductive areas and serve as both an RF electrode (not shown) as well as an acoustic lens. As shown in FIG. 6N, the tip 684 may be separable from the transducer 686 when creating a channel to protect the transducer 686 from heat or RF energy. The tip 684 may be placed in contact with the transducer 686 for operation in an ultrasound mode, or the device 682 may contain a separation medium 688 which permits acoustic coupling of the transducer 686 with the tip 684 when separated.
[0103] FIGS. 6 P- 6 U illustrate variations of RF electrode tip 690 configurations for use with the present invention. As illustrated, the electrodes may be placed around a circumference of a tip, longitudinal along a tip, spirally along a tip, or a combination thereof. The electrodes 692 , 694 may be used with a device having an acoustic lens or the electrodes may be employed solely as an RF hole-making device. While the variations illustrated in FIGS. 6 P- 6 U show bipolar RF devices, the invention may also use a single electrode (monopolar.) The tip 690 may contain a first electrode 692 separated from a second electrode 694 by an electrical insulator 696 (e.g., ceramic, or plastic insulator). In variations of the device where electrodes are positioned on an acoustic lens, a sufficient amount of surface area of the lens must remain uncovered so that sufficient coupling remains for transmission of a signal between the lens and tissue. FIG. 6V illustrates a co-axial variation of a bi-polar RF tip having a first electrode 692 , a second electrode 694 , and an insulator 696 .
[0104] [0104]FIGS. 6W and 6X illustrates additional variations of the lens of the present invention. FIG. 6W illustrates a device 724 with an acoustic lens 726 having an oblate spheroid shape. FIG. 6X illustrates a device 728 with an acoustic lens 730 having a prolate spheroid shape. FIG. 6Y illustrates a device 732 having a conical-shaped acoustic lens 734 . These variations are only intended to illustrate variations of the lens. It is contemplated that the shape of a lens may not follow a mathematical description such as conical, prolate, oblate or hemispherical. The design of the shape relates to the distribution pattern of the signal over the lens. The shapes can affect the distribution pattern by making it wider or narrower as needed. In any case, the lens is of a shape that provides coverage over the front face of the device.
[0105] [0105]FIG. 7A illustrates a variation of the invention where a device 700 includes a heat-sink member 702 . The heat-sink member 702 may preserve surround tissue during creation of the collateral channel. Or, the heat-sink member 702 may be a section of conductive material or a balloon. The heat-sink member 702 may be in fluid communication with a lumen 704 that provides a fluid, such as saline, that conducts heat away from the area surrounding the channel.
[0106] [0106]FIG. 7B illustrates another variation of a device 710 having a fluid delivery assembly 706 which assists in preserving surrounding tissue while a channel is being created. The fluid delivery assembly 706 may spray, mist, or otherwise apply fluid 708 to the area surrounding the channel. For example, cooled saline may be applied to the area to prevent excessive heating of the target area.
[0107] The invention includes the use of hole-making assembly on the side of the device with a transducer assembly on the tip of the device. For example, FIG. 7C illustrates a variation of an RF electrode 712 for use with the present invention. The electrode 712 may be a protrusion extending from a conductive member 716 that is covered with an insulating material 714 . In this variation, the electrode 716 limits the depth of the channel due to the amount of material extending from the conductive member 716 . The conductive member 716 may be connected to a source of RF energy (not shown) or may use another heating element (not shown). FIG. 7D illustrates another variation of an electrode configuration. In this variation, the electrode comprises a spherical member 718 extending from an elongate member 722 . The electrode 718 is retractable through the elongate member 722 by use of an actuator 720 . The actuator 720 may be conductive and connected to a source of RF energy to conduct energy through the electrode 718 . Again, the design of the electrode 718 limits the depth of penetration of the electrode 718 while creating a channel in tissue. The electrodes described herein may also be used in conjunction with a device having a Doppler arrangement.
[0108] Also, a variation of the invention contemplates the delivery of drugs or medicines to the area of the collateral opening. Also contemplated is the use of a fibrin, cyano-acrylate, or any other bio-compatible adhesive to maintain the patency of the opening. For example, the adhesive could be deposited within the collateral channel to maintain patency of the channel or to create a cast implant of the channel. The adhesive could also coat the channel, or glue a flap to the wall of the airway. Also, the use of a bioabsorbable material may promote the growth of epithelium on the walls of the conduit. For example, covering the walls of a channel with small intestine submucosa, or other bioabsorbable material, may promote epithelium growth with the bioabsorbable material eventually being absorbed into the body.
[0109] [0109]FIG. 4 illustrates a variation of a device 400 having the ability to create multiple openings within the walls of the natural airway 100 . The holes may be created by dilation, cutting, electrical energy, microwave energy, ultrasonic energy, laser, chemical, or any process as mentioned above. This device 400 may also be used to deploy multiple probes to determine the location of a blood vessel (not shown) using one of the procedures mentioned above.
[0110] [0110]FIG. 5A illustrates an implant or conduit 500 placed within a natural airway 100 . As shown, the airway 100 has a portion of its wall removed, thereby providing a collateral opening 112 within the airway 100 . The implant 500 typically has a porous structure which allows gasses to pass between the airway and the channels 112 and into the lung. Moreover, the structure of the insert 500 also maintains patency of the airway 100 and the channel 112 .
[0111] Any variation of a conduit described herein may comprise a barrier layer which is impermeable to tissue. This aspect of the invention prevents tissue in-growth from occluding the channel. The barrier layer may extend between the ends of the body or the barrier layer may extend over a single portion or discrete portions of the body of the conduit.
[0112] [0112]FIG. 5B illustrates an conduit 500 having an expandable structure within an airway 100 . Usually, the conduit 500 has a porous wall that allows the passage of gasses through the wall. The conduit 500 is delivered via a delivery device 502 which may also contain an expandable member (not shown) which expands the conduit 500 . As shown in FIG. 5C, the conduit may have piercing members 504 attached on an outer surface which enable the conduit 500 to create an incision within the airway 100 .
[0113] [0113]FIG. 5C illustrates the conduit 500 after being expanded by an expandable member 506 , e.g. a balloon device, an expandable mechanical basket, or an expandable wedge. In this example, the conduit 500 expands through the walls of the airway 100 at sections 508 . In this variation, the conduit 500 is lodged within the walls of the airway 100 .
[0114] [0114]FIG. 5D illustrates a grommet-like insert 503 where the lumen of the insert 503 extends longitudinally through the collateral channel. In this example, an expanding member 501 , e.g., a balloon, an expanding mechanical basket, or the like is used to secure the conduit 503 within the collateral channel.
[0115] Although not illustrated, the invention includes conduits having a length to diameter ratio approximately 1:1. However, this ratio may be varied as required.
[0116] The cross-section of an implant may be circular, oval, rectangular, eliptical, or any other multi-faceted or curved shape as required. The cross-sectional area of an implant 500 may be between 0.196 mm 2 to 254 mm 2 .
[0117] The conduit may also be any device capable of maintaining a patent opening, e.g., a plug, that is temporarily used as a conduit and then removed after the channel has healed in an open position. In another variation the plug may be a solid plug without an opening that is either bio-absorbable or removable. In such a case, the plug may be placed within an opening in tissue and allow the tissue to heal forming a collateral channel with the plug being ultimately absorbed into the body or removed from the body.
[0118] Another variation of the conduit is illustrated in FIG. 5E. In this example the conduit 510 comprises a cone 514 with a grommet 512 for attachment to a wall of the airway 100 . The cone 514 may be porous or have other openings 516 to facilitate the passage of gas through the collateral channel. In the event that the distal opening of the cone become occluded, the porous cone permits the continued exchange of gasses between the collateral channel and the natural airway.
[0119] Another variation of the conduit is illustrated in FIG. 5F. For example, the conduit 518 may be configured in a ‘t-shape’ with a portion 520 of the conduit extending through the collateral channel. Again, the conduit 518 may be constructed to have a porous wall to allow gas exchange through the wall. The conduit may be configured in a variety of shapes so long as a portion of the conduit extends through the collateral channel. The portion may be formed into a particular shape, such as the ‘t-shape’ described above, or, the portion may be hinged so that it may be deployed within the channel. In such a case, a portion of a wall of the conduit may have a hinge allowing the wall of the conduit to swivel into a channel.
[0120] Yet another variation of the conduit is found in FIG. 5G. In this example, the conduit 522 is constructed with a geometry that reduces the chance that the conduit 522 will migrate within the airway 100 .
[0121] [0121]FIG. 5H illustrates an example of a conduit 524 having an asymmetrical profile. The conduit 524 may have a flange 526 at either or both ends of the body 528 . Although not shown, the flange 526 may have a cone-like profile to facilitate placement within an airway. As illustrated in FIG. 5J, the asymmetrical profile of the conduit 524 assists in preventing obstruction of the airway.
[0122] [0122]FIG. 5K illustrate a variation of the conduit 530 having a self-cleaning mechanism. In this example, the self cleaning mechanism is a floating ball bearing 532 . The ends of the conduit 530 have a reduced diameter 534 which prevents the bearing 532 from escaping. As gas passes through the conduit 530 , the bearing 532 moves about the conduit 530 clearing it of debris. The shape of the bearing 532 and the size and shape of the reduced diameter 534 may be varied to optimize the self-cleaning effect of the device.
[0123] [0123]FIGS. 5L and 5M illustrate another variations of a self-expanding conduit 536 . In this example, as shown in FIG. 5L, the conduit 536 may be constructed from a flat material 538 having a spring or springs 540 . As shown in FIG. 5M, the conduit 536 is formed by rolling the assembly. The spring 540 provides an expanding force against the material 538 . The conduit 536 may also be constructed so that the flat material 538 is resilient thus eliminating the need for springs 540 .
[0124] [0124]FIG. 5N illustrates another variation of an expandable conduit 542 constructed from a braided material. The conduit 542 may be constructed so that the diameter is dependent upon the length of the device 542 . For example, the diameter of the device 542 may decrease as the length is stretched, and the diameter may increase as the length of the device 542 is compressed. Such a construction being similar to a ‘finger cuff’ toy.
[0125] FIGS. 5 O- 5 Q illustrate another variation of a grommet-type conduit. FIG. 5O illustrates a conduit 544 having expandable ends 546 . In one variation the ends 546 of the device 544 may flare outwards as illustrated in FIG. 5P. FIG. 5O illustrates another variation of the device 544 in which the ends 546 compress in length to expand in diameter.
[0126] [0126]FIGS. 5R and 5S illustrate variations of a conduit having an anchor. In FIG. 5R, the conduit 548 has an anchor 550 at a distal end of a hollow plug 540 . The anchor 550 may be tapered to facilitate entry into the airway 100 wall or may have another design as required. The anchor 550 also contains ventilation openings 552 to facilitate gas exchange through the device. FIG. 5S illustrates another variation of the device.
[0127] [0127]FIG. 5T illustrates a variation of a conduit 561 having flanges 563 at either end to assist in placement of the conduit within an airway wall (not shown). The ends of the conduit 565 may be tapered to ease placement through a collateral channel. The conduit has an opening 565 to facilitate passage of air. To simplify construction, the conduit 561 may be constructed from a biocompatible material, such as stainless steel, or plastic.
[0128] [0128]FIG. 5U illustrates a variation of the invention having multiple openings for gas flow. The conduit 560 has a first hollow end 564 which can extend through a wall of the airway 100 and a second hollow end 566 which can remain parallel to the airway 100 . This example also includes an opening 562 which allows gas to flow through the airway 100 .
[0129] [0129]FIG. 5V illustrates a variation of the device having a one-way valve 570 . The valve 570 allows the conduit 568 to permit exhaust of the air sac but prevents the conduit 568 from serving as another entrance of gas to the air-sac. The valve 570 may be placed at ends of the conduit or within a lumen of the conduit. The valve 570 may also be used as bacterial in-flow protection for the lungs.
[0130] [0130]FIG. 5W illustrates another variation of a conduit 572 . In this variation, the conduit 572 may be a sponge material, or constructed of an open cell material 574 , which allows air flow through the material. Or, the conduit 572 may have lumens 576 which allow flow through the conduit 572 . To assist the conduit 572 in remaining within a channel, the conduit material may be selected such that it expands as it absorbs moisture. Also, the sponge material/open cell material may be bioabsorbable to allow for temporary placement of the conduit 572 .
[0131] FIGS. 8 A- 8 F illustrate another variation of a conduit 800 of the present invention. The conduit 800 has a center section 802 having extension members 804 located at either end of the center section 802 . The center section 802 illustrated is tubular but may be of any other shape as needed for the particular application. The conduit of the invention has a passageway extending between the ends of the conduit suited for the passage of air. The variation of the conduit 800 illustrated in FIG. 8A has a center section 802 comprising a mesh formed from a plurality of ribs 806 . FIGS. 8A and 8B illustrate the conduit 800 in a reduced profile while FIGS. 8C and 8D illustrate the conduit 800 in an expanded profile after expansion of the center section 802 of the conduit 800 . As shown in FIGS. 8E and 8F, each free end 808 of each extension member 804 is unattached to the center section 802 and is bendable about the respective end of the center section 802 to which it is attached. Accordingly, once a conduit 800 is placed within a collateral channel (not shown), the extension members 804 are bent about the end of the center section 802 and form a cuff or grommet which assists in keeping the conduit 800 within a collateral channel. Accordingly, the cross section and number of extension members 804 located about either end of the conduit 800 may be selected as necessary to assist in placement and securing of the conduit 800 within a channel.
[0132] The conduits described herein may have a fluid-tight covering, as discussed below, about the center section, the extension members, or the entire conduit. Also, the conduit may be designed to limit a length of the center section to less than twice the square root of a cross sectional area of the center section when the center section is in the expanded profile.
[0133] FIGS. 8 G- 8 I illustrates another variation of a conduit 812 for use with the invention. In this variation, the conduit 812 is formed from a rolled sheet of material 810 . The rolled sheet 810 may be heat treated to preserve the shape of the conduit 812 or the sheet 810 may simply be rolled to form the conduit 812 . In those cases where the sheet of material 810 comprises a shape-memory alloy, it is desirable to process the material 810 so that it exhibits super-elastic properties at or above body temperature.
[0134] [0134]FIG. 8G illustrates a variation of extension members 820 for use with a conduit (not shown) of the present invention. In this variation, the extension members 820 have an attachment 822 between adjacent extension members 820 . FIG. 8H illustrates the extension members 820 as the conduit (not shown) is expanded and the extension members 820 are bent on the conduit. The attachment 822 assists in preventing the extension members 820 from deviating from a preferred position. As illustrated in FIG. 8I, the conduit 826 may have cut or weakened sections 824 to facilitate expansion of the conduit 826 and bending of the extension members in a desired manner (as shown by the section of 828 ).
[0135] FIGS. 8 J- 8 K illustrate various additional cross sectional designs of conduits. FIG. 8J illustrates a possible conduit design 830 having extension members 834 attached to a center section 832 . FIGS. 8K and 8L illustrate additional variations of conduit designs. As illustrated in FIGS. 8K and 8L, the extension members 840 , 846 and center sections 838 , 844 are designed to form a diamond pattern upon expansion of the conduit FIG. 8K further illustrates a variation of an extension member 840 having an opening 841 to facilitate tissue in-growth and thereby secures placement of the conduit. FIG. 8M illustrates an expanded conduit 848 having the diamond pattern referred to above. The conduit 848 also contains a fluid-tight barrier 851 on the center section 850 of the conduit 848 . Although not illustrated, fluid-tight barrier may be placed throughout a conduit. Another feature of the variation of FIG. 8M is that the extension members have a diamond pattern construction, this construction assists in maintaining alignment of the extension members allowing for a preferred aligned expansion of the extension members.
[0136] FIGS. 8 N- 8 O illustrate another variation of a conduit 860 of the present invention. In this variation, the conduit design 854 may have extension members 856 at only one end of the conduit 860 . In this variation, the center section of the conduit may comprise a body portion 858 . The conduit 860 may have a covering about a portion of the conduit 860 . The covering may extend throughout the length of the conduit 860 or it may be limited to a portion of the conduit 860 . As illustrated in FIG. 8O, when expanded, the conduit 860 may form a reduced area 858 near the extension members 856 . As mentioned above, the conduit cross section 854 may be designed such that the a diamond pattern is formed upon expansion of the conduit 860 , as illustrated in FIG. 8O.
[0137] [0137]FIG. 8P illustrates a sheet of material 810 having extension members 814 extending from either end of the sheet 810 . Although the sheet 810 is illustrated to be solid, a conduit may be formed from a sheet having openings within the center section of the sheet. FIG. 8Q illustrates the conduit 812 where the rolled sheet 810 comprises a center section 818 of the conduit 812 and the extension members 814 from either end of the center section 818 . As illustrated in FIG. 8Q, the sheet 810 may be overlapped for a reduced profile and expanded into an expanded profile. FIG. 8R illustrates a free end 816 of each extension member 814 as having been bent away from a central axis of the conduit 812 . As with any variation of a conduit of the present invention, the extension members 814 of the conduit 812 may be bent away from a central axis of the conduit 812 up to 180° with respect to the central axis. As mentioned above, the cross section and number of extension members 814 located about either end of the conduit 810 may be selected as necessary to assist in placement and securing of the conduit 810 within a channel.
[0138] In those cases where the conduit 812 of FIG. 8Q comprises a non-shape memory alloy the conduit 812 will be actively mechanically expanded. In those cases where the conduit 812 is comprised of a shape memory alloy, such as a super-elastic alloy, the conduit 812 may be pre-formed to assume a deployed shape which includes a grommet formed by extension members 814 and an expanded center section 818 , such as the shape illustrated in FIG. 8R. Next, the super-elastic conduit 812 may be restrained or even rolled into the shape illustrated in FIG. 8Q. Because the conduit 812 is formed of a super-elastic material, no plastic deformation occurs. When the super-elastic conduit 812 is then placed within a collateral channel, the conduit 812 may naturally resume its pre-formed, deployed shape.
[0139] [0139]FIG. 8S illustrates another variation of a conduit 862 having a first portion 864 and a second portion 866 and a passageway 868 extending therethrough. The first portion 864 may be a conduit design as described herein. In particular, the first portion 864 is configured to secure the conduit 862 to the airway wall 100 . Accordingly, the first portion 864 may or may not have a center that is expandable. The walls of the first portion 864 may be fluid-tight (either through design, or a fluid tight covering) to prevent tissue in-growth through the collateral channel. Alternatively, the first portion 864 may be partially fluid-tight to facilitate tissue in-growth to improve retention of the conduit 862 to the airway wall 100 . However, in the latter case, the first portion 864 should be designed to minimize tissue in-growth within the channel to prevent substantial interference with airflow through the conduit 864 . As with the first portion 864 , the walls of the second portion 866 of the conduit may or may not be fluid-tight. If the second portion 866 is not fluid-tight, the larger area provides for improved airflow from lung tissue through the passageway 868 and into the airway. The second portion 866 may also be designed to be partially fluid-tight to encourage airflow through the conduit 862 but reduce the probability of blockage of the conduit 862 .
[0140] FIGS. 8 T- 8 U illustrate another variation of a conduit 870 . For example, the conduit 870 may be formed from a tube that is slit to form extension members at a first portion 872 and second portion 876 with a center section 874 between the portions. The conduit 870 may be expanded as shown in FIG. 8U such that the first 872 and second 876 portions maintain the center portion 874 in a collateral channel in an airway wall. The center section 874 may or may not be expandable.
[0141] [0141]FIG. 8U illustrates the second portion 876 of the conduit 870 to expand in its center, however, the conduit 870 may be designed in other configuration as well (e.g., expanded to have a larger diameter at an end opposite to the center section 874 .) However, a central aspect of this design is that the second portion 870 provides a large area in the lung tissue to permit a larger volume of air to pass from the lung tissue into the conduit 870 . This design has an added benefit as the second portion 876 cannot be easily blocked by flaps of parenchyma tissue. A simple variation of the conduit 870 may be constructed from a metal tube, such as 316 stainless steel, titanium, titanium alloy, nitinol, etc. Alternatively, the conduit may be formed from a rigid or elastomeric material.
[0142] The conduits described herein may be comprised of a metallic material (e.g., stainless steel), a shape memory alloy, a super-elastic alloy (e.g., a NiTi alloy), a shape memory polymer, a polymeric material or a combination thereof. The conduit may be designed such that its natural state is an expanded state and it is restrained into a reduced profile, or, the conduit may be expanded into its expanded state by a variety of devices (e.g., a balloon catheter.) The conduit described herein may be manufactured by a variety of manufacturing processes including but not limited to laser cutting, chemical etching, punching, stamping, etc.
[0143] The conduits described herein may be coated with an elastomer, e.g., silicone, polyurethane, etc. The coatings may be applied, for example, by either dip coating, molding, or liquid injection molding (for silicone). Or, the coating may be a tube of a material and the tube is placed either over and/or within the conduit. The coating(s) may then be bonded, crimp, heated, melted, or shrink fit. The coatings may also placed on the conduit by either solvent swelling applications or by an extrusion process. Also, a coating of may be applied by either wrapping a sheet of PTFE about and/or within the conduit, or by placing a tube about and/or within the conduit and securing the tubes.
[0144] As mentioned above, the number of and cross sectional area of the extension members on a conduit may be selected as needed for the particular application. Also, the extension members may be bent such that they anchor into the tissue thereby securing placement of the conduit. Or, the extension members or the center section may contain barbs or other similar configurations to better adhere to the tissue. Moreover, the orientation of the extension members may vary as well. For example, the extension members may be configured to be radially expanding from the center section, or they may be angled with respect to a central axis of the conduit. Another variation of the invention includes a radioactive conduit which inhibits or prevents the growth of tissue within the conduit.
[0145] Although the conduits of the current invention have been described to contain expandable center sections, the invention is not necessarily limited as such. Instead, the design of the conduit may require extension members on the ends of a conduit with a non-expandable center section.
[0146] FIGS. 9 A- 9 D illustrate a conduit 900 of the present invention. The deployment of the conduit 900 is intended to show an example of a possible means of deployment only. Accordingly, the inventive conduit may be delivered at an angle via an articulating or jointed device, the conduit may be delivered on a device that is adapted to locate and create the collateral channel, or the conduit may be delivered on a device having other features as needed for the particular application.
[0147] [0147]FIG. 9A illustrates the conduit 900 being delivered to a collateral channel in an airway wall 114 via a delivery device (e.g., a balloon catheter 902 .) The conduit 900 may be attached to the delivery device 902 using the natural resiliency of the conduit 900 . Or, in those cases where the conduit is spring loaded, the conduit 900 restrained in a reduced profile and may be removably affixed to the delivery device 902 using an adhesive, or a removable sleeve such as a heat shrink tube. In this example, the balloon catheter 902 has several balloons including a distal balloon 904 , a proximal balloon 906 , and a center balloon (not illustrated in FIG. 9A). FIG. 9B illustrates the inflation of the distal 904 and proximal 906 balloons to situate the extension members 908 . Accordingly, the extension members 908 for a flange or collet about the airway wall 114 . The balloons 904 , 906 may be inflated simultaneously, or in a desired sequence. In any case, deployment of the balloons 904 , 906 may serve to center the conduit 900 in the collateral channel.
[0148] [0148]FIG. 9C illustrates inflation of the center balloon 912 which causes expansion of the center section 910 of the conduit 900 . If the conduit 900 is affixed to the delivery device 902 , expansion of the center balloon 912 causes release of the conduit 900 by release of the adhesive or breaking of the heat shrink tubing (not shown). In any case, the means of attachment may be bioabsorbable and remain in the body, or may remain affixed to the delivery device 902 and is removed with removal of the delivery device 902 . FIG. 9D illustrates the conduit 900 affixed to the airway wall 114 after the delivery device 902 is removed from the site. Another method of deploying a conduit includes restraining the conduit about a delivery device using a wire or string tied in a slip-knot or a series of slip-knots. When the conduit is delivered to a desired location, the proximal end of the wire or string may be pulled which releases the wire/string and deploys the conduit. FIGS. 9E and 9F illustrate possible ways to manipulate a conduit 914 for placement in an airway wall 114 using a delivery device 916 . FIG. 9E illustrates deployment of a delivery device 916 to place a conduit 914 within an opening in an airway wall 114 . The conduit 914 may be placed over a balloon 918 (or other expandable section) of the delivery device 916 . FIG. 9F illustrates deployment of the balloon 918 to place and expand the conduit 914 . In the variation illustrated in FIGS. 9E and 9F, a balloon 918 serves several functions. The balloon 918 first expands and starts bending the extension members 920 . The balloon 918 continues to center the conduit 914 on the tissue and simultaneously begins to expand the conduit 914 and secures the conduit to the tissue.
[0149] [0149]FIGS. 9G and 9H illustrate additional variations of deployment devices. In these variations, the deployment devices 922 , 926 contain hourglass-shaped balloons 924 , 928 . The hour glass-shaped balloons 924 , 928 contain an interior profile 923 . For deployment of a conduit (not shown) of the present invention, the conduit is placed on the balloon 924 , 928 . As the balloon 924 , 928 expands, the conduit expansion matches the interior profile 923 of the balloon 924 , 928 . Accordingly, the hour glass-shaped balloon 924 , 928 may be used to set the angle and orientation of the expandable members of a conduit as well as the expansion of a center section of the conduit.
[0150] [0150]FIG. 9I illustrates another variation of an hour glass shaped balloon delivery device 930 . This variation of the hour glass shaped balloon 932 is designed to expand extension members (not shown) of a conduit (not shown) at a particular angle 934 . The orientation of the balloon 932 may be designed as needed to impart the desired angle to the extension members of the conduit The balloons described herein may be constructed polyethylene terephthalate (PET) or any other material which is used in the construction of balloon catheters.
[0151] The invention further includes methods of evaluating individuals having a diseased lung to assess inclusion of the individual for the procedure.
[0152] The method comprises the steps of performing pulmonary function tests on the individual. The pulmonary function tests may obtain such values as FEV (forced expiratory volume), FVC (forced vital capacity), FEF 25%-78% (forced expiratory flow rate), PEFR (peak expiratory flow rate), FRC (functional residual capacity), RV (residual volume), TLC (total lung capacity), and/or flow/volume loops.
[0153] FEV measures the volume of air exhaled over a pre-determined period of time by a forced expiration immediately after a full inspiration. FVC measures the total volume of air exhaled immediately after a full inspiration. FEF 25%-75% measures the rate of air flow during a forced expiration divided by the time in seconds for the middle half of expired volume. PEFR measures the maximum flow rate during a forced exhale starting from full inspiration. FRC is the volume of air remaining in the lungs after a full expiration. RV is the FRC minus the expiratory reserve volume. TLC is the total volume in the lungs at the end of a full inspiration. Flow/volume loops are graphical presentations of the percent of total volume expired (on the independent axis) versus the flow rate during a forced expiratory maneuver.
[0154] The invention further comprises methods to determine the completion of the procedure. This variation of the invention comprises the step of performing pulmonary function tests as described above, creating collateral channels in the lungs, performing a post-procedure pulmonary function test, obtaining clinical information, comparing the results of the tests, evaluating the clinical information with the results of the test to determine the effectiveness of the procedure.
[0155] Another method to determine the completion of the procedure includes checking the resistance of airflow upstream from a location of a collateral channel. The method includes making a collateral channel, checking airflow, measuring resistance to airflow, and repeating the procedure until acceptable resistance is obtained. Because the collateral channel allows for the release of trapped air, the resistance to airflow should decrease. A body plethysmograph or other suitable equipment used to measure in pulmonary medicine may be used to determine the resistance to airflow.
[0156] A measurement of total lung volume may be used to determine when the lung is suitably deflated and therefore when enough collateral channels are created. Or, non-invasive imaging may be used to determine pre and post procedure lung volume or diaphragm position.
[0157] An evaluation of the effectiveness of the procedure may also include creating a collateral channel then sealing the channel with a balloon catheter. The distal end of catheter is then opened for a measurement of the flow of trapped air through the catheter.
[0158] This variation of the invention includes obtaining clinical information regarding the quality of life of the individual before and after any procedures, physical testing of the pulmonary system of the individual, and a general screening for pulmonary condition.
[0159] The invention herein is described by examples and a desired way of practicing the invention is described. However, the invention as claimed herein is not limited to that specific description in any manner. Equivalence to the description as hereinafter claimed is considered to be within the scope of protection of this patent.
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The devices and methods disclosed herein are directed to altering gaseous flow within a lung to improve the expiration cycle of, for instance, an individual having Chronic Obstructive Pulmonary Disease. More particularly, these devices and methods produce and to maintain collateral openings or channels through the airway wall so that expired air is able to pass directly out of the lung tissue to facilitate both the exchange of oxygen ultimately into the blood and/or to decompress hyper-inflated lungs. The devices and methods also disclose locating and selecting a site for creation of a collateral opening.
FIELD OF THE INVENTION
The invention is directed to methods and devices to altering gaseous flow within a lung to improve the expiration cycle of an individual, particularly individuals having Chronic Obstructive Pulmonary Disease (COPD). More particularly, methods and devices are disclosed to produce and to maintain collateral openings or channels th rough the airway wall so that expired air is able to pass directly out of the lung tissue to facilitate both the exchange of oxygen ultimately into the blood and/or to decompress hyper-inflated lungs.
BACKGROUND OF THE INVENTION
The term “Chronic Obstructive Pulmonary Disease” (COPD) is generally used to describe the disorders of emphysema and chronic bronchitis. Previously, COPD was also known as Chronic Obstructive Lung Disease (COLD), Chronic Airflow Obstruction (CAO), or Chronic Airflow Limitation (CAL). Some also consider certain types of asthma to fall under the definition of COPD. Emphysema is characterized by an enlargement of air spaces inside the lung. Hence, Emphysema is an anatomic definition and it can only be presumed in a living patient. Chronic bronchitis is characterized by excessive mucus production in the bronchial tree. Chronic bronchitis is a clinical definition and denotes those individuals who meet criteria defining the disease. It is not uncommon for an individual to suffer from both disorders.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to controls employing switch pads generally and, more particularly, but not by way of limitation, to a novel switch pad that includes an integrated squeak and rattle eliminator.
2. Background Art
Automobile controls often use an information display that requires a lens to be assembled in front of that display. Typically, the lens is secured to a relatively hard, component part either by a molded in snap feature or by a secondary operation requiring heat staking, ultrasonic welding, or an applied adhesive. The problems that can occur with these approaches are as follows: (1) snaps can break during assembly or relax under heat load, resulting in a squeak or rattle caused by rubbing of the lens against the component part; (2) heat staking or ultrasonic welding depends on set-up consistency which may not be repeatable, also resulting in a squeak or rattle; and (3) applied adhesive can be inconsistent and cause unsightly seepage into a visible or "show" area.
Accordingly, it is a principal object of the present invention to provide a squeak and rattle eliminator for an automobile display that is reliable.
A further object of the invention is to provide such a squeak and rattle eliminator that is simple and does not cause unsightly seepage.
An additional object of the invention is to provide such a squeak and rattle eliminator and method of manufacture in which the squeak and rattle eliminator is an integral part of a switch pad.
It is another object of the invention to provide such a squeak and rattle eliminator and method of manufacture that require no tooling in addition to that required to produce a switch pad.
Other objects of the present invention, as well as particular features, elements, and advantages thereof, will be elucidated in, or be apparent from, the following description and the accompanying drawing figures.
SUMMARY OF THE INVENTION
The present invention achieves the above objects, among others, by providing, in a preferred embodiment, a control assembly, comprising: a housing; a control element assembly disposed in said housing; a pushbutton assembly disposed in said housing; a switch pad disposed between said control element assembly and said pushbutton assembly; a faceplate covering an end of said housing; a display lens disposed between said switch pad and said faceplate and having a front surface thereof adjacent a rear surface of a flange surrounding an opening defined through said faceplate to permit viewing through said display lens of an information display in said housing; and a gasket disposed between said front surface of said display lens and said rear surface of said flange to prevent squeaking and rattling caused by mechanical interaction of said display lens and said faceplate.
BRIEF DESCRIPTION OF THE DRAWING
Understanding of the present invention and the various aspects thereof will be facilitated by reference to the accompanying drawing figures, provided for purposes of illustration only and not intended to define the scope of the invention, on which:
FIG. 1 is an isometric front view of one conventional method of attaching a lens to a panel.
FIG. 2 is an isometric rear view of another conventional method of attaching a lens to a panel.
FIG. 3 is an isometric front view of an additional conventional method of attaching a lens to a panel.
FIG. 4 is an isometric front view of a further conventional method of attaching a lens to a panel.
FIG. 5 is an isometric view of a switch pad according to the present invention.
FIG. 6 is an exploded isometric view of a control assembly employing the present invention.
FIGS. 7 and 8 are isometric views of alternative methods of using the present invention.
FIG. 9 is a fragmentary, side elevational, cross-sectional view of a lens mounted according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference should now be made to the drawing figures on which similar or identical elements are given consistent identifying numerals throughout the various figures thereof, and on which parenthetical references to figure numbers direct the reader to the view(s) on which the element(s) being described is (are) best seen, although the element(s) may be seen on other figures also.
FIG. 1 illustrates one conventional method of attaching a lens 20 to a trim panel 22 which surrounds an opening 24 defined in the trim panel, through which opening will be visible some sort of information display (not shown). It may be assumed that trim panel is or will be installed in a vehicle dashboard, for example, although the lenses and trim panels described herein may be employed in other applications as well. In this case, lens 20, which is typically clear or translucent plastic, has a plurality of snaps, as at 30, integrally molded with the lens. Lens 20 is secured to trim panel 22 by means of inserting the plurality of snaps 30 into a corresponding plurality of complementary openings, as at 32, defined through the trim panel and arrayed along opposite sides of opening 24, with the snaps being plastically deformed as they are inserted in the openings. As noted above, problems with this type of arrangement are that one or more snaps 30 may break during insertion and later exposure to a heat load, for example from the display, may cause the snaps to relax and create a squeak and/or rattle as lens 20 moves relative to trim panel 22.
FIG. 2 illustrates another conventional method of attaching a lens 40 to cover an opening 42 defined in a trim panel plate 44. Here, a plurality of stake posts, as at 46, similar to snaps 30 (FIG. 1), are inserted through clearance holes, as at 48, defined through trim plate 44. This method suffers from the same problems as does the use of snaps 30 described above with reference to FIG. 1.
FIG. 3 illustrates an additional conventional method of attaching a lens 50 to cover an opening 52 defined in a trim panel 54. Here, lines of adhesive 56 are applied to lens 50 above and below the area of the lens which will be visible through opening 52 and then the lens is pressed to the rear surface of trim panel 54. As noted above, this method can suffer from inconsistent application of the adhesive and there may be unsightly seepage of the adhesive.
FIG. 4 illustrates a further conventional method of attaching a lens 60 to cover an opening 62 defined in a trim panel 64. Here, lens 60 is placed against the rear surface of trim panel 64 and then ultrasonically welded to the trim panel along lines 66 similar to lines of adhesive 56 (FIG. 3). As noted above, this method requires additional manufacturing equipment and an additional manufacturing step.
FIG. 5 illustrates a switch pad, constructed according to the present invention, and generally indicated by the reference numeral 100. Switch pad 100 is formed of a resilient material such as rubber and, as is described more fully below, is disposed as a gasketing member between a push button assembly and a printed circuit board in a dashboard control panel, for example.
Continuing to refer to FIG. 5, switch pad 100 includes integrally molded therein a plurality of chimneys or surrounds, as at 110, for LEDs or lamps (none shown); a plurality of openings, as at 114, for lamps (none shown); a rectangular central opening 116 for a display lens (not shown on FIG. 5); and four pads, as at 118, disposed at each corner of rectangular central opening 116. The elements of switch pad 100 described so far are conventional and the particular arrangement thereof is shown for illustrative purposes only. Switch pad 100 further includes integrally molded therewith a display lens gasket 120. It will be seen that, as molded, display lens gasket 120 is attached to switch pad 100 by means of four integrally molded segments, as at 122.
FIG. 6 illustrates a control assembly in which the present invention may be employed, the control assembly being indicated generally by the reference numeral 130, which may be assumed to be, for illustrative purposes only, a control assembly for mounting in the dashboard of a vehicle (not shown). Control assembly 130 includes, in positions of assembly, a case 140, a circuit board assembly 142 containing control elements of the control assembly, switch pad 100 (shown as molded), a display lens 144, a pushbutton assembly 146, and a faceplate 148.
When control assembly 130 is assembled, display lens 144 will cover a display 150 on circuit board assembly 142, with the distal ends of the four legs, as at 152, of the display lens engaging the four pads 118 on switch pad 100 (FIG. 5). The front of display lens 144 will fit against a flange 160 formed around an opening 162 defined through faceplate 148. The function of gasket 120 in switch pad 100 (FIG. 5) as a squeak and rattle eliminator will now be discussed.
FIG. 7 illustrates one method of using gasket 120 of switch pad 100 as a squeak and rattle eliminator by providing a cushion between the front of display lens 144 and the rear surface of flange 160 on faceplate 148. Here, during the assembly operation, gasket 120 has been separated from switch pad 100 by severing segments 122 (FIG. 5) which, if made thin enough, can simply be manually broken. Then, gasket 120 is placed on a flange 170 formed around the edge of display lens 144 and the elements of control assembly 130 (FIG. 6) joined together.
FIG. 8 illustrates an alternative method of using gasket 120 of switch pad 100 as a squeak and rattle eliminator. Here, segments 122 have been made sufficiently robust that the segments may be stretched without the severing thereof so that gasket 120 may be stretched to place it in position on flange 170.
FIGS. 7 and 8 also illustrate more clearly the engagement of the distal ends of legs 152 of display lens 144 and pads 118 on switch pad 100, which engagement is the same regardless of which method of using gasket 120 is employed.
FIG. 9 illustrates a portion of assembled control assembly 130 (FIG. 6) which includes display lens 144 inserted through opening 162 in faceplate 148, with gasket 120 disposed between flange 160 on the faceplate and flange 170 on the display lens. So arranged, any possibility of squeaking or rattling of display lens 144 caused by mechanical interaction of the display lens and surrounding elements is eliminated by the cushioning provided by gasket 120. Either of the methods shown on FIGS. 7 and 8 may be used to provide the required cushioning.
An important feature of the present invention is that gasket 120 is incorporated into switch pad 100 which is an existing part, as it is molded and, therefore, no separate manufacturing step is required and no special equipment such as an ultrasonic welder or heat staker is required.
Switch pad 100 with integral gasket 120 is preferably molded of rubber using conventional techniques known in the art. Rubber offers the capability of molding a single part with varying degrees of hardness and color. For example, white may be required for light reflection at lamp clearance holes on switch pad 100, while black may be required for gasket 120. More or less robust rubber material may be employed for segments 122 depending on whether gasket 120 will be used in the manner indicated on FIG. 7 or in the manner indicated on FIG. 8. The various colors, as well as varying hardness, can easily be molded into switch pad 100 using conventional manufacturing techniques.
In the embodiments of the present invention described above, it will be recognized that individual elements and/or features thereof are not necessarily limited to a particular embodiment but, where applicable, are interchangeable and can be used in any selected embodiment even though such may not be specifically shown.
Terms such as "upper", "lower", "inner", "outer", "inwardly", "outwardly", and the like, when used herein, refer to the positions of the respective elements shown on the accompanying drawing figures and the present invention is not necessarily limited to such positions.
It will thus be seen that the objects set forth above, among those elucidated in, or made apparent from, the preceding description, are efficiently attained and, since certain changes may be made in the above construction without departing from the scope of the invention, it is intended that all matter contained in the above description or shown on the accompanying drawing figures shall be interpreted as illustrative only and not in a limiting sense.
It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.
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In a preferred embodiment, a control assembly, including: a housing; a control element assembly disposed in the housing; a pushbutton assembly disposed in the housing; a switch pad disposed between the control element assembly and the pushbutton assembly; a faceplate covering an end of the housing; a display lens disposed between the switch pad and the faceplate and having a front surface thereof adjacent a rear surface of a flange surrounding an opening defined through the faceplate to permit viewing through the display lens of an information display in the housing; and a gasket disposed between the front surface of the display lens and the rear surface of the flange to prevent squeaking and rattling caused by mechanical interaction of the display lens and the faceplate.
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CROSS REFERENCE TO RELATED APPLICATIONS
Applicants claim priority under 35 U.S.C. §119 of Spanish Application No. 200302428 filed Oct. 27, 2003.
OBJECT OF THE INVENTION
The present invention relates to a sterile feeding bottle which is manufactured in disposable plastic and/or rubber materials, resistant to heat, including that produced by microwaves, and which has the special feature of incorporating a solute and a solvent which are separate from each other but which can be mixed by simple and novel means which are incorporated in the feeding bottle, for the preparation of a compound, and without coming into contact with any of the components, or any of the elements of the feeding bottle itself, including the teat.
The object of the invention is to produce a feeding bottle that is used only once and which is simple, easy, quick and convenient to use, and which at any time and place and in any situation, can be used to prepare and administer a ready-made, sterile compound, without the need to carry the ingredients, components of this compound or feeding bottle, and without the need to have to sterilize them by any chemical or mechanical method, as required traditionally, and without any handling whatsoever, avoiding any possible contamination, all this being done in such a way that, once used, the feeding bottle is thrown away.
BACKGROUND OF THE INVENTION
Feeding bottles that are currently being commercialized and used for administering feed for babies, are not only not disposable, but they also have to be sterilized and subsequently handled during the different stages of preparation before being administered. This is true both in their use in the home and in teaching or health centres, which is obviously detrimental to the health of children as there is a reduced guarantee of sterility with excess handling in each case.
Although disposable feeding bottles are known, their commercialization is for the administration of saline solutions, medicines and other pharmacological substances.
In short, the conventional feeding bottles used for administering formula to unweaned or new-born babies are designed for administering feed which requires a considerable amount of preparation time, as well as numerous and complicated steps for their preparation (washing, sterilizing, measuring, mixing, etc.). And, therefore, in rushed situations, emergencies or where there is uncertainty of having the adequate means, if there is no kitchen available, etc., for example when staying in a hotel, a tent or away from home in general, preparing a feeding bottle can be a real problem.
The inconvenience of each and every one of the above steps mentioned for preparing a feeding bottle and the handling thereof, is worth mentioning here. In both homes and teaching centres, including hospitals, there is a continuous risk to guaranteed hygiene and sterility, which is so important for infants of under one year, and especially for new-born and unweaned babies.
DESCRIPTION OF THE INVENTION
The feeding bottle being the object of the invention has been designed to resolve the aforementioned problems, based on a simple but very effective solution, since it involves a feeding bottle which is used only once, which is sterile and which has a compartment housed inside the body of the feeding bottle, a compartment which contains a precise measure of the solute for mixing with the solvent, itself also precisely measured, and being contained in the body of the feeding bottle.
On top of the opening are two lids which are both sealed, positioned axially in such a way that when one of the lids is turned, the lower part of the compartment containing the solute is opened, thus enabling the solute to fall inside the body of the feeding bottle to mix with the solvent or other contents, while turning of the second lid produces an opening in the upper seal of the solute compartment, so that the inside thereof is opened to the teat, mounted on the upper end, through a neck which is positioned specifically in this upper part and onto which the teat is fitted, together with the upper lid.
In this way, the feeding bottle is prepared without the need for contact with any of the inner components, i.e. without having contact with either the solute or the solvent, or even with the teat, which is already covered with a sealed lid, and the opening of which enables the feeding bottle to be administered or given to the unweaned baby.
Obviously, when the solute is mixed with the solvent it must be shaken to make a uniform mixture, it being possible to heat the compound if necessary, the bottle being thrown away once administered.
The size of the bottle will be that of any other feeding bottle, being easy to store and carry, and long-lasting and, although the solute and solvent will have an expiry date, as long as they do not come into contact with each other, they will also last for an appropriate period of time.
In summary, the feeding bottle disclosed makes preparing a baby's bottle simple, convenient and hygienic, allowing the prepared feed to be administered to the baby without danger of contamination, since everything is sterilized and there has been no contact with any of the components, which have not been handled in any way.
Obviously, both the amount of solute and the amount of solvent will correspond with the exact, suitable doses and conditions to fully guarantee the hygiene required by babies and their feed.
In one variation of embodiment, the feeding bottle may include a second inner compartment, in the opposite end, which will obviously be the lower part of the body of the feeding bottle, to contain another solute for mixing with the earlier preparation, and the second compartment of which will also have a corresponding screw-on lid for the opening thereof.
DESCRIPTION OF THE DRAWINGS
To accompany the description provided and in order to provide a better understanding of the characteristics of the invention, in accordance with a preferred example of practical embodiment thereof, a set of drawings is attached as an integral part of said description, wherein the following is represented in a purely illustrative and non-limitative way:
FIG. 1 Shows a side elevational view of the feeding bottle being the object of the invention, wherein the screw-on lids can be seen in an axial position and, in the upper end, is the corresponding teat, covered or protected by a lid as shown by the broken line.
FIG. 2 Shows an exploded view of the feeding bottle in the previous figure.
FIG. 3 Shows a cross-section view of the upper part of the feeding bottle in FIG. 1 , wherein the compartment containing the solute and the two screw-on lids can be seen, as well as the neck through which the inside of the body of the feeding bottle and the teat, also shown in this figure, will be joined.
FIG. 4 Shows a side elevational view like that in FIG. 1 , but with the feeding bottle incorporating a second compartment for the solute in its lower part, with the corresponding screw-on lid.
FIG. 5 Shows an exploded view of the feeding bottle in the previous figure.
PREFERRED EMBODIMENT OF THE INVENTION
Looking at the figures provided, it can be seen how the feeding bottle of the invention is made up of a conventional cylindrical body ( 1 ), of a material suitable for resisting high temperatures, including the heat in a microwave. The body ( 1 ) of said feeding bottle houses, inside in its upper part, a compartment ( 2 ) containing a solute for mixing with a solvent contained in the body itself ( 1 ). This compartment or recipient ( 2 ) for the solute is situated on top of a neck ( 3 ) duly positioned on the inside of the mouth of the body ( 1 ) of the feeding bottle.
Two sealed lids ( 4 ) and ( 5 ) are fitted or mounted on top of this opening, together with a ring ( 6 ) with a cylindrical or bevelled portion of neck ( 7 ), the corresponding teat ( 8 ) being supported between the lid ( 4 ) and the circular body ( 6 ), the teat being protected by an upper lid which is also sealed ( 9 ), since both of said lids ( 4 ) and ( 5 ) are sealed at the outset.
The feeding bottle made up in this way, is supplied with the solute inside the recipient or compartment ( 2 ) and with the solvent inside the body ( 1 ) of the bottle, everything being duly sterilized from the time the feeding bottle is manufactured and is suitable for preparing the compound, which will obviously have expiry dates as the feeding bottle is to be used only once.
The feed is mixed first by screwing the lid ( 5 ) which opens the lower part ( 2 ) of the recipient or compartment ( 2 ), the solute falling onto the solvent contained in the body ( 1 ), a uniform mixture being produced simply by shaking.
Subsequently, and after screwing the lid ( 4 ), the upper seal ( 2 ″) is perforated and the inside of the body ( 1 ) containing the mixed compound is thus joined up with the teat ( 8 ) through the passage formed by the tube or neck ( 7 ).
In one variation of embodiment shown in FIG. 5 , it can be seen how the base of the neck of the feeding bottle ( 1 ) incorporates a lid ( 4 ′) which closes the corresponding opening, after which there is a second compartment or recipient ( 2 ′) identical to the aforementioned one, with the additional neck ( 3 ) positioned in the same way inside the body ( 1 ) of the feeding bottle, so that via this second compartment ( 2 ′) a second solute can be mixed with the earlier compound obtained with the solvent and the solute, the recipient or compartment ( 2 ′) being opened using the lid ( 4 ′), in the same way as the compartment ( 2 ) was opened using the lid ( 5 ) in the upper part or opening of the body of the feeding bottle ( 1 ).
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The present invention relates to a sterile feeding bottle which is manufactured in disposable plastic and/or rubber materials, resistant to heat, including that produced by microwaves, and which has the special feature of incorporating a solute and a solvent which are separate from each other but which can be mixed by simple and novel means which are incorporated in the feeding bottle, for the preparation of a compound, and without coming into contact with any of the components, or any of the elements of the feeding bottle itself, including the teat.
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RELATED APPLICATIONS
[0001] This application is a national phase application claiming benefit of priority under 35 U.S.C. §371 to Patent Convention Treaty (PCT) International Application Serial No: PCT/US2013/051415, filed Jul. 21, 2013, which claims benefit of priority to U.S. Provisional Patent Application Serial No. (“USSN”) 61/674,299, filed Jul. 21, 2012. The aforementioned applications are expressly incorporated herein by reference in their entirety and for all purposes.
TECHNICAL FIELD
[0002] This invention generally relates to inorganic chemistry and environmental pollution control. In particular, in alternative embodiments, the invention provides processes and methods for the recovery or the removal of metals, e.g., the so-called “Minor Elements” consisting of iron, aluminum and magnesium (expressed as oxides), from wet-process phosphoric acid using a continuous ion exchange approach. In alternative embodiments, processes and methods of the invention are used with a wet-process acid that is high in metal contaminants, e.g., the so-called “minor elements (ME)”. In alternative embodiments, use of processes and methods of the invention allows for the reduction of metal contaminants with minimal phosphate losses and dilution in order to produce a phosphoric acid that is suitable for the production of fertilizers and phosphoric acid products such as world-class diammonium phosphate fertilizer (DAP), merchant-grade phosphoric acid, superphosphoric acid, and other phosphoric acid products.
BACKGROUND
[0003] Phosphoric acid is a primary ingredient for the production of various phosphate products, including diammonium phosphate fertilizer (DAP); merchant-grade phosphoric acid (MGA); superphosphoric acid (SPA), and other various fertilizer and industrial-grade products. The phosphoric acid is made from the reaction of mined phosphate rock with sulfuric acid (H 2 SO 4 ), for the most part, to produce a phosphoric acid solution and a by-product gypsum material. Phosphoric acid can also be produced via the reaction of phosphate rock with other acids such as hydrochloric acid and nitric acid, but the majority of the production is with sulfuric acid.
[0004] Since the phosphate rock is a mined material, it generally contains a number of associated impurities. Typically the rock can contain levels of iron, aluminum, magnesium (the so-called “minor elements”), as well as limestone, excess silica, traces of uranium and rare earths, and appreciable levels of fluoride components. To some extent, many of these impurities dissolve into phosphoric acid during the reaction of the phosphate rock with the acid source.
[0005] Phosphate rock itself is quite variable depending on its source. Some rocks are quite low in associated impurities and in general do not required any extra levels of beneficiation to produce the desired end-products. Other rock sources can contain relatively high levels of impurities and in many cases these impurities can make it difficult, if not impossible, to produce specification products.
[0006] Further as various rock sources are mined the typical trend is to mine the highest quality material first, and then over time mine the lower grade ore. In some cases, even though there is phosphate rock still available at a mine, the contained impurities are too high, and the rock cannot be chemically processed using the conventional technologies, thus the low-grade ore becomes essentially valueless. This, in turn, results in less than full recovery of the potentially useable phosphate ore.
[0007] Since the presence of impurities, especially the so-called “minor elements”, can be detrimental to the phos-acid producer's ability to produce specification products, as well as diminish the potential phosphate rock that can be recovered from a given mine site, it would be desirable to have a method that can be used to reduce the dissolved impurities that are extracted into the acid and remove these impurities in such a manner that associated phosphoric acid losses are minimized and any phosphoric acid dilution is also held to a minimum. This would result in a significant increase in the quality of acid that could be produced by the phosphoric acid operation even with lower grade phosphate rock sources. Further, this would also greatly expand the potential phosphate rock reserve base for the phosphate mining operations and allow for better overall utilization of resources from a given developed mine site.
SUMMARY
[0008] The invention provides processes and methods for the recovery or the removal of metals, including the so-called “Minor Elements” consisting of iron, aluminum and magnesium, or their respective oxides, from a wet-process phosphoric acid using a continuous ion exchange approach. In alternative embodiments, processes and methods of the invention are used with a wet-process acid that is high in metal contaminants, e.g., iron, aluminum and magnesium, or their respective oxides—the so-called “minor elements (ME)”. In alternative embodiments, use of processes and methods of the invention allows for the reduction of metal contaminants, e.g., iron, aluminum and magnesium, or their respective oxides, with minimal phosphate losses and dilution in order to produce a phosphoric acid that is suitable for the production of fertilizers and phosphoric acid products such as world-class diammonium phosphate fertilizer (DAP), merchant-grade phosphoric acid, superphosphoric acid, and other phosphoric acid products.
[0009] In alternative embodiments, processes and methods of the invention are used to reduce the dissolved impurities that are extracted into the acid and remove these impurities in such a manner that associated phosphoric acid losses are minimized and any phosphoric acid dilution is also held to a minimum. This results in a significant increase in the quality of acid that can be produced by a phosphoric acid operation, particularly including use with lower grade phosphate rock sources.
[0010] In alternative embodiments, processes and methods of the invention allow for phosphate rock mining operations to increase the recovery of potentially useable rock from a given site by allowing for the processing of lower grade ore sources. This further enables the effective “expansion” of a phosphate rock resource without the need for development of additional mining area, by allowing the producer to stay on a developed site and utilize lower grade materials. Further this also allows for the development of lower grade mine sources that heretofore have been considered unusable. In many countries, practicing the processes and methods of the invention allow for enhanced phosphate rock production capabilities, and allow for continued phosphoric acid operations with lower grade domestic or regional ore, e.g., the case in Florida where the ore quality has steadily been declining over the decades.
[0011] In alternative embodiments, processes and methods of the invention allow for the removal of various impurities via the application of a continuous ion exchange approach. The impurities are removed from the phosphoric acid, via extraction onto a specific ion exchange resin. After loading, the resin is then subjected to various washing steps and subsequently contacted with an acid solution, e.g., a sulfuric acid solution where the impurities are removed from the resin and recovered as an impurity-sulfate solution. This solution can be disposed of, or depending on the composition may be suitable for further processing to recover a useable ME-superphosphate material or a useable ME-sulfate product, e.g. magnesium sulfate. Other acids can be used for regeneration of the resin, e.g. nitric acid or hydrochloric acid, but these would be limited to sites where these acids are used for the production of phosphoric acid. Most wet-process facilities use sulfuric acid, and these represent the vast majority of the sites where this exemplary technology could be practiced.
[0012] In alternative embodiments, the regenerated resin is then washed and returned to extraction service for additional impurity removal from the phosphoric acid. The continuous ion exchange approach allows for this process to be carried out effectively and in an economically attractive manner.
[0013] In alternative embodiments, the invention provides methods or processes++ for the removal of one or more minor element (ME) components, or a mixture of minor element components, or an impurity or a contaminant, from a wet-process phosphoric acid comprising use of a continuous ion exchange system, comprising:
[0014] (a) providing a phosphoric acid solution, or a solution comprising a phosphoric acid, or a phos-acid feedstock, comprising one or more minor element (ME) components, or a mixture of minor element components;
[0015] (b) providing a strong cationic exchange resin or equivalent material or composition capable of binding the minor element (ME) components, wherein the strong cationic resin is in the H+ form,
[0016] and optionally the strong cationic exchange resins or equivalent materials or compositions capable of binding the minor element (ME) components comprise:
a PUROLITE SST-60™ material, comprised of gel polystyrene crosslinked with divinylbenzene (DVB) and a sulfonic acid functional group (Purolite, Bala Cynwyd, Pa.), or equivalents; a PUROLITE C100™ resin, comprised of gel polystyrene crosslinked with divinylbenzene (DVB) and a sulfonic acid functional group (Purolite, Bala Cynwyd, Pa.), or equivalents; a DOWEX MSC 650™ material (Dow Chemical, Midland, Mich.), or equivalents; a resin, a composition or a material, or a non-resin solid or a semi-solid material, comprising chelating groups, functionalities or moieties that can bind ME components, and optionally that comprise a sulfonic acid functional group, iminodiacetic groups, chelating aminomethyl phosphonic acid groups or aminophosphonic groups, or similar chelating functionalities or moieties, wherein optionally the compositions comprise beads, wires, meshes, nanobeads, nanotubes, nanowires or other nano-structures, or hydrogels; (c) providing a regeneration solution comprising a strong acid,
[0022] wherein optionally the strong acid comprises a sulfuric acid (H 2 SO 4 ), a nitric acid (HNO3) or a hydrochloric acid (HCl), and optionally for the sulfuric acid the strength can be from about 5% to up to 98%, or can be in the range of about 20% to about 40%; and optionally with other acids the strength can vary from about 5% up to a concentrated level, or up to about 35%, 40%, 50%, 60%, 70%, 80%, 90% or 98%, or can be in the range of about 62% for nitric acid and about 37% for hydrochloric acid, or equivalent;
[0023] (d) applying the solution or phosphoric acid solution or phos-acid feedstock of (a) to the strong cation exchange resin under conditions such that the impurities, contaminants, or minor element (ME) components, remain on the cationic exchange resin,
[0024] wherein optionally an effluent is produced that is substantially free of impurities, contaminants, or minor element (ME) components, and substantially most of the impurities, contaminants, or minor element (ME) components remain bound to the strong cation exchange resin,
[0025] wherein optionally a phosphoric acid strength can range from about 12% to about 18% (e.g., as P 2 O 5 ) (the so-called “recycle acid strength”) to about 25% to about 30% P 2 O 5 (a normal filter acid strength), and optionally higher strength acids can be used or processed with ranges from about 42% P 2 O 5 up to about 54% P 2 O 5 ; and optionally about 12% to about 18% P 2 O 5 (a recycle acid strength) or about 25% to about 30% P 2 O 5 ) (a filter acid strength); and
(e) removing the impurities, contaminants, or minor element (ME) components, or eluting the impurities, contaminants, or minor element (ME) components, from the strong cation resin using the “regeneration” solution, resulting in (or thereby producing) a solution of the acid, or the sulfuric acid (H 2 SO 4 ), or equivalent, containing or comprising the impurities, contaminants, or minor element (ME) components as an eluate.
[0027] In alternative embodiments, the minor element components, or impurities or contaminants, comprise a cationic form of the minor element (ME) materials, or can comprise an iron (optionally as a Fe +2 or Fe +3 ), or an aluminum (optionally in the Al+ 3 form), or a magnesium (optionally as Mg +2 ), and optionally a cationic calcium (Ca +2 ) is also removed from the acid phase onto the resin.
[0028] In alternative embodiments, the phosphoric acid solution, solution comprising a phosphoric acid, or phos-acid feedstock, is first treated, or pre-treated, with a clarification process or a filtering process, or a clarification aid, wherein optionally the clarification process, filtering process or clarification aid comprises an activated clay, an activated carbon, an activated silica, or equivalents, or any combination thereof.
[0029] In alternative embodiments, the methods or processes of the invention further comprise treating the impurity-, contaminant- and minor element-containing effluent acid solution with a lime and/or a lime-limestone mixture to precipitate the contained (the eluted) minor elements as a hydroxide material; or, neutralizing the impurity-, contaminant- and minor element-containing effluent acid solution to precipitate the contained (the eluted) minor elements as a hydroxide material
[0030] In alternative embodiments, the methods or processes of the invention further comprise separating the precipitated material for disposal. In alternative embodiments, the methods or processes of the invention further comprise recycling the treated water phase.
[0031] In alternative embodiments, the methods or processes of the invention further comprise treating the minor element-containing effluent acid solution with a mixture of ground phosphate rock, or equivalent. In alternative embodiments, the treated ground phosphate rock or equivalent is used to produce a phosphate fertilizer product, optionally comprising a fast release P 2 O 5 ; a slow release P 2 O 5 ; secondary nutrients; and/or minor element nutrients, optionally with subsequent recycling of the water of the acid phase back to the extraction system.
[0032] In alternative embodiments, the methods or processes of the invention further comprise evaporating the regeneration solution to selectively crystallize the minor element fractions, wherein optionally the crystallizing results in (or produces) an ME-sulfate salt, and optionally subsequently recovering the ME-sulfate salt, optionally as a marketable secondary/minor element fertilizer material, and optionally recycling the concentrated sulfuric acid (H 2 SO 4 ) fraction to the primary extraction system.
[0033] In alternative embodiments, the strong cation resin is designed as a continuous ion exchange system operated to allow for the massive loading of one of the minor element components for recovery of a higher purity eluate, or product, wherein optionally the minor element component comprises a magnesium, and a higher purity magnesium sulfate product is recovered. In alternative embodiments, the strong cation resin is designed as a continuous ion exchange system operated by restricting the flow of the “regeneration” solution in order to preferentially load one of the minor element materials on the resin, or in the “regeneration” solution. In alternative embodiments, the strong cation resin is designed as a continuous ion exchange system having one or more of the zones, and the continuous ion exchange system is operated in an up-flow mode to allow for periodic resin bed expansion and flushing of any accumulated solids from the resin.
[0034] In alternative embodiments, the concentration of the strong acid, sulfuric acid, nitric acid or hydrochloric acid or equivalent in the “regeneration” solution is increased, optionally to concentrations in excess of about 40% for H 2 SO 4 ; optionally in excess of about 50% for nitric acid or in excess of about 30% for hydrochloric acid, and optionally the method or process operates at an elevated temperature, optionally in excess of about 140 degrees F., but less than about 190 degrees F., and optionally between about 145 degrees F. and about 160 degrees F., such that the resulting “spent”, or effluent, regeneration solution containing or comprising the impurities, or the ME eluate, upon cooling, minor elements (MEs) sulfates crystallize from the solution as a mixed ME-sulfate product, thus allowing for or producing a concentrated acid, or sulfuric acid (H 2 SO 4 ), for recycle.
[0035] In alternative embodiments, the invention provides industrial processes for the removal of one or more minor element components, or a mixture of minor element components, from a wet-process phosphoric acid comprising use of a continuous ion exchange system, comprising an industrial process as set forth in FIG. 1 , or any portion or sub-process thereof.
[0036] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
[0037] All publications, patents, patent applications cited herein are hereby expressly incorporated by reference for all purposes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] The drawings set forth herein are illustrative of embodiments of the invention and are not meant to limit the scope of the invention as encompassed by the claims.
[0039] Figures are described and discussed herein.
[0040] FIG. 1 schematically illustrates an exemplary process of the invention, an overall process flow diagram for an exemplary impurity reduction process of the invention, referred to as “the Minor Element Reduction (MER) process”. Also shown in FIG. 1 is two exemplary alternatives for the treatment of the regeneration solution from the continuation ion exchange (or “CIX”) regeneration stage.
[0041] Like reference symbols in the various drawings indicate like elements.
[0042] Reference will now be made in detail to various exemplary embodiments of the invention, examples of which are illustrated in the accompanying drawings. The following detailed description is provided to give the reader a better understanding of certain details of aspects and embodiments of the invention, and should not be interpreted as a limitation on the scope of the invention.
DETAILED DESCRIPTION
[0043] In alternative embodiments, the invention provides processes and methods for the recovery or the removal of iron, aluminum and magnesium (as cationic species) the so-called “Minor Elements”, from a wet-process phosphoric acid stream using a continuous ion exchange approach. In alternative embodiments, processes and methods of the invention allow for phosphate rock mining operations to increase the recovery of potentially useable ore or rock by allowing for the processing of lower grade ore or rock sources, thus enabling an effective “expansion” of the phosphate rock source without the need for development of additional mining area. Thus, the producer can stay on a developed site and utilize lower grade materials for a longer period of time.
[0044] In alternative embodiments, as illustrated in FIG. 1 , the exemplary Minor Element Reduction (MER) reduction process of the invention comprises pretreating a phos-acid (e.g., by filtering), or receiving a pretreated phos-acid, e.g., a filtered phos-acid (a nominal 26% P 2 O 5 ) (stream 1) from a main phos-acid plant, before its input into the continuous ion exchange system. The pretreatment can comprise, or the pretreatment can further comprise, the phos-acid being treated with a clarification aid (2) in order to reduce the suspended solids content in the acid stream. In alternative embodiments, this treatment can be modified according to specific needs, and results in the reduction of the suspended solids, along with some removal of the darker color to remove suspended solids from the acid phase, and to partially reduce longer-chain color body (organic) materials. The extent of pretreatment required is specific to each phosphoric acid source and will vary accordingly. In alternative embodiments, activated clay, e.g. calcium or sodium bentonite clays is suitable for this purpose.
[0045] In alternative embodiments, the underflow solids materials (3) recovered in this step can be filtered and disposed of to a gypsum pond, or alternatively returned to the phos-acid plant and combined with a filter feed slurry, e.g., a mixture of gypsum and phos-acid. In alternative embodiments, return of the solids to the phos-acid plant is preferred, if possible, in order to minimize P 2 O 5 losses and dilution of the phos-acid.
[0046] In alternative embodiments, the pretreated acid (4) is then processed in a continuous ion exchange (CIX) system, where it is contacted with a specific ion exchange resin, or equivalent material capable of binding the ME components, in a continuous fashion. In general a “strong acid” cation exchange resin or equivalent material is used.
[0047] Examples of such resins or equivalent materials include, and optionally the strong cationic exchange resins or equivalent materials or compositions capable of binding the minor element (ME) components comprise:
a PUROLITE SST-60™ material, comprised of gel polystyrene crosslinked with divinylbenzene (DVB) and a sulfonic acid functional group (Purolite, Bala Cynwyd, Pa.), or equivalents; a PUROLITE C-100™ resin, comprised of gel polystyrene crosslinked with divinylbenzene (DVB) and a sulfonic acid functional group (Purolite, Bala Cynwyd, Pa.), or equivalents; a DOWEX MSC 650™ material (Dow Chemical, Midland, Mich.), or equivalents; a resin, a composition or a material, or a non-resin solid or a semi-solid material, comprising chelating groups, functionalities or moieties that can bind ME components, and optionally that comprise a sulfonic acid functional group, iminodiacetic groups, chelating aminomethyl phosphoric acid groups or aminophosphonic groups, or similar chelating functionalities or moieties, wherein optionally the compositions comprise beads, wires, meshes, nanobeads, nanotubes, nanowires or other nano-structures, or hydrogels;
[0052] The primary requirement is that the resin or equivalent material be of the so-called “strong” cation form and be in the hydrogen (H+) form.
[0053] The minor element (ME) components, along with other cations, are removed from the acid and exchanged for an H+ ion that is on the resin, (which converts the ME-phosphate salt to phos-acid). In alternative embodiments, the treated acid (5) with lowered minor elements (ME) is then directed to a surge tank and returned to the phos-acid plant for normal downstream processing.
[0054] It is important to recognize that the ME-phosphate materials in the phos-acid are converted to the acid form. In this manner the P 2 O 5 that would normally remain in the ME-phosphate form (which has little ammoniation potential) is now converted to an acid form which can be readily ammoniated.
[0055] The general exchange mechanism involved in the ME removal stage is as follows:
[0000] 3R—H++ME-PO 4 →3R-ME+H 3 PO 4 ,
[0000] where R is the solid ion exchange resin: note that the “impurity” ME is converted to H 3 PO 4 which is the desired form for phosphate (P) in the acid stream.
[0056] In alternative embodiments, the ion exchange resin, now loaded with the ME and other cationic materials, is then water washed (6) in a continuous fashion. In alternative embodiments, the water flows are controlled to minimize overall P 2 O 5 dilution. The water can be obtained from recycled water originating in the spent regeneration solution treatment options (1 and 2). Make-up water can be provided via process water make-up from the phosphoric acid plant.
[0057] In alternative embodiments, the ME-loaded resin is then continuously regenerated with a solution of an acid, e.g., a sulfuric acid or an equivalent (7). In alternative embodiments, the H 2 SO 4 strength is in the 10% to 30% range, depending on the ultimate disposition of the spent ME-sulfate stream. Other acids can be used, depending on the acids that are used for the digestion of the phosphate rock at the wet-process phos-acid facility. In the case of other acids, the ME in the spent regeneration solution will be in the salt form of the acid used for regeneration. For example, with nitric acid the ME's in the spent regeneration solution will be in the nitrate form, i.e. magnesium nitrate, iron nitrate, etc. In alternative embodiments, exemplary processes that have the most attractive applicability for the phosphate operations are those that use sulfuric acid for digestion, thus, at least for these exemplary processes, the ME's would more than likely be in the sulfate form.
[0058] In alternative embodiments the acid that removes the ME and other cationic materials from the resin is sulfuric acid, and to produce a ME/cationic-sulfate eluate solution, i.e. the so called “Spent Regeneration Solution” (SRS), the hydrogen component (H+) from the acid is loaded back onto the resin to allow for resin reuse. In alternative embodiments the regenerated resin is again washed with water, and then returned to ME/cation removal service as the cycle is repeated.
[0059] In alternative embodiments, an exemplary cationic exchange mechanism involved in the resin regeneration stage is as follows:
[0000] R-ME+H 2 SO 4 →R—H++ME-SO 4
[0060] In alternative embodiments, equivalents to sulfuric acid (H 2 SO 4 ) are used to “regenerate” the cationic exchange resin, i.e., to elute the “contaminants”, metals and the like binding to the resin before elution with acid. Examples of these acids are nitric and hydrochloric.
[0061] The SRS ( 8 ) now contains the ME/cationic sulfate impurities along with residual free H 2 SO 4 . It is transferred to the ME-loaded regeneration solution treatment stage for further processing. The invention provides several exemplary options or alternatives for the treatment of this solution, depending on the specific characteristics of the solution and the location of the facility. In many cases it may be that the solution can be converted to a saleable product.
[0062] In the first exemplary option, Option 1, the regeneration solution is treated with a mixture of limestone and lime ( 9 ) and the ME-components are precipitated as insoluble salts ( 10 ). This solid material can then be removed from the aqueous phase, if desired, and the sludge disposed of to the existing gypsum stack system. The aqueous solution ( 10 ) resulting from the treatment step is reusable water and can be returned to the CIX system. This method allows for economic treatment of the solution and overall economic attractiveness for the MER process.
[0063] In the second exemplary option, Option 2, the loaded regeneration solution is mixed with ground phosphate rock ( 11 ), and the rock itself used as the treatment agent. After reaction, the rock material can be sold as a partially acidulated rock ( 12 ), or PAR product, and used as a modified superphosphate material. This product would be a low P 2 O 5 analysis material that would have both fast release (water soluble) as well as a slower release (low water solubility) P 2 O 5 fractions, and would also contain sulfate as well as the other minor elements, which in themselves are vital plant nutrients, for example, the so-called secondary and minor nutrients.
[0064] In alternative embodiments of the exemplary PAR Option 2, the regeneration of the resin is operated to produce a concentrated ME-sulfate solution, and the ME is eventually crystallized from the solution as ME slurry. The regenerated solution is heated to a level that is sufficiently high to allow for the minor element sulfates to stay in solution. The spent regeneration solution is cooled to allow for the crystallization of the ME-sulfate. The ME-sulfate would be removed and recovered, and the concentrated sulfuric acid returned to the continuous ion exchange system.
[0065] In an exemplary Option 3, if the amount of recovered ME is sufficient then there is the possibility of recovering specific marketable ME materials such as magnesium sulfate (MgSO 4 ) In some cases, these recovered ME-sulfates may have market value in their own right, thus the P 2 O 5 “impurity” can be converted to a useable co-product.
[0066] In FIG. 1 , the exemplary Option 3 alternative embodiment is shown for the case where a mixed ME-Sulfate product would be produced. The spent regeneration solution ( 8 ) would be sent to ME-Salt Recovery System and the solution concentrated to crystallize the ME-sulfate from the solution. In this case, the system would also be operated with a higher sulfuric acid solution, and at higher temperature in order to minimize the resulting water handling requirements. In alternative embodiments, the resulting crystallized ME-salt is dried then sold as a secondary/minor element product ( 13 ). The free sulfuric acid resulting from the crystallization ( 14 ) can be recycled to the so-called exemplary “CIX” extraction process of the invention.
[0067] A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.
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In alternative embodiments, the invention provides processes and methods for the recovery or the removal of the so-called “Minor Elements” consisting of iron, aluminum and magnesium (expressed as oxides), from wet-process phosphoric acid using a continuous ion exchange approach. In alternative embodiments, use of processes and methods of the invention allows for the reduction of these Minor Elements with minimal phosphate losses and dilution in order to produce a phosphoric acid that is suitable for the production of fertilizer products such as world-class diammonium phosphate (DAP), merchant-grade phosphoric acid, superphosphoric acid, and other phosphoric acid products. Further, use of the invention would allow the use of lower grade phosphate rock or ore, which would greatly expand the potential phosphate rock reserve base for phosphate mining activities, and allow for better overall utilization of resources from a given developed mine site.
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CROSS REFERENCE TO RELATED APPLICATIONS
The benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application Ser. No. 61/397,581 filed on Jun. 14, 2010 is hereby claimed, and U.S. Provisional Patent Application Ser. No. 61/397,581 is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to maintenance and janitorial equipment, and more particularly, to a bucket that may be moved from location to location and may store and transport warning signs (this is, “wet floor” signs) that indicate a floor is wet.
2. Brief Description of the Related Art
Equipment for holding and transporting cleaning items is commercially available. One example of a bucket having storage receptacles is shown in my U.S. Design patent 350,632 which was issued on Sep. 13, 1994. Cleaning supplies, such as for example, spray bottles, towels, brushes and sponges, as well as other cleaning items suited to the type of maintenance/cleaning to be performed, may be required to be carried from room to room, such as, in office complexes, hotels, schools and other buildings.
Often buckets are cumbersome to maneuver. Wheeled buckets have been constructed, but they generally are difficult to move when a quantity of water or cleaning solution is held in the bucket. In addition, the wheels may move over wet or treated surfaces (e.g., floors treated with cleaning solution) which may corrode the wheels or connectors attaching the wheels. After several uses, the traditional wheeled buckets may become very difficult to maneuver.
Another drawback with buckets is that the buckets must be moved with cleaning supplies and equipment, such as wet floor signs, mops, and other items. Generally, the items are carried as the bucket is pulled or pushed with a mop. However, often, supplies like wet floor signs may be misplaced between uses.
A need exists for an improved bucket device which is easy to maneuver and may be used to store and transport items, such as wet floor signs.
SUMMARY OF THE INVENTION
A bucket is provided having a storage component for storing items, in particular for storing wet floor signs. According to a preferred embodiment, the bucket is configured with one or more storage components provided on the exterior, so that the bucket may be used to contain water or other cleaning fluid.
A handle preferably is provided to facilitate repositioning the bucket when the bucket is in use.
According to preferred embodiments a mop wringer may be provided on the bucket to facilitate use of the bucket with floor mopping operations.
According to preferred embodiments, the bucket further provides specially configured construction for facilitating movement of the bucket, even when filled with water or cleaning solution. Preferred embodiments include wheels for moving the bucket and signage that may be held thereon.
Preferably, the bucket has a triangular configuration that defines a triangular interior volume. According to a preferred configuration, two side walls are provided and connect with a rear wall, and the walls are connected to a floor (e.g., a bottom wall) to form an enclosure.
A preferred construction of the bucket is designed for use in connection with floor cleaning applications, in particular, mopping.
The bucket is configured to provide holding and storage for signage, such as wet floor signs that are displayed after a floor has been cleaned.
The bucket may be used in connection with floor cleaning and preferably has storage or holding components that may be configured to hold and store signs, so that the signs may be held in a single place, generally with the bucket. The bucket also is constructed so that the signs, as well as the bucket and its contents, may be easily moved from place to place.
It is a common practice to place wet floor signs at locations where mopping or cleaning has been done so that those approaching the wet floor are warned of the potential danger of slippage. This practice is used especially when cleaning floors of a building, such as common areas of apartments, schools or offices. According to preferred embodiments, the present device is designed with one or more designated holders configured to hold one or more wet floor signs so that the signs may be readily transported to the cleaning location where they are used, and when the signs are not in use, they may be readily stored on the bucket, which guards against the signs being misplaced and/or lost when not in use.
These and other advantages are provided by my invention.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
FIG. 1 is a view in perspective of a first embodiment of the bucket of the invention.
FIG. 2 is a left side view of the bucket of the invention shown in FIG. 1 .
FIG. 2 a is a left side of the bucket of FIG. 1 , in which a wet floor warning sign 100 is held in each compartment 22 of the second side wall 13 .
FIG. 3 is a right side view of the bucket of the invention shown in FIG. 1 .
FIG. 3 a is a right side view of the bucket of the invention shown in FIG. 1 , in which a mop wringer (shown schematically) has been positioned on the bucket of the invention.
FIG. 4 is a view in top plan of the bucket of the invention shown in FIG. 1 .
FIG. 5 is a back view of the bucket of the invention shown in FIG. 1 .
FIG. 6 is a front view of the bucket of the invention shown in FIG. 1 .
FIG. 7 is a view in bottom plan of the bucket of the invention shown in FIG. 1 .
FIG. 8 is a view in perspective of an alternative embodiment of the bucket of the invention.
FIG. 9 is a left side view of the bucket of the invention shown in FIG. 8 .
FIG. 10 is a right side view of the bucket of the invention shown in FIG. 8 .
FIG. 11 is a view in top plan of the bucket of the invention shown in FIG. 8 .
FIG. 12 is a back view of the bucket of the invention shown in FIG. 8 .
FIG. 13 is a front view of the bucket of the invention shown in FIG. 8 .
FIG. 14 is a view in bottom plan of the bucket of the invention shown in FIG. 8 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 1-8 , there is illustrated a movable bucket 10 constructed in accordance with a preferred embodiment of my invention. The bucket 10 is configured having a floor 11 , a first side wall 12 , a second side wall 13 , and a rear wall 14 . Preferably, the side walls 12 , 13 and rear wall 14 connect with the floor 11 to define a triangular volume 16 which defines a bucket space, that is, the interior space of the bucket 10 for holding wash water (which may include cleaning solutions) used for mopping floors. Preferably, one or both of the side walls 12 , 13 are constructed to have a planar or substantially planar configuration. As illustrated in the preferred embodiment, the first side wall 12 is constructed having a generally planar surface portion 20 . The first side wall 12 is shown provided with one or more compartments, such as the compartment 22 for holding signs, such as, for example, wet floor signs 100 . The compartment 22 may be dimensioned to accommodate standard size wet floor signs. For example, one common size for wet floor signs is about 27 inches in height by about 11 inches in width. Generally wet floor signs 100 are comprised of two panels that may be folded or hinged together for storage, and unfolded for use (to form an a-frame configuration). Accordingly, preferred dimensions of the compartment 22 include an opening which will receive the sign width. Preferably, the sign length may be accommodated. According to one embodiment, the wet floor signs, such as that 100 , may be stored on the bucket 10 by orienting the sign lengthwise so that the length of the sign is held laterally by the compartment 22 .
According to a preferred embodiment, the compartment 22 may be constructed from a cavity formed in a side wall, such as the first side wall 12 . The first side wall 12 may, for example, be constructed to form at least one common wall 12 a of the bucket 10 that defines the triangular volume 16 of the bucket 10 . The compartment 22 may be formed in part by at least one exterior wall portion 12 b of the bucket 10 that is spaced from the common wall 12 a that defines the triangular volume 16 of the interior space. Preferably, the bucket 10 is made from steel, a plastic, or a polymer. When the bucket is made from plastic or a polymer, preferably it is molded and each compartment 22 provided on the bucket 10 is formed by integrally molding it during the molding of the bucket 10 as a whole. The space 24 between the common wall 12 a and the container exterior wall portion 12 b defines a storage area of the compartment 22 . According to a preferred construction, the storage compartment 22 may be provided with an opening 25 for insertion of one or more signs 100 . The opening 25 opens into the storage area space 24 to provide access to the storage area space 24 . According to a preferred embodiment, the storage compartment opening 25 may include a ramped portion disposed in the wall 12 (not shown) to facilitate directing a sign 100 into the compartment space 24 .
In a preferred embodiment shown in FIGS. 1-8 , the bucket 10 is provided with a pair of storage compartments 22 on each side wall 12 and 13 .
For illustrative purposes, as shown in FIG. 1 a , two signs 100 are shown held in the compartments 22 of the first side wall 12 . Signs may also be held in the compartments 22 of the second side wall 13 .
The bucket 10 is movable. Preferably, wheels 30 , 31 , 32 are provided to facilitate moving the bucket 10 . The wheels 30 , 31 , 32 may be pivotally mounted so that they are able to pivot as the bucket 10 is moved so that the wheels 30 , 31 , 32 may align themselves in a direction that the bucket 10 is being transported. According to alternate embodiments, one or more wheels 30 , 31 , 32 may be pivotally mounted, while others may be fixed. For example, one preferred configuration includes a pivotally mounted front wheel 30 and fixedly mounted rear wheels 32 , 33 . An alternate configuration provides a fixed front wheel 30 and pivotally mounted rear wheels 32 , 33 . Optionally, one or more of the wheels 30 , 31 , 32 may be provided with a locking mechanism that may be actuated to lock a wheel in place, and consequently, release the lock when desired. Preferably, the wheels 30 , 31 , 32 are constructed from a corrosion and water resistant material which is not prone to rusting or being corroded by chemicals. The wheel mounting mechanism also is constructed from materials which are corrosion and/or rust resistant.
The bucket 10 preferably has a handle 40 which is connected to the first side wall 12 and second side wall 13 . The handle 40 is pivotally connected to the side walls 12 , 13 , so that the handle 40 may be raised for grasping when the bucket 10 is to be moved, and may be lowered away from the bucket opening 19 when the bucket 10 interior volume 16 is to be accessed. Connectors, such as, for example, holes 41 and 42 in the side walls 12 and 13 through which the ends of the handle 40 extend, or a fastener, or pivot member, are preferably provided to mount the handle 40 to the side walls 12 , 13 . Alternately, the handle 40 may be snap fit, or installed on the bucket 10 by another suitable connection mechanism.
In a preferred embodiment of the invention, the side walls 12 and 13 and the rear wall 14 have a length of about 28 inches and a height of about 12 inches, and the compartments 22 have a length of about 13 inches and a height of about 10 inches.
According to preferred embodiments, the bucket 10 may be provided as a kit with one or more signs that are configured to correspond to the dimensions of the storage compartment 22 , so that the signs may be stored therein.
The triangular shaped bucket 10 preferably provides at least one substantially planar side wall.
Preferably, the bucket 10 is constructed from materials which are water resistant, and also are resistant to general bathroom cleaners, such as typical cleaners used to clean toilets, glass, bathroom hardware and fixtures.
In a preferred embodiment of the invention shown in FIG. 3 a , a mop wringer 60 , such as Rubbermaid's mop bucket wringer (model no. RU6127) or the mop wringer of U.S. Pat. No. 4,047,261 (which are incorporated herein by reference) for example, may be provided on the bucket 10 by positioning the mop wringer 60 on the rear wall 14 of the bucket 10 , with the main portion 60 a of the mop wringer 60 residing in and above the triangular volume 16 of the bucket 10 . A wet mop may be wrung out when desired by inserting the wet mop head into the mop wringer 60 and pulling on the mop wringer handle 60 b to cause the mop wringer 60 to squeeze the mop head to wring out liquid (e.g., wash water) therefrom.
FIGS. 9 to 14 show an alternative embodiment of the invention. The bucket 10 ′ shown in FIGS. 9 to 14 is substantially the same as the bucket 10 shown in FIGS. 1 to 8 , except the walls 12 ′, 13 ′ and 14 ′ of the bucket 10 ′ when viewed in top plan form an isosceles triangle, rather than the equilateral triangle formed by walls 12 , 13 and 14 of the bucket 10 when walls 12 , 13 and 14 of bucket 10 are viewed in top plan.
While the invention has been described with reference to specific embodiments, the description is illustrative and is not to be construed as limiting the scope of the invention. For example, though not shown, the storage compartments described herein may be provided with a cover for covering the opening to the storage area. Various modifications and changes may occur to those skilled in the art without departing from the spirit and scope of the invention described herein and as defined by the appended claims.
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A bucket having a triangular shape wherein three side walls and a floor define a triangular interior volume, the bucket having wheels for facilitating moving the bucket from one location to another location, and there being a storage compartment provided in a sidewall of the bucket for storing signs, such as, for example, wet floor signs.
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BACKGROUND OF THE INVENTION
[0001] The present application is a continuation of co-pending U.S. patent application Ser. No. 13/396,471 filed Feb. 14, 2012, which claims priority to U.S. Provisional Application No. 61/443,070 filed on Feb. 15, 2011, the entire contents of which are specifically incorporated herein by reference without disclaimer.
[0002] 1. Field of the Invention
[0003] This invention relates to transgenic fish, particularly blue transgenic fish.
[0004] 2. Description of Related Art
[0005] Transgenic technology involves the transfer of a foreign gene into a host organism enabling the host to acquire a new and inheritable trait. Transgenic technology has many potential applications. For example, it can be used to introduce a transgene into a fish in order to create new varieties of fish. There are many ways of introducing a foreign gene into fish, including: microinjection (e.g., Zhu et al., 1985; Du et al., 1992), electroporation (Powers et al., 1992), sperm-mediated gene transfer (Khoo et al., 1992; Sin et al., 1993), gene bombardment or gene gun (Zelenin et al., 1991), liposome-mediated gene transfer (Szelei et al., 1994), and the direct injection of DNA into muscle tissue (Xu et al., 1999). The first transgenic fish report was published by Zhu et al., (1985) using a chimeric gene construct consisting of a mouse metallothionein gene promoter and a human growth hormone gene. Most of the early transgenic fish studies have concentrated on growth hormone gene transfer with an aim of generating fast growing fish. While a majority of early attempts used heterologous growth hormone genes and promoters and failed to produce these fish (e.g. Chourrout et al., 1986; Penman et al., 1990; Brem et al., 1988; Gross et al., 1992), enhanced growth of transgenic fish has been demonstrated in several fish species including Atlantic salmon, several species of Pacific salmons, and loach (e.g. Du et al., 1992; Delvin et al., 1994, 1995; Tsai et al., 1995).
[0006] The zebrafish, Danio rerio , is a model organism for vertebrate developmental biology. As an experimental model, the zebrafish offers several major advantages such as easy availability of eggs and embryos, tissue clarity throughout embryogenesis, external development, short generation time and easy maintenance of both the adult and the young. Transgenic zebrafish have been used as an experimental tool in zebrafish developmental biology. However, for the ornamental fish industry the dark striped pigmentation of the adult zebrafish does not aid in the efficient display of the various colors that are currently available on the market. More recently, Lamason et al. (2005) in their report showed that the Golden zebrafish carry a recessive mutation in the slc24a5 gene, a putative cation exchanger, and have diminished number, size, and density of melanosomes, which are the pigmented organelles of the melanocytes and hence are lightly pigmented as compared to the wild type zebrafish. The availability of such fish having modified pigmentation for transgenesis with fluorescent proteins would result in better products for the ornamental fish industry due to better visualization of the various colors.
[0007] Many fluorescent proteins are known in the art and have been used to investigate various cellular processes, including fluorescent proteins exhibiting a green, red, yellow, blue, or purple color. Although transgenic experiments involving fluorescent proteins have provided new markers and reporters for transgenesis, progress in the field of developing and producing ornamental fish that express such proteins has been limited.
SUMMARY OF THE INVENTION
[0008] In certain embodiments, the present invention concerns making transgenic fluorescent fish and providing such fish to the ornamental fish industry.
[0009] In some embodiments, transgenic fish or methods of making transgenic fish are provided. In certain aspects, the transgenic fish are fertile, transgenic, fluorescent fish. In a particular embodiment, the fish for use with the disclosed constructs and methods is the Golden zebrafish. Zebrafish skin color is determined by pigment cells in their skin, which contain pigment granules called melanosomes (black or brown color), xanthosomes (yellow color), erythrosomes (orange or red color), or iridosomes (iridescent colors, including white color). The number, size, and density of the pigment granules per pigment cell influence the color of the fish skin. Golden zebrafish have diminished number, size, and density of melanosomes and hence have lighter skin when compared to the wild type zebrafish. Golden zebrafish have a mutation in slc24a5 gene, rendering the fish skin lighter or less pigmented (Lamason et al., 2005).
[0010] In certain specific embodiments there are provided transgenic zebrafish comprising specific transgenic integration events, referred to herein as transformation events. These fish are of particular interest because, for example, they embody an aesthetically pleasing blue color. Transgenic fish comprising these specific transgenic events may be homozygous or heterozygous (including, for example, hemizygous) for the transformation event. Homozygous fish bred with fish lacking a transformation event will in nearly all cases produce 100% heterozygous offspring. Eggs, sperm, and embryos comprising these specific transgenic events are also included as part of the invention.
[0011] In one such embodiment regarding a specific transgenic integration event, a blue transgenic zebrafish is provided comprising chromosomally integrated transgenes, wherein the zebrafish comprises the “Blue zebrafish 1 transformation event,” sperm comprising the Blue zebrafish 1 transformation event having been deposited as ECACC accession no. 11012802. The chromosomally integrated transgenes may be present on one integrated expression cassette or two or more integrated expression cassettes. In certain aspects, such a transgenic zebrafish is a fertile, transgenic zebrafish. In more specific aspects, such a zebrafish is a transgenic Golden zebrafish. Such a transgenic zebrafish may be homozygous or heterozygous (including, for example, hemizygous) for the transgenes or integrated expression cassette(s).
[0012] Also disclosed are methods of providing a transgenic zebrafish comprising the Blue zebrafish 1 transformation event to the ornamental fish market. In some embodiments, the method comprises obtaining a transgenic zebrafish comprising chromosomally integrated transgenes, wherein the zebrafish comprises the “Blue zebrafish 1 transformation event,” sperm comprising the Blue zebrafish 1 transformation event having been deposited as ECACC accession no. 11012802, and distributing the fish to the ornamental fish market. Such fish may be distributed by a grower to a commercial distributor, or such fish may be distributed by a grower or a commercial distributor to a retailer such as, for example, a multi-product retailer having an ornamental fish department.
[0013] In some aspects, methods of producing a transgenic zebrafish are provided comprising: (a) obtaining a zebrafish comprising chromosomally integrated transgenes, wherein the zebrafish comprises the “Blue zebrafish 1 transformation event,” sperm comprising the Blue zebrafish 1 transformation event having been deposited as ECACC accession no. 11012802; and (b) breeding the obtained zebrafish with a second zebrafish to provide a transgenic zebrafish comprising the Blue zebrafish 1 transformation event. The second zebrafish may be a transgenic or non-transgenic zebrafish.
[0014] In further embodiments, also provided are methods of producing a transgenic organism, the method comprising using sperm comprising the Blue zebrafish 1 transformation, such sperm having been deposited as ECACC accession no. 11012802, to produce transgenic offspring. Such offspring may be, for example, a zebrafish, a species of the Danio genus, a fish species related to zebrafish, or another fish species. In some aspects, the fish may be produced using in vitro fertilization techniques known in the art or described herein.
[0015] As used in this specification, “a” or “an” may mean one or more. As used herein in the claim(s), when used in conjunction with the word “comprising,” the words “a” or “an” may mean one or more than one.
[0016] The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.” As used herein “another” may mean at least a second or more.
[0017] Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.
[0018] Any embodiment of any of the present methods, kits, and compositions may consist of or consist essentially of—rather than comprise/include/contain/have—the described features and/or steps. Thus, in any of the claims, the term “consisting of” or “consisting essentially of” may be substituted for any of the open-ended linking verbs recited above, in order to change the scope of a given claim from what it would otherwise be using the open-ended linking verb.
[0019] Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
DETAILED DESCRIPTION OF THE INVENTION
Transgenic Fish
[0020] In some aspects, the invention regards transgenic fish. Methods of making transgenic fish are described in, for example, U.S. Pat. Nos. 7,135,613; 7,700,825; 7,834,239, each of which is incorporated by reference in its entirety.
[0021] It is preferred that fish belonging to species and varieties of fish of commercial value, particularly commercial value within the ornamental fish industry, be used. Such fish include but are not limited to catfish, zebrafish, medaka, carp, tilapia, goldfish, tetras, barbs, sharks (family Cyprinidae), angelfish, loach, koi, glassfish, catfish, discus, eel, tetra, goby, gourami, guppy, Xiphophorus, hatchet fish, Molly fish, or pangasius. A particular fish for use in the context of the invention is zebrafish, Danio rerio . Zebrafish are increasingly popular ornamental animals and would be of added commercial value in various colors. Zebrafish embryos are easily accessible and nearly transparent. A fish that is of particular use with the disclosed constructs and methods is the Golden Zebrafish. Zebrafish skin color is determined by pigment cells in their skin, which contain pigment granules called melanosomes. The number, size, and density of the melanosomes per pigment cell influence the color of the fish skin. Golden zebrafish have diminished number, size, and density of melanosomes and hence have lighter skin when compared to the wild type zebrafish. Golden zebrafish have a mutation in the slc24a5 gene, which codes for a putative cation exchanger localized to intracellular membrane, thus rendering the fish skin lighter or less pigmented (Lamason et al., 2005).
[0000] Fertilization from Frozen Sperm
[0022] Fish sperm freezing methods are well-known in the art; see, e.g., Walker and Streisinger (1983) and Draper and Moens (2007), both of which are incorporated herein by reference in their entireties. To obtain transgenic fish disclosed herein, frozen zebrafish sperm may be used to fertilize eggs, as described in Draper and Moens (2007).
[0023] Eggs are collected as described in Draper and Moens (2007). Briefly, two females are placed in tricaine solution at 16 mg/100 mL water. After gill movement has slowed, one of the fish is removed and rinsed in water. The fish is placed on a paper towel to dry briefly and then transferred to a small plastic dish. With slightly damp fingers, one finger is placed on the dorsal side of the fish. The eggs are removed by gently pressing on the ventral side of the fish, starting just behind the pectoral fins and moving toward the tail.
[0024] The eggs from the female zebrafish are squeezed into a 35 mm plastic Petri dish. The sperm are thawed at 33° C. in a water bath for 8-10 sec. 70 μl room temperature Hanks solution is added to the vial and mixed. The eggs are then immediately added to the vial and gently mixed. The sperm and eggs are activated by adding 750 μl of fish water and mixing. The mixture is incubated for 5 min at room temperature. The dish is then filled with fish water and incubated at 28° C. After 2-3 hrs, fertile embryos are transferred to small dishes where they are further cultured.
[0025] Parichy and Johnson, 2001, which is incorporated by reference in its entirety, provides additional examples regarding in vitro fertilization.
[0026] The invention further encompasses progeny of a transgenic fish containing the Blue zebrafish 1 integration event, as well as such transgenic fish derived from a transgenic fish egg, sperm cell, embryo, or other cell containing a genomically integrated transgenic construct. “Progeny,” as the term is used herein, can result from breeding two transgenic fish of the invention, or from breeding a first transgenic fish of the invention to a second fish that is not a transgenic fish of the invention. In the latter case, the second fish can, for example, be a wild-type fish, a specialized strain of fish, a mutant fish, or another transgenic fish. The hybrid progeny of these matings have the benefits of the transgene for fluorescence combined with the benefits derived from these other lineages.
[0027] The simplest way to identify fish containing the Blue zebrafish 1 transformation event is by visual inspection, as the fish in question would be blue colored and immediately distinguishable from non-transgenic fish.
Examples
[0028] Certain embodiments of the invention are further described with reference to the following examples. These examples are intended to be merely illustrative of the invention and are not intended to limit or restrict the scope of the present invention in any way and should not be construed as providing conditions, parameters, reagents, or starting materials that must be utilized exclusively in order to practice the art of the present invention.
Example 1
Blue Transgenic Zebrafish
[0029] Transgenic fish exhibiting a blue color are provided. The specific transgenic events embodied in these fish are designated Blue zebrafish 1. Sperm from these fish may be used to fertilize zebrafish eggs and thereby breed transgenic zebrafish that comprise these specific transgenic integration events. Sperm from this line was deposited with the European Collection of Cell Cultures (ECACC), Porton Down, Salisbury, SP4 OJG, United Kingdom, on Jan. 28, 2011, under the provisions of the Budapest Treaty as “Blue zebrafish 1” (accession no. 11012802; cell line ZEBRAFISH 2011.2 BZF001).
[0030] The fluorescent transgenic fish have use as ornamental fish in the market. Stably expressing transgenic lines can be developed by breeding a transgenic individual with a wild-type fish, mutant fish, or another transgenic fish. The desired transgenic fish can be distinguished from non-transgenic fish by observing the fish in white light, sunlight, ultraviolet light, blue light, or any other useful lighting condition that allows visualization of the blue color of the transgenic fish.
[0031] The fluorescent transgenic fish should also be valuable in the market for scientific research tools because they can be used for embryonic studies such as tracing cell lineage and cell migration. Additionally, these fish can be used to mark cells in genetic mosaic experiments and in fish cancer models.
[0032] All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents that are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the invention as defined by the appended claims.
REFERENCES
[0033] The following references, to the extent that they provide exemplary procedural or other details supplementary to those set forth herein, are specifically incorporated herein by reference.
U.S. Patent No. 7,135,613 U.S. Patent No. 7,700,825 U.S. Patent No. 7,834,239 Brem et al., Aquaculture, 68:209-219, 1988. Chourrout et al., Aquaculture, 51:143-150, 1986. Delvin et al., Nature, 371:209-210, 1994. Draper and Moens, In: The Zebrafish Book, 5 th Ed.; Eugene, University of Oregon Press, 2007. Du et al., Bio/Technology, 10:176-181, 1992. Gross et al., Aquaculature, 103:253-273, 1992. Khoo et al., Aquaculture, 107:1-19, 1992. Lamason et al., Science, 310(5755):1782-1786, 2005. Penman et al., Aquaculture, 85:35-50, 1990. Powers et al., Mol. Marine Biol. Biotechnol., 1:301-308, 1992. Sin et al., Aquaculature, 117:57-69, 1993. Szelei et al., Transgenic Res., 3:116-119, 1994. Tsai et al., Can. J. Fish Aquat. Sci., 52:776-787, 1995. Walker and Streisinger, Genetics 103: 125-136, 1983. Xu et al., DNA Cell Biol., 18, 85-95, 1999. Zelenin et al., FEBS Lett., 287(1-2):118-120, 1991. Zhu et al., Z. Angew. Ichthyol., 1:31-34, 1985.
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The present invention relates to transgenic blue ornamental fish, as well as methods of making such fish by in vitro fertilization techniques. Also disclosed are methods of establishing a population of such transgenic fish and methods of providing them to the ornamental fish industry for the purpose of marketing.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates in general to electrical submersible well pump assemblies, and in particular to an electrical submersible pump supported on coil tubing.
2. Description of the Prior Art
Electrical submersible pumps for oil wells include a centrifugal pump mounted to a downhole electrical motor. In a conventional installation, the upper end of the pump secures to a lower end of a string of production tubing. The production tubing comprises threaded sections of tubing secured together, each about 30 feet long. The motor usually locates below the pump. A power cable extends from the surface and straps to the exterior of the tubing. The tubing supports the weight of the pump assembly. The weight of the power cable is also supported by the tubing through the straps which secure the power cable to the tubing. The well fluid is produced through the tubing to the surface.
Periodically, the pump assembly must be pulled to the surface for replacement or maintenance. Also, the well may require maintenance. This requires a pulling unit which will unscrew and pull the sections of production tubing from the well. Pulling the pump and putting it back into the well on the sections of tubing can be time consuming. It also requires a unit which has a draw works for pulling the production tubing.
Proposals have been made in the past to eliminate the production tubing. Conventional electrical power cable cannot support the weight of the pump assembly, and in fact cannot even support its own weight in most wells. Consequently, a special power cable that would be weight supporting would be required. Although proposals has been made to utilize weight supporting cable, it is not common practice.
Also it has been proposed to support the electrical submersible pump assembly on coil tubing. Coil tubing is a continuous length of tubing that when pulled, will wind on a large reel located at the surface. The coil tubing is of smaller diameter than typical production tubing but it is of steel and will support weight. Although proposals have been made, there are no installations of electrical submersible pumps on coil tubing known to Applicant.
SUMMARY OF THE INVENTION
In this invention, the electrical submersible pump assembly is supported on coil or continuous tubing. The cable extends through the coil tubing for supplying electrical power to the pump assembly. The cable has an outer diameter that is less than the inner diameter of the tubing, resulting in an annulus surrounding the cable. Standoff means extends in this annulus for frictionally engaging the cable with the coil tubing to support the weight of the cable with the tubing.
Preferably, the annulus serves as a flow passage means for circulating fluid from the surface. Preferably the production from the pump flows around the exterior of the coil tubing to the surface. Cooling or lubricating fluid is circulated down the annulus surrounding the cable.
In one embodiment, the standoff members comprise elastomeric rings which encircle the cable and are spaced apart from each other along the length of the cable. The rings have flow passages extending through them for allowing fluid to be circulated through the annulus.
In another embodiment, the standoff means comprises a plurality of longitudinal elastomeric standoff members. These standoff members are strips extending longitudinally along the cable. Each strip is circumferentially spaced apart from the other strips to concentrically support the cable in the continuous tubing. Spaces between the strips define flow passages through the annulus.
In a third embodiment, the standoff members comprise longitudinally extending tubes. These tubes are also spaced circumferentially around the cable and extend continuously to the surface. The tubes frictionally engage the outer diameter of the cable and the inner diameter of the continuous tubing. The tubes serve as flow passages for circulating cooling or lubricant fluids to the pump.
In all three embodiments, preferably the elastomeric standoff members are of a material that expands when contacted by lubricating oil, a swelling agent, or heat. The expanding causes the standoff members to tightly grip the cable and the inner wall of the coil tubing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view illustrating an electrical submersible well pump installation constructed in accordance with this invention.
FIG. 2 is an enlarged perspective view illustrating a portion of the continuous tubing and electrical cable of the pump assembly of FIG. 1.
FIG. 3 is a transverse sectional view illustrating an alternate embodiment of standoff members for the electrical cable and continuous tubing of FIG. 1.
FIG. 4 is a transverse sectional view illustrating another alternate embodiment of standoff members for the cable and continuous tubing of FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, the well includes casing 11 which will be cemented in place. In the embodiment shown, a tubular liner 13 extends through the casing 11. Liner 13, which serves as production tubing, is of a conventional type, having sections secured together by threads. A pump assembly 15 is supported inside the liner 13. A releasable packer 17 will support the pump assembly 15 in liner 13, and seal the annulus around pump assembly 15.
Pump assembly 15 includes a centrifugal pump 19 conventional design. Pump 19 has a lower end located below packer 17. Pump 19 has intake ports 21 below packer 17 and discharge ports 23 located above packer 17 for discharging well fluid pumped from the well. An electrical motor 25 rotates pump 19. Motor 25 is located above pump 19 and secures to an adapter 27. Adapter 27 may be of various types, and has means for securing to a lower end of a length of coil tubing 29.
Coil tubing 29 is metal, flexible tubing of a type that will coil onto a reel (not shown) located at the surface while coil tubing 29 is out of the well. This type of coil tubing 29 has been used for a variety of purposes.
As shown also in FIG. 2, an electrical cable 31 extends through the coil tubing 29 from the pump assembly 15 to the surface. Electrical cable 31 supplies power to motor 25 and may be of conventional type. A tree 33 at the upper end of casing 11 provides pressure and valve control. A flow line 35 extends from tree 33 for delivering well fluids pumped by pump 19.
Referring to FIG. 2, electrical cable 31 is conventional, having three electrical conductors 37, one for each phase of the electrical motor 25. Electrical conductors 37 are encased in insulating layers 39. An elastomeric jacket 41 surrounds insulating layers 39, which will be generally spaced 180 degrees apart along the longitudinal axis of jacket 41. An outer elastomeric layer 43 surrounds jacket 41.
The transverse cross section of electrical cable 31 is cylindrical. The outer diameter of outer layer 43 is significantly less than the inner diameter 45 of coil tubing 29. This results in an annulus 47 surrounding electrical cable 31.
A standoff means is employed to support electrical cable 31 in coil tubing 29. In the embodiment of FIG. 2, the standoff means comprises a plurality of standoff rings 49. Standoff rings 49 are preferably elastomeric rings of a donut shape similar to an O-ring. However, the rings 49 could be a combination of other materials, such as a metal clamping ring with an elastomeric outer diameter or coating. Each standoff ring 49 is axially spaced apart from adjacent standoff rings 49, preferably by several inches. Each standoff ring 49 has an inner perimeter which will frictionally engage the outer diameter of electrical cable 31. The outer perimeter frictionally engages inner diameter 45 of coil tubing 29. The frictional contact is sufficient to transfer the weight of electrical cable 31 to the coil tubing 29. Standoff rings 49 are preferably of an elastomeric material which will swell or expand upon application of lubricating oil and heat from downhole well temperatures. Elastomeric materials which swell with heat and oil contact and which are suitable for use as a standoff ring 49 are known. U.S. Pat. No. 4,513,215, April 23, 1985. David I. Del Serra, describes a suitable material, all of which material is hereby incorporated by reference.
A split 51 in each standoff ring 49 enables the standoff ring 49 to be placed around electrical cable 31 during the manufacturing process. A plurality of flow passages 53 extend through each standoff ring 49 parallel to the longitudinal axis of coil tubing 29. Each flow passage 53 is preferably a small hole extending from an upper side to a lower side of each standoff ring 49, but could also be a channel along the outer diameter of each ring 49. Flow passages 53 are spaced circumferentially around the standoff rings 49. Flow passages 53 could allow fluid to be pumped down annulus 47 for lubricating or cooling of the pump assembly 15, for cooling of the motor 25, and for transfer of cable 31 heat to the coiled tubing 29. The fluid pumped down passages 53 could also cause swelling or expansion of the standoff rings 49.
Electrical cable 31 is installed in coil tubing 29 during manufacturing of coil tubing 29. Coil tubing 29 is preferably manufactured in a process in which a seam of the coil tubing will be welded as the tubing is formed from a strip into a cylindrical tube. The cable 31 will be positioned on the strip prior to the strip being folded into a cylindrical shape and the seam welded. The standoff rings 49 will be inserted around the electrical cable 31 by spreading apart the split 51. Then a section of the coil tubing 29 will be formed and welded along the seam. This process will be continued until the desired length of coil tubing 29 has been fabricated with electrical cable 31 inside. Then, the coil tubing 29 will be coiled on a reel (not shown) with the electrical cable 31 inside.
To install the pump assembly 15, the operator will connect the lower end of coil tubing 29 to adapter 27. The operator lowers the pump assembly 15 using the coil tubing reel. The pump assembly 15 will land in packer 17 in a conventional manner. The weight of the pump assembly 15 while being lowered into the well will be supported by the coil tubing 29. The weight of the electrical cable 31 will be supported by the coil tubing 29 through the frictional engagement of the standoff rings 49.
During operation, power will be supplied through conductors 37 to rotate motor 25, which in turn rotates pump 19. Well fluid will be drawn in from the well through ports 21 and pumped out ports 23 above packer 17. The well fluid flows up through liner 13 around the exterior of coil tubing 29.
At the same time, the operator may wish to supply a cooling fluid or lubricating fluid to pump assembly 15. The operator can handle this by pumping fluid from the surface down the annulus 47 and through the flow passages 53.
The cross sectional view of FIG. 3 represents an alternate embodiment, with common components to those in FIG. 1 being designated the same numeral with the addition of the prefix numeral "1". In this embodiment, longitudinal standoff members 55 are employed rather than annular standoff rings 49 (FIG. 2). Standoff members 55 are strips of an elastomeric material a few feet in length. The elastomeric material is also preferably of a type that swells with contact with oil and heat. Each standoff member 55 extends a few feet along the length of electrical cable 131. Axial spaces (not shown) may exist between upper and lower ends of standoff members 55 above and below each other.
Standoff members 55 are spaced circumferentially around electrical cable 131, with flow passages 57 located between. In the embodiment shown, three standoff members 55 are shown, each spaced 120 degrees apart from the other. Standoff members 55 frictionally grip both the outer diameter of electrical cable 131 and the inner diameter of coil tubing 129. After the assembly has been installed in the well, the operator can pump oil down the flow passages 57, which not only then provides cooling, but also causes swelling of the standoff members 55 to provide greater frictional retention.
In the embodiment of FIG. 4, common components to that of FIG. 1 will be indicated with the same numeral with the prefix "2". In this embodiment, the standoff members comprise tubes 59. Preferably, three tubes 59 are employed, each spaced 120 degrees apart from the other. Each tube 59 has a portion or side that frictionally engages the outer diameter of electrical cable 231 and an opposite side that frictionally engages the inner diameter of coil tubing 229. Cooling or lubricating fluids can be pumped down and circulated back up the tubes 59, or the fluid could be delivered to associated equipment, such as packers, or to the wellbore for chemical treatment. The frictional engagement of the tubes 59 supports the weight of the electrical cable 231. Tubes 59 extend continuously from the pumping assembly to the surface. Tubes 59 are also preferably of a material which swells upon application of heat and oil.
The invention has significant advantages. The standoff members will support the weight of the cable within the coil tubing. Making the outer diameter of the cable significantly less than the inner diameter of the coil tubing provides an annular space through which fluids can be circulated for cooling or lubricating.
While the invention has been shown in only three of its forms, it should be apparent to those skilled in the art that it is not so limited but is susceptible to various changes without departing from the scope of the invention.
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An electrical submersible well pump assembly supported on a continuous length of coil tubing. An electrical cable extends through the coil tubing from the pump assembly to the surface for supplying electrical power to the pump assembly. The cable is of lesser diameter than the inner diameter of the tubing, resulting in an annulus. Standoff members locate in the annulus to centralize the cable. Standoff members frictionally engage the inner diameter of the tubing and the outer diameter of the cable to transfer weight of the cable to the coil tubing. Flow passages extend through the annulus surrounding the cable to enable lubricant and coolant fluid to be pumped from the surface to the pump assembly.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation application of and claims priority to U.S. application Ser. No. 10/516,528, filed on Dec. 2, 2004, now U.S. Pat. No. 7,648,627, which is a nationalization of PCT/EP03/05377, filed on May 22, 2003 and published in German, which claims priority under 35 U.S.C. §119(a) to DE 102 24 750.1, filed on Jun. 4, 2002.
TECHNICAL FIELD
The invention relates to an apparatus for the treatment of a medical fluid comprising a fluid treatment machine and a cassette insertable therein substantially consisting of a rigid base body of the cassette with fitted chambers and passages and a foil covering them.
BACKGROUND
Cassettes are used in medical engineering, in particular to convey dialysis fluid, blood and the like.
A cassette can include a base body with fitted chambers and passages which is closed by a flexible foil to cover the passages and chambers. The cassette can be inserted into a special receiving chamber, e.g., in a dialysis machine. This chamber can, for example, be opened via a pivotable door. The cassette can be inserted into the chamber, with the flexible foil lying opposite a corresponding mating piece at the machine so that the cassette can be operated with the aid of actuators and sensors on the machine side.
Conventional extracorporeal blood circuits or blood tubing systems are usually present in a differential construction. This means that a functional division onto different components is present. Such components (e.g., bubble traps, flow chambers or injection positions) are connected to one another by tubes and are as a rule connected individually to the respective dialysis machine. The design of such blood tubing systems is very complex in manufacture and handling, with the corresponding effort naturally being extremely time consuming with more complex systems such as an online hemodiafiltration.
On the other hand, conventional extracorporeal blood circuits which are installed in this differential construction have the advantage that they can be designed substantially more flexibly for the respective treatment depending on the demand. Previously known apparatuses for the use of cassettes typically were only usable for a very specific application.
SUMMARY
Certain aspects of the invention relate to a generic apparatus comprising a fluid treatment machine and a cassette insertable therein such that a large flexibility for different applications is made possible while maintaining the fast and simple exchangeability.
In some aspects of the invention, actuators and sensors are arranged in a generic apparatus for the treatment of a medical fluid for the operation of the apparatus with an inserted cassette such that cassettes are insertable in different integration shapes.
Due to the clearly defined arrangement of corresponding sensors and actuators, cassettes of different complexity can be inserted into the fluid treatment machine in accordance with the desired application. It is therefore not necessary to provide different apparatus for different applications.
A cassette for a standard hemodialysis can thus be insertable here, for example. The corresponding pump chambers, measuring sensors and further actuators, such as valves, etc., are provided at pre-determined locations in the fluid treatment machine. Additional pumps, actuators, valves, etc. are provided in the fluid treatment machine which do not have to be actuated when the cassette is used for standard hemodialysis. They are, for example, only in use when a cassette is used for online hemodiafiltration or online hemofiltration. Further passages, pump chambers, etc. are provided at corresponding positions in the corresponding cassettes which are associated with these actuators, pumps or valves. Furthermore, a cassette for an acute dialysis treatment can be inserted in which in turn the pumps, actuators and valves provided on the side of the fluid treatment machine are associated with corresponding pumping chambers, passages, etc. The associated control electronics can be selected depending on the inserted cassette for the control of the pumps, actuators, sensors, etc.
DESCRIPTION OF DRAWINGS
Details and advantages of the invention will be explained in more detail by way of example in the following with reference to the Figures. There are shown:
FIG. 1 : a schematic plan view of a cassette for standard hemodialysis;
FIG. 2 : a schematic plan view of a cassette in accordance with the invention according to a further embodiment of the invention for use in online hemodiafiltration or online hemofiltration;
FIG. 3 : a plan view of a cassette in accordance with a further embodiment of the present invention which can be used for acute treatment;
FIG. 4 : a schematic plan view of a further aspect of the invention which substantially corresponds to that in accordance with FIG. 1 , but has an integrated dialyzer;
FIG. 5 : a further aspect of the invention which substantially corresponds to that in accordance with FIG. 2 , but has an integrated dialyzer;
FIG. 6 : a further embodiment of the invention which substantially corresponds to that in accordance with FIG. 3 , but has an integrated dialyzer;
FIG. 7 : a three-dimensional representation of a fluid treatment machine as an embodiment of the apparatus in accordance with the invention without an inserted cassette;
FIG. 8 : a representation corresponding to FIG. 7 , but with an inserted cassette;
FIG. 9 : a representation in accordance with FIG. 7 , but with a different embodiment variant of a cassette differing from the cassette shown in FIG. 8 ;
FIG. 10 : a detail of a venting unit in the apparatus in accordance with the invention;
FIG. 11 : a detailed view of a contour of a measuring chamber in a cassette in accordance with one of the aforesaid embodiment variants;
FIG. 12 : a partially sectional representation of a pump chamber of the cassette in accordance with the present invention;
FIG. 13 : a partially sectional representation through a passage of the cassette in accordance with an embodiment variant of the invention;
FIG. 14 : a cross-sectional view of a valve;
FIG. 15 : a diagrammatic view of the valve of FIG. 14 in use in a disposable cartridge;
FIG. 16 : a perspective view of a fluid guide body having an open main passage and a secondary passage opening therein in accordance with an embodiment of the invention in a sectional representation;
FIG. 17 : a perspective view of a base body of the cassette of FIG. 1 in a partial section, wherein a covering film is pressed onto the fluid guide body by a valve actuator and closes the secondary passage;
FIG. 18 : a perspective view similar to FIG. 17 , wherein the secondary passage is represented in its open position; and
FIG. 19 : a schematic, 3D representation of a section of an elastic matt according to an embodiment of the present invention;
FIG. 20 : a section along the section line A-A′ in FIG. 19 ;
FIG. 21 : a section along the section line B-B′ in FIG. 19 ;
FIG. 22 : a section along the section line C-C′ in FIG. 19 .
DETAILED DESCRIPTION
In FIG. 1 , a cassette 10 in accordance with an embodiment of the present invention is shown which can be used for standard hemodialysis. In FIG. 1 , the surface of the cassette 10 is divided into a hatched region B (two partial areas) and a non-hatched region A. Both the surface of the cassette 10 and the surface of an associated machine block 108 (shown in FIG. 7 ) are divided into the covering surface regions A and B. Components of actuators or sensors to be coupled, which are common to all cassettes as basic variants (e.g., all the cassettes for standard hemodialysis) are accommodated in the surface region A (not hatched in FIG. 1 ), and the surface region B denotes a region in which actuators or sensors to be used optionally are provided in the machine block 108 (shown in FIG. 7 ). As discussed below, FIG. 2 illustrates a cassette that includes operable components in a region corresponding to a surface region B.
The cassette consists of a base body 12 of a cassette which consists of polypropylene in the embodiment shown here. A cover foil 14 (shown in FIGS. 10 , 12 , 13 , 17 , and 18 ) consisting, for example, of a polyolefin elastomer mixture, is applied to the base body 12 of the cassette 10 . The passages and recesses, which will be looked at in more detail later, are covered by this cover foil 14 . An arterial injection septum 16 is provided in the arterial line 18 to the dialyzer and a venous injection septum 20 is provided in the venous line 22 to the dialyzer. The dialyzer itself and the corresponding tube connection are not shown in any more detail in the embodiment shown here. Reference number 24 designates the blood inlet from the patient and reference number 26 designates the blood outlet to the patient. The respective tubes, which likewise consist of a polyolefin elastomer mixture, are also not shown here for reasons of simplification. Passages 28 are recessed in the base body 12 of the cassette 10 . They are acted on by a row of valves 30 .
These valves 30 have a valve body with a pressure passage and a sealing cap which cooperates with the valve body such that it closes the end of the pressure passage on the valve body side with respect to the environment, with a pressure space being able to be built up between the pressure passage and the sealing cap so that the sealing cap has a deformable sealing region for entry into the fluid passage in order to close this as required.
FIG. 14 shows one of the valves 30 in a sectional view, which is rotation-symmetric about a vertical axis. The valve 30 includes a valve body 112 with a pressure channel 114 , which ends in a pressure chamber 116 . A sealing cap 118 with a deformable area 120 , which bounds the pressure chamber 116 , is placed over the valve body 112 .
The pressure channel 114 of the valve body 112 is elongated, so that it can be inserted, for example, through the body or a wall of a counterpart of the disposable cassette 10 on the device side (i.e., through the machine block 108 ) and can be screwed down with a lock nut 122 . A thread is provided on the outer wall of the portion of the valve body 112 that forms the pressure channel 114 to allow the lock nut 122 to secure the valve body 112 to the machine block 108 . The valve body 112 has sealing surfaces 124 for sealing the valve body 112 in the machine block 108 . The sealing cap 118 includes protruding bulges 126 , which surround the valve body 112 in such a way that they lie adjacent to the sealing surfaces 124 and are pressed when the valve 30 is assembled.
Still referring to FIG. 14 , the upper area of the valve 30 is the area on the fluid passage side (i.e., the side nearest the cassette 10 ). A projection 130 of the sealing cap 118 lies on the end of the valve body 112 , on the fluid passage side. A shoulder 128 of the sealing cap 118 is provided to ensure that that the sealing cap 118 fits into its associated fluid passage in the cassette 10 .
The valve 30 is shown diagramatically in use in FIG. 15 . The base body 12 of the disposable cassette 10 in which liquid passages 28 are formed is shown in diagrammatic representation. The corresponding counterpart of the disposable cartridge body on the device side (i.e., the machine block 108 ) is shown pressed against the cassette 10 .
The valve 30 is inserted into a suitably shaped housing (e.g., recess) 138 of the machine block 108 and screwed down with the lock nut 122 . The shoulder 128 lies adjacent to the edges of the liquid passage 28 . The movement of the deformable area 120 when an excess pressure or partial vacuum is applied or with venting of the pressure channel 114 is indicated by arrow 140 . Reference number 142 indicates the direction in which the pressure is applied in order to close the valve 30 . As shown in FIG. 15 , the housing 138 in the machine block 108 is rotation-symmetric about the pressure channel 114 of the valve 30 , and the liquid passage 28 extends perpendicular to the plane of the figure.
A cut-out for accommodating the shoulder 128 can be provided either in the base body 12 of the cassette 10 or in the machine block 108 . It is also possible for the shoulder 128 to be accommodated in a suitable opening in a cover mat located between the cassette 10 and the machine block 108 .
For the sake of clarity, FIG. 15 does not show the cover foil 14 of the cassette 10 , which closes off the fluid passage 28 against the surroundings. The cover foil 14 (shown in FIGS. 10 , 12 , 13 , 17 , and 18 ) can be fixed on the side of the base body 12 of the cassette 10 that is pressed against the machine block 108 . The cover foil 14 is sufficiently flexible so that it can follow the deformation of the deformable area 120 of the sealing cap 118 of the valve 130 .
For the operation of the valve 30 with the cassette 10 , the valve body 112 is inserted through the housing 138 of the machine block 108 , so that the pressure channel 114 extends through the machine block 108 . The lock nut 122 is tightened up so that the protruding bulges 126 create a seal between the valve body 112 and the machine block 108 . By simply screwing the lock nut 122 onto the valve body 112 , a tight and reliable connection of the valve 30 with the machine block 108 is thus provided.
The machine block 108 with the valve 30 is pressed against the cassette 10 , whereby the shoulders 128 of the sealing cap 118 fit tightly with the edges of the liquid passage 28 . By pressing the machine block 108 against the disposable cassette 10 , several valves 30 can be simultaneously fitted into their corresponding liquid passages 28 at the desired points.
The dialysis liquid, for example, flows through the fluid passage 28 when the valve 30 is in the opened state. If excess pressure is applied via the pressure channel 114 in the direction of the arrow 142 , the deformable area 120 of the sealing cap 118 is deformed into the liquid passage 28 until the valve 30 is finally closed. The loading on the sealing cap 118 is reduced by the projection 130 of the sealing cap 118 , without the movement of the deformable area 120 being significantly impaired. The cover foil 14 of the cassette 10 is deformed together with the sealing cap 118 into the liquid passage 28 .
If the fluid passage 28 is to be opened again, the pressure channel 114 is vented and the deformable area 120 of the sealing cap 118 is relaxed. By applying a partial vacuum to the pressure channel 114 , the deformable area 120 is placed against the convex curvature of the pressure chamber 116 and correspondingly increases the cross-section of the fluid passage 28 . By simply applying or removing a pressurization to the pressure channel 114 , therefore, the flow rate through the fluid passage 28 can be controlled.
When the disposable cartridge is removed, the valve 30 can be removed or replaced simply by loosening lock nut 122 , e.g., for maintenance or in the event of malfunction.
The sealing cap 118 is a simple low-cost shaped part, which on account of its closed design can easily be cleaned and thus satisfies the hygiene requirements in dialysis, but which can also easily be replaced when necessary.
When the disposable cassette 10 is again compressed between the machine block 108 and the base body 12 , the valve 30 fits into the fluid passage 28 very well by pressing the shoulder 128 with the edge of the fluid passage 28 . On account of the elastic stretching of the deformable area 120 of the sealing cap 118 , there is a very good tolerance compensation both in the depth of the fluid passage 28 as well as in respect of lateral misalignment, without a significant additional expenditure of force. The deformable area 120 guarantees that only small forces are required to block the fluid passage 28 .
Other details regarding the valves 30 and their operation with disposable cartridges, such as the cassette 10 described above, are discussed in DE 100 46 651, which is incorporated by reference herein.
Referring again to FIG. 1 , an arterial measuring chamber 32 and a venous measuring chamber 34 are furthermore recessed in the base body 12 of the cassette 10 . The basic design of these measuring chambers is shown in FIG. 11 . Referring to FIG. 11 , the flow direction of the fluid, i.e., of the blood through the chambers 32 , 34 , is indicated by the arrows. The measuring chambers 32 and 34 have a widened passage section to be able to receive the sensors 36 . The contour of the measuring chambers 32 , 34 corresponds to a diffuser nozzle geometry such as is shown in FIG. 11 . A diffuser 38 , which runs out in a nozzle 40 , is arranged in the region of the inflow region of the fluid. The widened cross-section in the diffuser 38 is relatively rapid in comparison to the narrowed cross-section in the nozzle 40 . The sensors 36 , which are made in the form of multi-functional sensors, are arranged in the region of the arterial or venous measuring chamber 32 , 34 .
More specifically, each of the sensors 36 for measuring selected parameters of the medical fluid passing in the arterial and venous measuring chambers 32 , 34 is disposed on a measurement plate that has a peripheral seal along its outer edge and that is in contact with the flexible membrane (i.e., the foil 14 ). The measurement plate has an inlet that leads to the foil 14 so that a vacuum can be established between the measurement plate and the foil 14 .
Several sensors can be mounted on the measurement plate, and since the flexible membrane (i.e., the foil 14 ) can be brought in close contact with the measurement plate, the medical fluids are separated from the sensors on the measurement plate only by the foil 14 . Because of the peripheral seal disposed on the measurement plate, the foil 14 can be brought in close contact with the underside of the measurement plate by applying a vacuum, so that very close contact can be established between the sensors and the medical fluid in the measurement chamber. The contact surface of at least one of the sensors is preferably flush with the underside of the measurement plate, so that it is possible to establish direct measurement contact between the respective sensor and the flexible membrane.
Because of advances in miniaturization and integration technology of sensors, it is possible to arrange multiple sensors on an area a few square centimeters in size. Each respective sensor is preferably mounted in a recess in the measurement plate, with the measurement surface of the sensor being in flush contact with the underside of the measurement plate. The sensors are preferably securely glued to the measurement plate.
For example, a pressure sensor and a temperature sensor may be used. Pressure sensors have become available formed on individual semiconductor chips due to advances in integration of Microsystems, so that the chips carrying the sensor are only a few square millimeters in size. Because the sensor surface can be brought in direct contact with the foil 14 , it is possible to measure both positive and negative pressures. As a result, the thermal energy balance and the venous pressure in a dialysis machine can be measured with the pressure sensor and the temperature sensor.
In some implementations, the seal of the measurement plate is made of a rubber ring which is inserted into a groove in the measurement plate and projects slightly above the edge of the measurement plate. As soon as a vacuum is established between the membrane (i.e., the foil 14 ) and the measurement plate, the foil 14 is pressed tightly against the underside of the measurement plate by the ambient air pressure, and the seal guarantees that no additional air can flow into the area between the measurement plate and the foil 14 .
The measurement plate can be made of a metal disk into which the respective sensors are inserted. In some implementations, the metal disk is kept at a constant temperature by, for example, Peltier elements. This design permits a more accurate temperature measurement of the medical fluid.
Before performing the individual measurements, a vacuum is first applied to the inlet so that the film (i.e., the foil 14 ) is placed in close contact with the sensors. Then, the sensors are activated by a control unit (not shown), so that the respective measurements can begin.
The above-described sensor arrangement is described in greater detail in DE 198 37 667, which is incorporated by reference herein.
Referring again to FIG. 1 , an arterial port 42 and a heparin port 44 are provided at the cassette, which are each connected via corresponding passages to the passage carrying the arterial blood in each case via phantom valves 46 . The phantom valves 46 are used in the cassette 10 in accordance with the invention instead of conventional open T-branches. In these phantom valves, the passage wall is not interrupted from the aspect of the main blood flow. Reference number 48 designates a venous port which likewise opens into a blood-carrying passage 28 , here in the venous part of the blood-carrying passages, via a phantom valve 46 .
As FIG. 16 shows, and as discussed above, the fluid guide body (i.e., the base body 12 ) of the cassette 10 has a main fluid passage 28 , which is integrally worked into the base body 12 and is closed by a covering film (i.e., the foil 14 ), which is not shown in FIG. 16 .
The fluid guide body (i.e., the base body 12 ) further has a secondary passage 144 that leads away from the rear side of the base body 12 , which is remote from the open side of the main passage 28 , onto the opposite front side of the base body 12 and opens there into the main passage 28 . As FIG. 17 shows, the secondary passage 144 passes through a base 146 of the main passage 28 . The secondary passage 144 extends into the main passage 28 in the form of a volcano-like funnel 148 whose height corresponds to the depth of the main passage 28 so that an orifice 150 of the secondary passage 144 is arranged vertically coincident with the rims of the main passage 28 .
The secondary passage 144 is positioned symmetrically in the center of the main passage 28 and extends perpendicularly to the longitudinal direction of the main passage 28 . The planar designed orifice 150 is in the plane which is set up by the rims of the main passage 28 .
As FIG. 16 shows, the funnel 148 has a streamlined cross-section. In more precise terms, the outside of the wall of the secondary passage 144 in the main passage 28 is formed in streamlined manner, with the longitudinal axis of the streamlined shape corresponding to the longitudinal axis of the main passage 28 . Vortexes, turbulences and an increased flow resistance are thereby avoided at the secondary passage 144 . The medical fluid flowing through the main passage 28 can flow past the secondary passage 144 in laminar fashion.
As FIG. 16 shows, the contours of the main passage 28 are also formed extending in streamlined fashion around the secondary passage 144 . The side walls of the main passage 28 opposite the funnel 148 bulge in streamlined fashion around the funnel 148 so that the fluid flow forking around the funnel 148 finds approximately the same flow cross-section and can flow past the funnel 148 without speed changes.
To be able to close the open side of the secondary passage 144 and simultaneously the orifice 150 of the secondary passage 144 , the covering film (i.e., the foil 14 ), which can be welded or connected in another way to the base body 12 , lies on the base body 12 . To seal the main passage 28 , the foil 14 can be welded to the base body 12 along the rims of the main passage 28 . The sealing can, however, also be effected by pressing the foil 14 along the rims of the main passage 28 by a valve plunger 152 .
The valve plunger 152 has a continuous, planar plunger surface 154 that is formed by an elastic (e.g., elastomer) machine membrane. Due to the vertically coincident arrangement of the orifice 150 with the rims of the main passage 28 , the secondary passage 144 can be closed without stretching of the foil 14 , if the foil 14 is pressed onto the base body 12 . The orifice 150 is formed for this purpose as a planar valve seat 156 , which is in the plane set up by the rims of the main passage 28 and forms the front end of the funnel 148 .
FIG. 17 shows the closed state of the secondary passage 144 . The plunger surface 154 is pressed onto the base body 12 . Additional pressure can be applied by an actuating part 158 in the region of the orifice 150 of the secondary passage 144 in order to achieve a reliable sealing of the secondary passage 144 .
To open the secondary passage 144 , the actuating part 158 , which is connected to the plunger surface 154 in the region of the secondary passage orifice 150 , is moved away from the base body 12 . The plunger surface 154 is thereby raised from the orifice 150 of the secondary passage 144 in the region thereof. As FIG. 18 shows, the plunger surface 154 thereby deforms, which is allowed by the design of the same as an elastic membrane.
The foil 14 also lifts off the orifice 150 of the secondary passage 144 due to the raising of the plunger surface 154 . The pressure of the flow in the main passage 28 presses the foil 14 away from the orifice 150 . Optionally, this can also be supported actively by the interposition of a vacuum between the plunger surface 154 and the foil 14 , which is helpful in particular when a sample should be sucked from the fluid flow in the main passage 28 through the secondary passage 144 .
When the actuating part 158 lifts, the foil 14 stretches elastically. The deformation is here very low, however. It is in particular not plastic so that a formation of creases in the subsequent re-closing of the orifice 150 is prevented. As FIG. 18 shows, the secondary passage 144 is in flow communication with the main passage 28 in the raised state of the foil 14 .
Other details regarding the phantom valves 46 are described in DE 100 53 441, which is incorporated by reference herein.
Referring again to FIG. 1 , reference numbers 50 designate two pump chambers which serve to pump the blood. The design of the pump chambers 50 is shown in detail in FIG. 12 . The pump chambers 50 , which are activated via membrane pumps provided at the machine side (i.e., in the machine block 108 ), have substantially tangential inlets and outlets for a uniform throughflow of the total chamber, as shown in FIG. 1 . The shape of the pump chambers 50 is pre-determined by the correspondingly shaped base body 12 of the cassette 10 and can be approximately described as a spherical section. At the periphery, the base body 12 of the cassette 10 has a raised edge 52 around the pumping chambers 50 which serves as a stop bead. In addition, as shown in FIG. 12 , the peripheral edge of the spherical section is set somewhat lower so that in the pressing-out phase, that is in the phase in which the cover foil 14 is moved toward the base body 12 of the cassette 10 , a flushing edge or flushing passage 54 is formed. The flushing edge or flushing passage 54 is advantageously made in that the spherical pump surface at the machine side (i.e., the spherical pump surface in the machine block 108 ), which is not shown in FIG. 12 , has a smaller radius than the radius of the pump chamber 50 at the cassette side. The radius difference Δ r is shown in FIG. 12 . A wide flushing edge or flushing passage 54 is hereby formed. This flushing edge or flushing passage 54 is an annular space for the pumped blood in the extreme pressing-out position. This free annular space, on the one hand, avoids blood damage by being trapped between the foil surface and the injection molded surface (i.e., the base body 12 ) at the end of the pressing-out phase and, on the other hand, blood damage due to high flow speeds and shearing strains which would result at the start of the start-up phase if no free annular space were provided.
In the upper region of the cassette in the installed state, a venting chamber 56 is formed which is shown again in FIG. 10 in a sectional representation. A venting membrane 58 is arranged in this venting chamber via which correspondingly collected air can be separated since it is made as a partially permeable membrane which preferably has hydrophobic or oleophobic properties. Expanded or sintered polytetrafluoroethylene can preferably be used as the venting membrane. A venting stub 60 is arranged above the venting membrane 58 and its cooperation with the fluid treatment machine (not shown in more detail here) will be described later.
Bubbles are trapped in the venting chamber 56 by a slowing down of the blood flow. As shown in FIG. 10 , a rotation flow is generated for effective air separation with minimum area requirements on the cassette 10 . In this process, the generation of the final rotation flow is only created in the operating state of the cassette 10 in the fluid treatment machine 100 . The cover foil 14 of the cassette 10 is pulled into the fluid treatment machine 100 by a corresponding vacuum coupling system of which only one vacuum suction passage 102 is shown in FIG. 10 . An almost circular cross-section of the venting chamber 56 is thereby formed. The rotation flow of the blood is supported in that the passage opening into the venting chamber 56 also runs—together with its cover foil 14 —slightly into the machine side so that an almost tangential inflow within the chamber is achieved. An effective suction can take place at the machine side at the venting stub 60 . A low filling volume results overall here in the venting chamber 56 as a result of the construction.
The basic design of the passages 28 can be explained with reference to FIG. 13 . Generally, care is taken in the passage design of the passages 28 that a smooth foil surface and smooth passage surfaces are provided. Steps, dead spaces, turbulence and impact surfaces are avoided. Low changes in direction and speed are aimed for. Separations of flow are largely avoided. All passages 28 and also chambers 50 have an edge bead 52 which accompanies the passages and faces the cover foil 14 . On insertion of the cassette 10 into the fluid treatment machine 100 , the foil 14 is pressed onto the edge bead 52 such that all passages 28 are sealed against the environment. At the rear of the cassette, i.e., at the outer side of the passage wall, webs 62 are formed which accompany the passages and via which the rear pressing force is guided to the edge beads 52 in order thus to achieve a uniform linear distribution of force.
It can also be explained with reference to FIG. 13 that the base body 12 of the cassette 10 is welded to the cover foil 14 at the outer edge 64 .
As shown in FIG. 1 , the cassette 10 has a recessed centering fork 66 as a positioning aid which receives a centering pin on the machine side on insertion. Stop noses 68 are furthermore molded on which contact against corresponding machine surfaces on insertion. The cassette 10 is thereby guided in height and angle. When pressing the cassette 10 into the fluid treatment machine 100 , a latching with the fluid treatment machine takes place at a snap element not shown in more detail here such that the cassette 10 is fixed in an aligned manner. The cassette 10 has a molded handle 70 at the side disposed opposite the centering fork 66 for simplified handling.
The arterial injection septum 16 or the venous injection septum 20 are made in the embodiment shown here, in contrast to a conventional injection position, such that their base body is formed by the base body 12 of the cassette itself so that here only the elastic septum is fixed by a snap ring (not shown in detail here). The septum consists of an elastomer in the embodiment shown here.
FIG. 4 shows a modified embodiment of the cassette in accordance with FIG. 1 . This cassette 10 shown in FIG. 4 also serves standard hemodialysis and largely shows an identical design to the cassette 10 in accordance with FIG. 1 . To this extent, a detailed description of the already described components of the cassette 10 is superfluous. However, instead of the handle 70 in the embodiment in accordance with FIG. 1 , a dialyzer 72 is integrated in the side of the cassette 10 , with the lines 18 and 22 to the dialyzer opening directly into the dialyzer. The dialysate connections at the dialyzer, which can have a conventional design, are designated by 74 and 76 .
A cassette 10 is shown in FIG. 2 which is designed as an online hemodiafiltration cassette. It becomes clear from the arrangement of the different elements that the base body 12 of the cassette 10 starts from that base body of a cassette such as has already been described in FIG. 1 with reference to the embodiment for standard hemodialysis. All elements which are known from this configuration can be found in the same manner in the embodiment variant in accordance with FIG. 2 for online hemodiafiltration. To this extent, they will not be additionally explained again. However, those parts will be explained which are necessary for the operation of the hemodiafiltration cassette. This includes the substituate connector 80 via which the substituate fluid is fed into the passages 28 . Substituate passage valves 82 are provided at the passages and the passages 28 can be closed at the appropriate positions via these valves 82 . The substituate fluid is guided into two parallel pump chambers 84 , which form substituate pump chambers, via the passages 28 . The substituate pump chambers 84 substantially correspond to the pump chambers for the blood 50 as they have previously already been described in detail. Starting from the passage 28 , the substituate fluid is guided through a substituate tunnel 86 which is disposed on the opposite side of the base body 12 of the cassette 10 . The substituate tunnel 26 is suitably closed at the rear side, e.g., by a welded foil. The substituate fluid 86 can be led into the passage 28 carrying the blood via a port for pre-dilution 88 or via a port for post-dilution 90 . The ports are again made as phantom valves of the type described above.
The substituate region substantially formed by the substituate pump chambers 84 is surrounded by a substituate weld rim 92 to which the cover foil 14 is sealingly welded so that this region of the cassette 10 processing substituate is separated from the blood-carrying region.
In FIG. 5 , a modification of the embodiment variant in accordance with FIG. 2 is shown. Here, too, in a similar manner to the embodiment variant in accordance with FIG. 4 , a dialyzer 72 is integrated directly into the cassette 10 .
In FIG. 3 , a cassette 10 for acute treatment is shown as a further integrated embodiment of the cassette. It is designed identically to the embodiment variant in accordance with FIG. 1 in the region of the blood treatment part. With respect to the substituate part, it partly corresponds to the embodiment in accordance with FIG. 2 , with here only one substituate pump chamber 84 being provided which is fed by the substituate fluid led in via the substituate connector 80 and the passage 28 . In a similar manner as to the embodiment variant in accordance with FIG. 2 , substituate passage valves 82 are provided before and after the substituate pump chamber 84 . The further pump chamber, which is designated by 94 in the present embodiment variant for acute treatment, is connected to a filtrate outlet 96 via a passage 28 and opens into a filtrate connection 98 which is connected to the dialyzer not shown in any more detail here.
In FIG. 6 , in turn, a modified embodiment variant of the cassette 10 in accordance with FIG. 3 is shown. Here, a dialyzer 72 is in turn integrated instead of the handle, with here a connection 99 being provided between the dialyzer 72 and the passage 28 which carries the filtrate and which leads to the filtrate pump chamber 94 .
In FIG. 7 , an embodiment of the fluid treatment machine 100 is shown without an inserted cassette 10 . This fluid treatment machine 100 is designed such that all aforesaid cassettes can be inserted, with a basic extracorporeal blood circuit, i.e. a standard dialysis using an external dialyzer, being carried out by a corresponding program selection, for example on insertion of the cassette in accordance with the embodiment variant in accordance with FIG. 1 . When a cassette 10 in accordance with the embodiment of FIG. 2 is used, online hemodiafiltration or an online hemofiltration variant is, for example realized by use of the components required for this purpose with, optionally, automatic connections (not shown) to the fluid circuit of the basic unit. Highly integrated variants with an integrated dialyzer and an automatic dialyzer connection are also possible such as are shown by way of the cassette in the embodiment variants in accordance with FIGS. 4 and 5 . Acute dialysis treatment is possible when a cassette 10 is used in accordance with the embodiment of FIG. 3 .
The fluid treatment machine 100 substantially consists of a frame 104 which surrounds and/or includes or receives the most important components. A door 106 is fitted to the frame 104 , on the one hand, and the machine block 108 is guided in the frame, on the other hand. All forces occurring between the door 106 and the interior of the unit are absorbed by means of the frame 104 , namely the door hinge, door latch, pressing actuator system and the rear wall. The frame 104 furthermore contains the door latch 110 . The cassette 10 is received between the door 106 and the machine block 108 , as shown in the FIGS. 8 and 9 , and is sealed by pressing. Sensor system elements are included in the cassette region of the machine and they detect whether a cassette is correctly positioned in the fluid treatment machine. These, or further sensor system elements, can be designed such that they are suitable for recognizing the cassette type (e.g. with the aid of a barcode on the cassette).
The important elements for the control and monitoring of the extracorporeal blood circuit, such as pumps, valves, the sensor system, etc., are contained in the machine block 108 . This machine block 108 establishes the most important interface to the cassette 10 . The cassette surface is coupled to the unit here and the sealing of the cassette 10 , and thus the fixing of the flow paths, takes place by this. The machine block 108 is guided movably in the frame and fixes the cassette 10 , as already described above, until the door 106 is closed.
Hydraulic piston pumps are contained in the fluid treatment machine which are not shown in detail in FIGS. 7 , 8 and 9 here. They are, on the one hand, blood pumps or optional substituate feed pumps or ultrafiltrate pumps. They are hydraulically connected to the pump chambers (i.e., the blood pump chambers) C, D, and, in some cases, they are hydraulically connected to the optional filtrate pump chambers and/or the optional substituate pump chambers E, F. Furthermore, compressors for the generation of the required pneumatic pressure (overpressure or vacuum) not shown in more detail here are contained in the fluid treatment machine 100 . The fluid treatment machine 100 furthermore has—in a manner not shown in more detail—a pneumatic buffer container for the compensation of pressure fluctuations, a main electronics box, a heparin injection pump and a blood pressure monitor module.
A pressing actuator system on the rear wall of the frame 104 , likewise not shown in more detail, must be emphasized here. An inflatable air cushion is integrated here which can move the whole machine block 108 , which is movably supported in the frame 104 , and press it against the closed door 106 .
Furthermore, instead of individual air-carrying tubes, an air distributor plate is provided at the machine block 108 which contains main connections for the pneumatics and which guides compressed air and vacuum to the valves and actuators via passages integrated there without any substantial tubing, with them simultaneously terminating the machine block with respect to the interior of the fluid treatment machine 100 .
Optional modules can be provided in the fluid treatment machine 100 for the carrying out of the online hemodiafiltration. For instance, an online feed port for the automatic coupling of a cassette 10 to a dialysate circuit or an online flushing port for the return of flushing solution can be contained here.
The door 106 must be open for the insertion of the cassette 10 . The cassette 10 is inserted and, after positioning of the centering fork 66 , is fixed to the surface of the machine block by means of a snap hook.
The side of the machine block 108 facing the cassette 10 is lined with a soft elastomer mat 160 (shown in FIG. 19 ), which seals the cassette 10 after pressing has taken place.
Referring to FIG. 19 , during use, the elastic matt 160 is arranged between the fluid treatment machine (i.e., the machine block 108 ), of which no detail is shown here, and the cassette 10 . On the so-called machine side, namely on the surface which, when assembled, faces the fluid treatment machine 100 , matt channels 162 and connection channels 164 are formed. Furthermore, a recess 166 is arranged in the elastic matt 160 , into which in the assembled condition a machine-mounted valve, for example, engages and establishes a seal all around. It is easy to see that this machine-mounted valve interrupts the respective matt channel 162 which happens to join the recess 166 . In order to still make an air extraction possible, a connection channel 164 has been provided which connects the two interrupted branches of the matt channel 162 and connects them in turn with a further, parallel matt channel 162 . The structure shown here is, of course, only an example and can be changed in any way. While the channel structures are provided on the machine side of the elastic matt 160 , the disposable side, namely the side facing the cassette, is executed as a smooth, i.e., flat surface.
By referring to the sectional views of FIGS. 20 to 22 , the structure of the individual channels can be explained in more detail. The section A-A′ as per FIG. 19 is shown in FIG. 20 where a matt channel 162 becomes visible which, with the elastic matt 160 used here having a thickness of 4 mm, has a depth of 3 mm and a width of 2 mm. In the remaining matt material below the channel 162 , which has a thickness of 1 mm, a slit 168 is placed which takes on a type of valve function. When a vacuum is applied, the two areas of the elastic matt 160 adjacent to the slit 168 will open and enable the extraction of air gas. In an idle state or when an equilibrium is obtained, the two adjacent areas return to their original position and close the opening. In order to enhance this return effect, areas between the slits 168 are provided in the matt channel 162 , which on the one hand do not have a slit and, on the other hand, are less deeply recessed in the area of matt channel 162 . Referring to FIG. 21 , a corresponding area can be seen in section B-B′, which shows that, while the matt channel 162 in this area has the same width of 2 mm, it only has a depth of 1 mm.
Referring to FIG. 22 , a connection channel 164 is shown in the sectional view of C-C′, where said channel is narrower and not as deep as the matt channel 162 , which can be seen clearly in this view. In this case, both the width of the connection channel 164 and the depth are one millimeter each.
With the elastic matt 160 , it is guaranteed that the interior space of the fluid treatment machine, in its idle state, is protected by the self-closing feature of slits 168 . At the same time, an even air extraction is achieved between the fluid treatment machine and the cassette across its entire surface because parallel extraction takes place via numerous slits 168 . Thus, a minor blockage may not cause any detrimental effects for other areas.
With a thin matt 160 , as it has been presented in the embodiment for example, the opening effect of the slits can be utilized by applying a vacuum.
Since the elastic matt 160 is exchangeable, it can be replaced easily after contamination or a fault. It is especially advantageous that no structured shapes are required for the fixed components on the machine. On the side of the elastic matt 160 facing the machine, open structures can be formed so that no sub-surface tunnels or other closed structures are required. On the other hand, the side of the elastic matt 160 facing the cassette is largely formed as a smooth, closed surface which can be cleaned easily for example.
Other details regarding the elastic matt 160 are described in DE 101 57 924.1, which is incorporated by reference herein.
Referring again to FIG. 7 , after closing and locking the door 106 , pressing takes place by inflating the aforesaid air cushion. On opening and removing the cassette 10 , the pressing is cancelled again by letting out the air in the air cushion before opening the door 106 .
To achieve a sufficient pressing and to prevent a tilting of the machine block 108 by a non-uniform introduction of force, the air cushion has approximately the size of the machine block 108 or of the cassette 10 .
Since, however, further components, for example, control valves or the air distributor plate with the control valves, are now disposed between the air cushion and the machine block, the force transmission takes place by means of spacer bolts.
The traction between the door 106 , the frame 104 and the rear wall takes place by the door hinge, the latch 110 and connection bolts, not shown in any more detail here, between the frame and the rear wall.
As already mentioned, a constant pressing of the cassette 10 must take place for a proper operation. For this purpose, it is necessary for the door 106 to be locked during the treatment. This locking takes place via two latching bolts (not shown in any more detail here) at the upper right hand and lower right hand door region, with these moving into two corresponding bores inside the door 106 on actuation, which takes place automatically. The moving in and out takes place pneumatically. An erroneous opening of the door 106 on a failure of the pneumatics is precluded by the bolts moved into the door and by the lateral forces occurring by the pressure load of the door. To check whether the latching has taken place, Hall proximity sensors can be integrated which detect the movement of the bolts. In addition, this signal can be linked to information on the door position which can be picked up by a separate sensor. In addition, the latching bolt not shown in any more detail here can have a latch connection. This latch connection consists of a spring-loaded latch ball on the door side which latches into a corresponding arch of the latch bolt and can hold the door in the corresponding position. An introduction slope is provided for the simplified latching. To open the door from the latch position, the latch ball present here is drawn back by means of a mechanical system.
On the side of the fluid treatment machine 100 , the blood circuit substantially consists of at least one hydraulically controlled membrane pump having two independent pump chambers C and D which can be used as a highly precise flow pump or as a volumetric metering unit, a row of valves M, O and clamps N for the control of the flow path, a highly integrated sensor system G, H required for monitoring and control, an active air extractor, i.e., an air separation chamber I with a connected cassette venting A, of the blood circuit (air-free circuit) and a door 106 to fix the cassette 10 .
The fluid treatment machine 100 respectively comprises a pneumatic system for the overpressure and a pneumatic system for the underpressure. The underpressure serves, for example, to apply an underpressure between the foil 14 of the cassette 10 and the unit side to prevent a passage restriction on the plastic deformation of the foil, to raise the foil at feed positions and thus to be able to keep the access free, to avoid air compliance in the pump devices and to be able to ensure an air-free coupling between the sensor and the foil at specific sensor positions. The air suction requires openings in the unit side and a suction unit, i.e., a vacuum pump, connected to it, wherein the vacuum distribution should be ensured as uniformly and as reliably as possible over the whole surface. In the idling state, the openings should be at least largely closed to permit a good cleaning here. In operation, however, a problem-free air suction should be possible. This problem is solved by the elastomer mat of the type described above.
In the cassette 10 , no passage seals are contained except for the edge region and some safety weld connections. The sealing of all flow paths and passages must therefore take place by pressing. For this purpose, the cassette has sealing beads 52 on the passage rims which have already been described above and which are sealable on the pressing of the disposables between the machine block 108 and the door 106 by pressing into the elastic mat.
The air distributor plate not shown in any more detail here is located on the rear side of the machine block 108 and is connected to the, for example, two membrane pumps of the pneumatic system, namely the overpressure pump and the underpressure pump. The air distributor plate is sealed with respect to the rear side of the machine block by a sealing mat and permits the compressed air and vacuum feed via integrated passage structures so that every valve does not need its own tubing. A plurality of circuits are present on the air distributor plate, namely a vacuum circuit, a compressed air circuit which is directly connected to the compressor for the supply of components which always need compressed air, a compressed air circuit for the protection of sensitive components which may only be charged with compressed air under certain states, with it also being separable from the compressor by an on/off valve and an exhaust circuit.
By integration of a plurality of control valves on the air distributor plate, the electrical supply can also be collected via a small control board. Since a plurality of valves are only needed with specific options, a modular retrofitting capability must be ensured.
The sensor system and the pump connections are guided through the plate through apertures and cut-outs.
Sensors which are collected in integrated sensor modules in the present fluid treatment machine 100 are required for the monitoring and control of the extracorporeal blood circuit. Two respective modules work together as a pair. One module is accommodated in the door 106 and the counter-piece in the machine block 108 . Both the arterial branch should be monitored by the arterial measuring chamber G and the venous branch by the venous measuring chamber H. The integrated measurement sensor system is described in detail in the German patent applications DE 198 37 667 A and DE 101 43 137 of the same patent applicant. The sensors together have the following properties or provide the following possibilities:
measurement and monitoring of the blood volume;
measurement of the hematocrit;
measurement and monitoring of the thermal energy balance;
measurement and monitoring of the body temperature;
measurement of the conditions of the fistula (with circulation);
air detection;
fistula pressure measurement.
A multi-sensor module is usually fitted with an ultrasonic sensor for volume monitoring, measurement of the hematocrit and the air detection, with a temperature sensor for the automatic access analysis, body temperature monitoring and thermal energy balance, with a pressure sensor for the pressure monitoring and with an optical sensor for the automatic detection of blood.
The valves M and the pump valves O have a similar design to those valves described above.
In addition to the aforesaid valves which are shown in FIG. 7 , so-called phantom valves, which are not drawn in any more detail in this FIG. 7 , are additionally present. The design and function of the phantom valves are similar to the design and function of the phantom valves discussed above.
Reference letter N designates safety clamps which serve to achieve a safe state during an alarm in the extracorporeal blood circuit, with them interrupting the patient line and thus any blood flow from or to the patient. To avoid unwanted compliance effects, and since the system is designed for a flow reversal, this safety function must be ensured both on the arterial side and on the venous side so that two blocking clamps N are used which can be mechanically coupled.
The blocking clamps should be effective as close to the patient as possible in order to be able to minimize any interference and to satisfy high safety demands. For this reason, tube clamps are used which act directly on the patient tubes.
A possible embodiment, such as is provided here, consists of the clamping of the tubes against a clamping rail on the inner side of the door by means of a reclosable pneumatically opened clamping slide. Such a system is passively spring-closing, namely without pressure and without current and so is also advantageous in the case of a failure under safety aspects.
In FIG. 8 , a fluid treatment machine 100 is shown corresponding to FIG. 7 with an inserted cassette 10 corresponding to FIG. 2 . In FIG. 9 , in contrast, a fluid treatment machine 100 is shown with a cassette 10 corresponding to the embodiment variant in accordance with FIG. 5 , with the dialyzer in the cassette here having an automatic dialysate connection K and L to the fluid treatment machine 100 .
The new apparatus shown here follows a strictly modular approach while achieving a high flexibility and deployment possibility also with respect to future deployment possibilities and options. The integrated blood module permits the carrying out of the whole spectrum of the blood treatment procedures, namely standard hemodialysis, online hemodiafiltration, online hemofiltration and also acute treatment.
It must be pointed out with respect to the acute treatment that the machines serving the acute treatment, i.e., the acute dialysis or acute filtration, have to have a simple design in order to be able to be transported corresponding easily and to be able to work without a complex supply structure (e.g. water connection). In this system, therefore, work is carried out practically without exception with bags with premanufactured solutions. Using the embodiments shown in FIGS. 3 to 6 , acute hemofiltration can then be carried out easily in which the substituate is supplied from a bag and filtrate is removed from the filter into an empty bag with the pumps shown. Except for the connection of the bags, no further measure is necessary in this case. It would naturally nevertheless be possible to additionally make a dialysis possible with a corresponding effort. Furthermore, the substituate pump could alternatively be used as a dialysate supply pump if the connections inside the cassette were changed accordingly. Then dialysis fluid filled into bags could be supplied in balanced form to the filter via the membrane pump, while fluid is led out in a controlled manner via the filtrate pump. No further components would also be necessary for the fluid control in such a machine.
Each of these types of treatment can take place both in two-needle and in single-needle mode. Reference is made here to the German patent DE 100 42 324 C1 with respect to the description of the two-needle or single-needle mode.
Other embodiments are within the scope of the following claims.
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The invention relates to an apparatus for the treatment of a medical liquid comprising a liquid treatment machine and a cassette insertable therein substantially made of a rigid base body of the cassette with fitted chambers and passages and a foil covering them.
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CROSS-REFERENCE TO RELATED APPLICATIONS
The present divisional application claims priority to U.S. Provisional Patent Application Ser. No. 61/291,694, filed Dec. 31, 2009, entitled “VEHICLE AND MAST MOUNTING ASSEMBLY THEREFOR,” and U.S. patent application Ser. No. 12/696,861, filed Jan. 29, 2010, entitled “COMMUNICATIONS VEHICLE,” the disclosures of which are expressly incorporated by reference herein.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
The invention described herein was made in the performance of official duties by employees of the Department of the Navy and may be manufactured, used and licensed by or for the United States Government for any governmental purpose without payment of any royalties thereon.
BACKGROUND OF THE INVENTION
Oftentimes it is necessary in the commercial and military communications field to locate communications hubs and controllers in areas proximate significant events. In such situations, communications gear has been transported in cases and then assembled on site. When the communications equipment is desired at a different location, the gear is disassembled, closed up in the cases, moved to the new location, unpacked, and then reassembled.
SUMMARY OF THE INVENTION
In one embodiment, a communications assembly is provided including a shelter housing; a first cabling raceway disposed within the shelter housing, the first cabling raceway being exclusively dedicated for radio frequency transmitting cabling; a second cabling raceway disposed within the shelter housing, the second cabling raceway being exclusively dedicated for non-radio frequency data transmitting cabling; and a third cabling raceway disposed within the shelter housing, the third cabling raceway being exclusively dedicated for alternating current and direct current transmitting cabling.
In another embodiment, a method of assembling a communications assembly is provided, the method including obtaining a shelter housing having side walls, a front wall, a rear wall, a floor, and a top wall; coupling a first cabling raceway to the walls at a first height, the first cabling raceway extending generally parallel to the top wall; coupling a second cabling raceway to the walls at a second height, the second cabling raceway extending generally parallel to the top wall; coupling a third cabling raceway to the walls at a third height, the third cabling raceway extending generally parallel to the top wall; placing radio-frequency transmission cabling exclusively within the first cabling raceway; placing non-radio-frequency data transmission cabling exclusively within the second cabling raceway; and placing alternating current transmission cabling and direct current transmission cabling exclusively within the third raceway.
In still another embodiment, a communications vehicle is provided, including a vehicle frame; a shelter housing supported by the frame, the shelter housing defining an interior and an exterior; a first communication device located within the interior of the shelter housing; and a signal interface positioned on the shelter housing. The signal interface includes ports thereon in communication the first communication device. The first communication device includes software therein that permits the first communication device to control and operate a second communication device that is substantially similar to the first communication device, that is located in a shelter housing separate from the shelter housing containing the first communication device, and that is electrically coupled via a wire to the signal interface.
In another embodiment, a method of expanding a communications array is provided including the steps of providing a first shelter on a first vehicle frame, the first shelter including a first radio therein and a first signal interface accessible from the exterior of the first shelter, the first radio providing a plurality of communication channels; providing a second Shelter on a second vehicle frame, the second shelter including a second radio therein and a second signal interface accessible from the exterior of the second shelter, the second radio providing a plurality of communication channels; electrically coupling ports on the first signal interface to ports on the second signal interface; and controlling all provided communications channels with the first radio.
In another embodiment, a vehicle array is provided including a first vehicle including a power input interface and a power output interface; a second vehicle including a power input interface and a power output interface; a power generator having a power output interface; a first power cable linking the power output interface of the power generator to the power input interface of the first vehicle; and a second power cable linking the power output interface of the first vehicle to the power input interface of the second vehicle.
In another embodiment, a method of powering a vehicle array is provided including the steps of providing a first vehicle having a frame and a first shelter supported on the frame, the first shelter including a power input interface and a power output interface; providing a second vehicle having a frame and a second shelter supported on the frame, the second shelter including a power input interface and a power output interface; providing a power generator having a power output; coupling the power output of the power generator to the power input interface of the first vehicle such that the power generator provides power to electronics housed within the first shelter; coupling the power output interface of the first shelter to the power input interface of the second shelter to provide power to electronics housed within the second shelter.
In another embodiment, a method of transporting a communications array is provided. The method including the steps of providing a first vehicle having a frame and a first shelter supported on the frame at a first location, the first shelter including plurality of communications devices therein, the communications devices being coupled to each other and to a signal interface disposed on the first shelter, the signal interface providing a plurality of ports that are accessible on the exterior of the first shelter; providing a second vehicle having a frame and a second shelter supported on the frame at the first location, the second shelter including plurality of communications devices therein, the communications devices being coupled to each other and to a signal interface disposed on the second shelter, the signal interface providing a plurality of ports that are accessible on the exterior of the second shelter; providing interconnect cables that interface with the signal interfaces of the first and second shelters to provide data connections between the plurality of electronics in the first and second shelters; uncoupling the interconnect cables from the first and second shelters; driving the first and second vehicles to a second location; and coupling the interconnect cables to the signal interfaces of the first and second shelters to provide data connections between the plurality of electronics in the first and second shelters at the second location.
In another embodiment, a vehicle is provided including a frame, an engine supported by the frame, the engine operatively coupled to ground engaging members and capable of imparting motion to at least one of the ground engaging members; a shelter housing coupled to the frame and dependent upon the frame for supporting the shelter housing; a first communication device located within the interior of the shelter housing; and a signal interface positioned on the shelter housing, the signal interface including ports thereon in communication the first communication device; wherein the first communication device includes software therein that permits the first communication device to control and operate a second communication device that is substantially similar to the first communication device, that is located in a shelter housing separate from the shelter housing containing the first communication device, and that is electrically coupled via a wire to the signal interface.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of the vehicle of the present disclosure in a mobile configuration;
FIG. 2 is a side view of the vehicle of FIG. 1 in a stationary configuration;
FIG. 3 is a front left perspective view of the shelter carried by the vehicle of FIG. 1 ;
FIG. 4A is a top view of the shelter of FIG. 3 ;
FIG. 4B is a top view showing flattened out walls of the shelter of FIG. 3 ;
FIG. 4C is a side view of racks and electronics located within the shelter of FIG. 3 ;
FIG. 5 is a perspective view of a connection housing of the shelter of FIG. 3 ;
FIG. 6 is a plan view of a first set of connections present within the connection housing of FIG. 5 ;
FIG. 7 is a plan view of a second set of connections present within the connection housing of FIG. 5 ;
FIG. 8 is an exploded perspective view of the housing and connections of FIG. 6 ;
FIG. 9 is a side partially-cross sectional view of the housing and connections of FIGS. 6 and 8 ; and
FIG. 10 is an overhead view of four of the vehicles of FIG. 1 that are coupled together and to a power generator.
DETAILED DESCRIPTION
With reference first to FIG. 1 , a vehicle 10 is disclosed which as disclosed is depicted as a truck, and more particularly as a military vehicle. It should be understood that the disclosure is equally applicable to commercial vehicles for use, for example, in radio or TV broadcasting or in any other application in which mobile and extensible communications devices are utilized.
As shown, vehicle 10 comprises a frame 12 , and ground engaging members 14 which support the frame 12 . Engine 11 provides power to at least one ground engaging member 14 . As depicted, ground engaging members 14 are shown as tires and wheels, however it should be understood that other ground engaging members such as tracks or skis could be employed. The invention is equally applicable to any water flotation devices. As shown, a shelter assembly 16 is supported by the vehicle frame 12 and includes a mast assembly 18 . Shelter assembly 16 is positioned on frame 12 in a fixed manner such that parts of vehicle 10 such as ground engaging members 14 , engine 11 , and frame 12 , etc. have a fixed spatial relationship with shelter assembly 16 .
FIG. 1 shows vehicle 10 having mast assembly 18 and antennae 36 in stowed positions suitable for transport. FIG. 2 shows mast assembly 18 in a vertical position that is ready for extension. Additional details of the mast assembly 18 are provided in U.S. Provisional Patent Application Ser. No. 61/291,694, filed Dec. 31, 2009, entitled “VEHICLE AND MAST MOUNTING ASSEMBLY THEREFOR,” the disclosure of which has been expressly incorporated by reference herein.
With respect now to FIG. 2 , shelter assembly 16 is shown in greater detail. Shelter assembly 16 includes an enclosure 20 having a top wall 22 , a front wall 24 , lower wall 25 , side walls 26 , 28 and rear wall 30 . Shelter assembly 16 could also include a front work platform 32 including a hoist 34 , as well as a plurality of antennas positioned around enclosure 20 and shown generally at 36 . Walls 24 , 26 , 28 , 30 include or potentially include signal interface assemblies 112 disposed therein. Shelter assembly 16 further includes cabling raceways 510 , 512 , 514 disposed therein, shown in FIG. 4B .
Shelter assembly 16 houses a plurality of electronic racks 210 , 212 , 216 , 218 , 220 and safe 214 therein, shown in FIG. 4 . Electronic equipment 200 is located on electronic racks 210 , 212 , 216 , 218 , 220 according multiple considerations. These considerations include, but are not limited to, weight of the equipment 200 , center of gravity of shelter assembly 16 , interconnections needed between equipment 200 , cabling sizes of the interconnections, and cabling weight of the interconnections.
Equipment 200 is generally communications equipment including but not limited to: Ethernet switches, power distributors, speakers, headset interfaces, keyboards, filters, power supplies (uninterruptible or otherwise), PCI bus bays, servers, modems, encryption devices, secure terminal equipment devices, multi-band radios/transceivers (high frequency, very high frequency, and ultra high frequency), amplifiers for the radios, power supplies for the radios, mercury interface unit, GPS distribution system, low volume terminals, voice cable kit, and Ethernet kit.
As previously noted, equipment 200 requires interconnections. Equipment 200 further requires power. Raceways 510 , 512 , 514 are provided within for data, RF, and power cable routing and management. Raceways 510 , 512 , 514 include upper raceways 510 , middle raceways 512 , and lower raceways 514 . Each raceway 510 , 512 , 514 generally extends along walls 24 , 26 , 30 parallel to top wall 22 at different heights. Raceways 510 contain and route radio frequency (RF) cabling exclusively. Raceways 510 are located proximate the top of shelter assembly 16 because RF cables connect radios to antennae 36 and antennae 36 are located at the external top wall 22 of shelter assembly 16 . Raceways 512 contain and route data connections exclusively. Raceways 512 are positioned midway up walls 24 , 26 . Such positioning places raceways 512 and the cabling therein proximate the positioning of signal interface assemblies 112 that provide external connections for the data cabling. Raceways 514 contain and route power cables exclusively. Raceways 514 are internally divided to provide sub-raceways 514 a , 514 b . Raceways 514 a contain and route alternating current (AC) power cables exclusively. Raceways 514 b contain and route direct current (DC) power cables exclusively. Raceways 514 are located proximate lower wall 25 on walls 24 , 26 . However, raceways 514 do not abut shelter floor 27 . Separation from shelter floor 27 permits raceways 514 to remain straight while clearing any wall 26 irregularities necessitated by a wheel well of vehicle 10 . Furthermore, separation from shelter floor 27 decreases the likelihood of electrical complications should water collect on shelter floor 27 .
By separating the cabling into exclusive raceways 510 , 512 , 514 , the potential for cross-talk and data corruption is thereby lessened. Furthermore, the reduced likelihood of data corruption allows the use of interconnection wires having less shielding relative to those that would be needed in a mixed cabling environment. Cables having less shielding are lighter than the more heavily shielded cabling. Lower weight cabling, and lower weight in general, affect the weight distribution within shelter assembly 16 and the handling of vehicle 10 . In general, lower weight components and lower overall weight lessen the size and cost of support components needed to support shelter assembly 16 on vehicle 10 both while stationary and while in motion. Additionally, cables with less shielding have a generally smaller cross-sectional area than equivalent cables with more shielding. Accordingly, an increased number of wires can be fit in a given space, such as raceways 510 , 512 , 514 .
Raceways 510 , 512 , 514 allow the routing of data, RF, and power cables to relevant signal interface assemblies 112 and/or power interface assemblies 112 and/or antennae 36 . Signal interface assembly 112 is illustratively configured to provide for simple and efficient electrical communication between an exterior 40 of shelter assembly 16 and an interior 42 of shelter assembly 16 . More particularly, the signal interface assembly 112 permits communication (e.g., communication signals, electrical power, etc.) between equipment external to shelter assembly 16 and to equipment secured within shelter assembly 16 . As indicated above, signal interface assembly 112 may be positioned within a vertical support structure, such as vertical wall 24 , 26 , 28 , 30 of shelter assembly 16 .
Signal interface assemblies 112 illustratively include support 44 having frame 46 coupled to housing 48 . Frame 46 is illustratively formed of a durable material, such as aluminum, and includes an outer frame 50 and an inner frame 52 spaced apart from each other and defining a chamber 54 therebetween.
Outer frame 50 includes upper frame member 56 coupled to lower frame member 58 . Both upper frame member 56 and lower frame member 58 are angled relative to each other. Water deflector 59 is coupled to lower frame member 58 and is configured to prevent water from collecting at the bottom of signal interface assembly 112 . More particularly, deflector 59 is angled downwardly for directing water downwardly and outwardly from signal interface assembly 112 .
Upper frame member 56 includes first and second openings 62 and 64 defined by rectangular mounting flanges 66 and 68 , respectively. Outer surfaces of mounting flanges 66 and 68 define respective gasket seats 70 and 72 . A plurality of mounting apertures 74 and 76 extend through each mounting flange 66 and 68 , respectively.
Lower frame member 58 includes first and second openings 82 and 84 defined by rectangular mounting flanges 86 and 88 , respectively. Outer surfaces of mounting flanges 86 and 88 define respective gasket seats 90 and 92 . A plurality of mounting apertures 94 and 96 extend through each mounting flange 86 and 88 , respectively.
A plurality of outer or external electrical interface panels 100 , 102 , 104 are removably coupled the outer frame 50 by a plurality of fasteners, illustratively bolts 106 received within mounting apertures 74 , 76 , 94 , 96 of respective frame members 56 , 58 . Electromagnetic interference (EMI) gasket 108 is received intermediate each interface panel 100 , 102 , 104 and its respective gasket seat 70 , 72 , 90 , 92 . EMI gasket 108 is illustratively formed of an electrically conductive material, such as wire mesh material. In one illustrative embodiment, EMI gasket 108 comprises a carbon-filled cellular PTFE matrix. Pressure sensitive adhesive (PSA) may be supported by a rear surface of matrix.
Each outer electrical interface panel 100 , 102 and 104 may be customized with a variety of different electrical connectors or ports. As further detailed herein, panels 100 , 102 , and 104 are modular and may be easily removed and replaced with other panels 100 , 102 , and 104 as desired.
In the illustrative embodiment, electrical interface panel 100 includes connectors 114 , 116 , and 118 . Electrical interface panel 102 illustratively includes electrical connectors 120 . Protective caps 122 may be releasably coupled to connectors 120 and are retained to panel 102 by cords 124 . Electrical interface panel 104 illustratively includes electrical connectors 126 which may include threadably coupled protective caps 128 . It should be appreciated that external panels 100 , 102 , 104 can be used as internal panels, described below, as desired.
Inner frame 52 illustratively includes upper frame member 132 and lower frame member 134 disposed within common plane 136 . Upper frame member 132 includes first and second openings 138 (only one shown) defined by rectangular mounting flanges 142 . Outer surfaces of mounting flanges 142 define gasket seats 146 . A plurality of mounting apertures 150 extend through each mounting flange 142 . Lower frame member 134 includes first and second openings 158 (only one shown) defined by rectangular mounting flanges 162 . Outer surfaces of mounting flanges 162 define gasket seats 166 . A plurality of mounting apertures 170 extend through each mounting flange 162 .
A plurality of inner or internal electrical interface panels 100 , 180 , 182 are removably coupled the inner frame 52 by a plurality of fasteners, illustratively bolts 106 received within mounting apertures 150 , 170 of respective frame members 132 and 134 . Each inner electrical interface panel 100 , 180 , 182 may be customized with a variety of different electrical connectors or ports 114 , 116 , 118 , 184 . Panels 100 , 180 , 182 are modular and may be easily removed and replaced with other panels as desired.
In the illustrative embodiment, electrical interface panels 100 , 180 , 182 include connectors 114 , 116 , 118 , 184 , 185 suitable for receiving interconnect wires 186 able to transmit radio control signals, data signals, and radio transmissions as well as wires 188 able to transmit power.
Electrical wires or cables 186 , 188 interconnect outer panels 100 , 102 , 104 to inner panels 100 , 180 , 182 . More particularly, cables 186 , 188 extend through chamber 54 of the support 44 .
Housing 48 illustratively includes first and second vertical walls 220 interconnected by top and bottom walls 222 , 224 to define a protective enclosure surrounding frame 46 and protecting it from debris and external elements.
Movable cover 226 is coupled to housing 48 through a first or horizontal hinge 228 . Cover 226 is movable between a stowed position substantially vertical, shown in FIG. 5 , to a deployed position offset from vertical, shown in FIG. 9 , to a fully opened position approximately 180 degrees from the closed position.
A pair of side shields or wings 230 are supported by a pair of second or vertical hinges 232 . Side wings 230 are configured to move from a stowed position to a deployed position by rotating or pivoting about a substantially vertical axis.
By choosing the connectors and interface panels 100 , 102 , 104 , external access points are created to link electronics 200 within shelter assembly 16 to electronics 200 within other similar shelter assemblies 16 or elsewhere. In one example, vehicle 10 pulls a mobile power generator 1000 . Mobile power generator 1000 may have signal interface assemblies 112 of its own that, along with proper interconnect wiring, provide for interconnection with shelter assembly 16 . Alternatively, power generator 1000 may have hardwired cabling that couples to interface panels 100 , 102 , 104 . Shelter assembly 16 includes at least two interface panels 100 , 102 , 104 capable of transmitting power. In the provided example, power transmitting interface panels 100 , 102 , 104 are located in signal interface assembly 112 a located in the left rear side wall 28 of shelter assembly 16 , shown in FIG. 3 . A first power interface panel 100 , 102 , 104 receives power from an external source such as mobile power generator 1000 or from another shelter assembly 16 . A second power interface panel 100 , 102 , 104 is present to provide power to other shelter assemblies 16 . Thus, a plurality of shelter assemblies 16 can be daisy-chained together to receive power from a single mobile power generator 1000 or otherwise.
As previously discussed, electronic equipment 200 is located on electronic racks 210 , 212 , 216 , 218 , 220 according multiple considerations. By way of example shown in FIG. 4C , rack 210 includes, cryptographic security device 300 , pre/post selector 302 , High Frequency (HF) communications device 304 , and Data Terminal Set for radio communications 306 . Rack 212 includes tactical data system to fiber converter 308 , digital voice conferencing switch 310 , tactical HF and VHF radio 312 , and Multifunctional Information Distribution System 314 . Rack 216 includes Ethernet patch panels 316 , Multiservice Access Router 318 , Ethernet Switch 320 , multiband manpack radios 322 , 324 , and multichannel transceiver 326 . Rack 218 includes serial patch panels 328 , modems 330 , encryption device 332 , and data secure terminal equipment 334 . Rack 220 includes coded communications device 336 , PCI expansion chassis 338 , Common Aviation Command and Control System 340 , and universal power supply 342 .
Notably, High Frequency (HF) communications device 304 is able to provide/control/connect four channels of HF communication. However, electronics 200 overall are able to control more, for example 16, channels of HF communication. Accordingly, the limitations of High Frequency (HF) communications device 304 restrict the number of channels of HF communication controlled by a lone shelter assembly 16 . To overcome this limitation, external connectors 114 - 116 , present in signal interface assemblies 112 , are provided. External connectors 114 - 116 of one shelter assembly 16 are coupled, via CAT5 cable or otherwise, to one or more other shelter assemblies 16 . This connection allows the electronics 200 of one shelter assembly 16 a , FIG. 10 , to control and link the electronics 200 of the other shelter assemblies 16 b - d , including the High Frequency (HF) communications devices 304 thereof. Accordingly, while each shelter assembly 16 a - d contains a High Frequency (HF) communications device 304 that can control and link four channels of communication, by linking the shelter assemblies 16 , a single shelter assembly 16 can control and link up to sixteen channels of communication. Thus, operators in one shelter assembly 16 can control the electronics 200 in multiple shelter assemblies 16 . Similarly, a single power generator 1000 can couple to shelter assembly 16 a to provide power thereto. Shelter assemblies 16 b - c are then connected in a daisy-chain fashion to shelter assembly 16 a and power generator 1000 to provide power to all shelter assemblies 16 a - d as shown in FIG. 10 .
Accordingly, vehicle 10 provides a platform for transporting a shelter assembly 16 . When shelter assembly 16 is brought into the company of other similar shelter assemblies 16 , shelter assemblies 16 can be linked for data and power via connections in signal interface assemblies 112 . Furthermore, adjacent connected shelter assemblies 16 can be quickly detached. When detached, the respective shelter assemblies 16 can be quickly moved via respective vehicles 10 .
While this invention has been described as having an exemplary design, the present invention may 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.
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A vehicle is provided that includes a shelter thereon that includes electronics therein. The shelter includes ports on the exterior thereof that permit data and power exchange between the vehicle and another similarly configured vehicle. The vehicle further includes dedicated wiring raceways that separate wiring having different uses.
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[0001] This application is a divisional application of co-pending U.S. Ser. No. 13/713,700 filed Dec. 13, 2012, which claimed priority from Canadian application No. 2,761,922 filed Dec. 13, 2011, the priority of which is hereby claimed.
FIELD OF THE INVENTION
[0002] The invention relates generally to continuous sediment removal systems and methods and more particularly to a continuous sediment removal apparatus and method for removing aggregate from a receptacle or melting tank of a snow melting vehicle.
BACKGROUND OF THE INVENTION
[0003] Snow melting vehicles are known in the art and are used to dispose of large amounts of snow by melting the snow and discharging the meltwater, usually into storm drains. The conventional devices typically have a large receptacle or melting tank for receiving the snow and various systems for melting the snow, including water spray devices, grinding devices and heating-type devices which melt the snow.
[0004] It is known that the snow load can include aggregate, such as, for example, sand, gravel, stones, plastics of many shapes and sizes and various heavy metallic objects, which are inadvertently collected along with the snow. This is particularly a problem in big cities where any clogging of the sewers is undesirable and should be avoided.
[0005] In conventional snow melting systems, the entire system must be shut down and the water drained out of the snow receptacle or melting tank in order to gain access to and remove the various debris collected with the snow which accumulate in the snow melting tank during operation.
[0006] Accordingly, there is a need for a continuous system and process for removing aggregate from the receptacle or melting tank of a snow melting vehicle in order to ensure continuous operation thereof. This is desirable to avoid any disruptions during the snow melting operation of the vehicle, which will result in energy savings and increased efficiency.
SUMMARY OF THE INVENTION
[0007] It is, therefore, an aspect of the present invention to provide a continuous sediment removal apparatus and method for removing aggregate from a receptacle or melting tank of a snow melting vehicle.
[0008] One embodiment of the present invention will be a sediment removal apparatus for a snow melting vehicle having a receptacle for receiving a snow load to be transformed inside the receptacle into meltwater, the apparatus including a debris collecting system for displacing debris fallen to a bottom of the receptacle into a collecting chamber disposed adjacent the receptacle and a debris lifting system for raising the debris from the collecting chamber to a position above for gravity discharging the debris outside the collecting chamber.
[0009] The debris collecting system preferably includes a means for creating a water flow loop on the bottom platform of the receptacle for displacing the debris from the bottom of the snow receptacle into the collecting chamber. In a preferred embodiment, the water flow loop may be directed inside a channel disposed on the bottom platform. The debris are directed inside the channel and collected and pushed by the water flow toward and into the collecting chamber. In one particular embodiment, the bottom of the receptacle is inclined toward the channel for directing the debris inside the channel. For example, the inclination of the bottom of the receptacle may be about 15°.
[0010] The debris lifting system preferably includes a rotatable circular frame having a plurality of paddles or blades for lifting the debris above the water line in the collecting chamber. The collecting chamber may have a concave bottom wall and side walls dimensioned to facilitate the debris lifting action of the debris lifting system. Preferably, the debris can be discharged outside the collecting chamber via a discharge chute.
[0011] A snow melting vehicle includes the sediment removal apparatus according to the invention. In a preferred embodiment, a snow melting apparatus can be retrofitted with the sediment removal apparatus of the invention so as to maximize its continuous operation and enhance its feasibility.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The present invention will be further understood from the following detailed description of preferred embodiments of the invention, having regard to the accompanying drawings, in which:
[0013] FIG. 1 is a perspective view of a snow melting vehicle including a sediment removal system according to an embodiment of the present invention;
[0014] FIG. 2 is a view of a receptacle of a snow melting vehicle including the debris collecting system according to an embodiment of the invention;
[0015] FIG. 3 is a plan view of a sediment removal system according to an embodiment of the present invention; and
[0016] FIG. 4 is a cross-sectional view of a floor of a receptacle including a channel and a spaced apart angled cover top according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Reference will now be made in detail to the present preferred embodiments of the invention, an example of which is illustrated in the accompanying drawings.
[0018] Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.
[0019] An exemplary embodiment of the continuous sediment removal system for a snow melting vehicle is shown in FIG. 1 and is designated generally by reference numeral 10 .
[0020] As embodied and illustrated herein, a sediment removal apparatus for use with a snow melting vehicle 10 having a tank or receptacle 20 includes a debris collecting system and a debris lifting system. The debris collecting system moves the debris introduced into the tank 20 with the snow load and fallen on the bottom platform 12 of the tank 20 by means of a water flow into a collecting chamber 40 adjacent the tank 20 . The collecting chamber 40 houses the debris lifting system.
[0021] According to an aspect of the invention, the continuous removal apparatus is purposed to efficiently and continuously remove aggregate (size less than 40 mm), such as, eg. sand, rocks and other heavy small debris, from a meltwater slurry within the tank 20 , for obtaining a separation of the water and aggregate and allowing only a small quantity of the water to escape. This would be applicable to a situation where the water and debris are being dumped in continuously or randomly and will avoid the necessity to shut down the melting process and completely drain the water from the tank 20 in order to remove the debris from the tank 20 .
[0022] One of the main difficulties encountered in conventional snow melting systems is the jamming and wear on moving mechanical parts caused by the varied aggregate that must be removed. In accordance with the present invention, this can be addressed, inter alia, by using a water flow and resilient blades or paddles to apply force to remove the debris as opposed to steel parts pushing and lifting the debris.
[0023] According to an embodiment of the present invention, there is provided a water flow loop that continuously cycles the water through the water/debris tank 20 using a pump 34 , preferably housed in a pump chamber 31 , that is external to the tank 20 . Preferably, the water flow through the tank 20 runs in a partially open top trough or channel 36 disposed on the bottom platform 12 of the tank 20 . Preferably the bottom platform 12 is slanted for gravity directing the debris into the trough 36 .
[0024] According to the invention, the debris are caused by gravity to slide down the slanted floor 12 and get pushed by the water flow out the end of the tank 20 into the debris collecting chamber 40 . Depending upon the amount of turbulence in the tank and the type of aggregate, the angle of the platform 12 required to cause the debris to slide down can vary. Preferably, in accordance with one embodiment of the invention, the angle of the bottom platform 12 of the tank 20 can be about 15° so as to ensure operation of the invention with sand, crusher dust and gravel up to ½″ and rocks up to 1″. However different angles can be envisaged and operable as dictated by the nature of the debris material and water turbulence conditions in the tank 20 .
[0025] A few factors can be considered in determining the required pump 34 size to ensure the water flow is strong enough to move the debris dropped in the trough or channel 36 . It is understood that the water pump 34 is connected to the tank via pipes 35 , and can essentially cause a suction force at one end of the tank and a positive flow at the other end, and, as such, there can be little concern in moving the debris near those locations. However, the area in the middle of the tank 20 can lose a considerable amount of water flow force, due to, in part, the flow water mixing with the water in the tank. Therefore, it can be concluded, that the length of the tank 20 and the water speed are directly related for proper operation of the present invention. For example, in an embodiment of the present invention, a channel 36 can have a length of about 10 feet and the opening area at the end of the tank for the water to flow can be approximately 13 square inches. A water flow speed of between about 400 and 550 feet per minute can be used to ensure that there is enough force in the middle of the tank 20 to move the debris.
[0026] With water entering the tank 20 in a 4″ pipe and then being exposed to the ambient water, with the open top on the trough 36 the water can very quickly mix with the stationary water and lose its velocity. In a preferred embodiment, in order to keep most of this velocity a top 37 can be positioned on this trough 36 which will help it to hold the water velocity longer in the tank. This top 37 can be positioned with a 1″ gap between it and the trough on both sides to allow debris up to 1″ smallest dimension to fall inside the trough or channel 36 . In accordance with another preferred embodiment, in order to ensure good water flow in the middle, the trough cross section can be divided so that there is a lower or distal section that can be fully covered (and therefore does not mix with the tank water) to the middle section of the tank and then the proximal section can be uncovered and mixed with the slower water in the main section of the trough.
[0027] In case of oversized debris, such as, for example anything larger than 1″ in accordance with a preferred, but not limited to, embodiment of the present invention, an open mesh (not shown) may be positioned over the trough area to catch the debris and prevent it from falling into the trough. If there can be large amounts of large objects that may be collected this can quickly block the openings in the mesh and therefore prevent the other debris from falling into the trough. The surface area of this mesh will have to be increased by raising it and/or adding multiple levels and an easy method of lifting and removing the mesh for cleaning.
[0028] According to one mode of operation of the invention, after the water flow displaces the debris from the channel or trough 36 outside the main tank 20 into the collecting chamber 40 , the debris can be discharged outside the collecting chamber 40 . The collecting chamber can be provided with an effective method of removing the debris, according to the embodiments described hereinbelow.
[0029] According to one embodiment of the present invention, the collecting chamber 40 can be fully sealed. The collecting chamber can also have a volume and shape adapted to cause a significant slowing of the water flow to allow the debris to settle onto the bottom of the chamber. According to this embodiment, the water flow exit can be positioned at the top corner of the chamber in order to prevent the debris being sucked out of the chamber. In this embodiment, the chamber can have an isolating valve at the entrance and exit of the chamber. To determine when the chamber is filled enough to require cleaning a debris sensing level switch or a weight measurement apparatus and method can be used.
[0030] In order to remove the debris from the chamber the two isolating valves will have to be closed and the water pump should be turned off. This will prevent significant loss of primary chamber water. The chamber can then be opened and dumped with a small loss of water and also a small amount of down time if the opening method is automated.
[0031] According to another embodiment of the present invention, the secondary chamber 40 can include a spinning rotor frame 41 with wiper blades 42 , the blades being preferably made of a resilient material, such as rubber or polycarbonate. The spinning rotor frame 41 can be rotated via a drive chain 43 , for example. In one method of operation, the debris entering the collecting chamber 40 can be swept sideways and lifted by the blades 42 of the spinning wheel 41 . As illustrated and embodied herein, the wheel 41 raises the debris in an arc until it reaches the water surface. At this point any amount of water held on the wiper starts to flow off. Operation of the wheel 41 at a predetermined speed can allow a significant amount of the water to drain from the blades 42 before it nears the tops center location. A discharge chute can be conveniently provided in the top center area directly under so that the debris can be, thus, gravity discharged outside the collecting chamber. According to an embodiment of the invention, the debris can slide down the discharge chute and can be collected with a very low water concentration.
[0032] The wheel 41 turn rate can be adapted and operated based on the quantity of debris that is being removed and on the number of wiper blades 42 , in order to ensure that debris removal does not bring a large amount of water with it. In one embodiment of the invention, the wheel 41 can include twenty (20) paddles or blades 42 . For example, a rotor speed can be between about 5 and 7 rpm. As explained above, it can be appreciated that the rotor speed can vary depending on the debris concentration in the water.
[0033] For example, the blades 42 can be made of 60 Durameter™ neoprene with a view to lasting for a very long time while also still being quite cheap to replace. In one exemplary application of the invention, where a goal was to remove as little water as possible, a 1″ gap between the sides of the rubber blades and the walls of the secondary chamber casing can be provided so as to allow the water to pour out quicker as the blade 42 moves above the water line and prevent any jam of debris between the rotor structure and the chamber wall.
[0034] As embodied herein, an aspect of the present invention is the reduction of the amount of debris sucked through the pump 34 . As known in the art, debris going through a pump over time will cause erosion and wear the impeller and the pump casing down so that it will need to be replaced.
[0035] In order to mitigate the possible erosion of the pump, as illustrated and embodied herein the suction intake from the collecting chamber 40 to the pump 34 via pipe 35 can preferably be as close as practical to the top of the chamber or the water surface without, however, sucking air into the pump and the intake size should be larger to reduce effective suction pressure/area and reduce the forces pulling on the debris. Another preferred embodiment can use a screen to block the debris while having a large enough surface area so as to minimize that the scree can be blocked with debris by virtue of the suction force of the pump 34 . Moreover, as known in the art, cycling the pump backwards periodically can help to remove and debris from the screen.
[0036] Variations, adaptations, and modification to the above described preferred embodiments of the invention are possible without departing from the scope and content of the invention, as described in the claims appended hereto.
LIST OF REFERENCE CHARACTERS
[0000]
10 —snow melting vehicle
11 —burner
12 —tank bottom platform
20 —melting tank
31 —pump chamber
32 —discharge chute
33 —access area
34 —pump
35 —pipe
36 —channel
37 —angled cover top
40 —collecting chamber
41 —wheel
42 —blades
43 —drive chain
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A snow melting vehicle includes a receptacle for receiving a snow load to be melted inside the receptacle into meltwater and a debris collecting system for moving the debris fallen to the bottom of the receptacle into a collecting chamber disposed adjacent the receptacle. A debris lifting system is also provided for raising the debris from the collecting chamber to a position above the meltwater filling the collecting chamber, whereby the meltwater is substantially drained before the debris is gravity discharged outside the snow melting vehicle.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to remedial well bore sealing methods and compositions, and more particularly, to improved methods and compositions for sealing subterranean zones whereby their permeabilities are reduced and their strengths are increased.
2. Description of the Prior Art
In the drilling of oil and gas wells using the rotary drilling method, drilling fluid is circulated through the drill string and drill bit and back to the surface by way of the well bore being drilled. The drilling fluid maintains hydrostatic pressure on the subterranean zones through which the well bore is drilled and circulates cuttings out of the well bore. The drilling fluid includes gelled and particulate material which builds up on the walls of the well bore and prevents fluid loss into subterranean zones penetrated by the well bore. However, relatively large openings such as channels, fractures, vugs and the like are often encountered which communicate the well bore with one or more high permeable subterranean zones. Because of the size of such openings filter cake from the drilling fluid does not seal the openings and drilling fluid is lost from the well bore into the subterranean zones. This in turn causes drilling fluid circulation to be lost whereby the drilling operations must be terminated while remedial steps are taken to seal the subterranean zones. Highly permeable subterranean zones which produce water or other undesirable fluids into the well bore are also often encountered which must be sealed.
Heretofore, a variety of methods and sealing compositions have been developed and used for combating drilling fluid lost circulation problems and problems relating to formation fluids flowing into the well bore. However, such methods and compositions have often been unsuccessful due to inadequate viscosity development by the sealing compositions used. Also, the methods of placement of the sealing compositions have been inadequate to cause plugging of the weak highly permeable portions of the zones being treated and to prevent bypassing of such portions by the sealing compositions and/or the wash-out of the compositions.
After a well bore penetrating a subterranean hydrocarbon producing formation has been drilled, the well bore is often completed by sealing a string of pipe such as casing or a liner in the well bore. That is, a sealing composition such as a hydraulic cement slurry is pumped into the annular space between the walls of the well bore and the exterior of the string of pipe disposed therein. The cement slurry is permitted to set in the annular space thereby forming an annular sheath of hardened substantially impermeable cement therein. The cement sheath physically supports and positions the pipe in the well bore and bonds the pipe to the walls of the well bore whereby the undesirable migration of fluids between zones or formations penetrated by the well bore is prevented.
The cement compositions utilized in cementing pipe strings in well bores must often be lightweight to prevent excessive hydrostatic pressures from being exerted on weak permeable zones penetrated by the well bores. In some applications, the heretofore utilized lightweight cement compositions have still had densities such that the cement compositions can not be displaced into well annuluses all the way to the surface due to the hydrostatic pressure of the cement compositions exceeding the fracture gradient of one or more of the weak permeable zones penetrated by the well bores. The resulting upper unsupported portion of the casing can and often does experience early damage due to formation cave-ins, subsidence and the like.
Thus, there is a continuing need for improved methods and sealing compositions for sealing highly permeable subterranean zones through which fluids undesirably flow into or out of the well bores penetrating the zones and for simultaneously increasing the mechanical strengths of the zones.
SUMMARY OF THE INVENTION
The present invention provides improved methods and compositions for sealing a subterranean zone penetrated by a well bore into which fluids contained in the well bore are lost or from which fluids undesirably flow into the well bore. Simultaneously, the mechanical strength of the zone is increased whereby a higher hydrostatic pressure can be utilized in the well bore without fracturing the zone.
The compositions of this invention are low viscosity, polymeric epoxide compositions which form resilient high strength impermeable sealing masses. A polymeric epoxide composition of this invention is basically comprised of water, a polymerizable monomer, an effective amount of a polymerization initiator, a hardenable epoxide containing liquid and a hardening agent. The composition can also include a particulate filler to impart a desired density and rigidity thereto.
The methods of this invention basically comprise the steps of introducing a polymeric epoxide composition of the invention into a subterranean zone penetrated by a well bore into which fluids contained in the well bore are lost or from which fluids undesirably flow into the well bore, and then causing the composition to polymerize and harden in the zone.
It is, therefore, a general object of the present invention to provide improved remedial well bore sealing methods and compositions.
Other and further objects, features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of preferred embodiments which follows.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention provides methods and polymeric epoxide sealing compositions for sealing a subterranean zone penetrated by a well bore and simultaneously improving the mechanical strength of the zone. A polymeric epoxide composition of this invention is basically comprised of a polymerizable monomer, a polymerization initiator, an epoxide containing liquid and a hardening agent. A particulate solid filler material is preferably added to the composition to impart a desired density and/or degree of rigidity thereto.
A variety of polymerizable monomers can be utilized in the polymeric epoxide compositions. Examples of such monomers include acrylic acid, methacrylic acid, acrylamide, methacrylamide, 2-methacrylamido-2-methyl propane sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, N-N-dimethylacrylamide, vinyl sulfonic acid, N,N-dimethylamino-ethylmethacrylate, 2-triethylammoniumethyl methacrylate chloride, N,N-dimethylaminopropylmethacrylamide, methacrylamide, methacrylamidopropyl trimethylammonium chloride, N-vinyl pyrrolidone, vinylphosphonic acid, methacryloyloxyethyl trimethylammonium sulfate and mixtures thereof.
Additional more preferred monomers include hydroxyethylacrylate, hydroxymethylacrylate, hydroxyethylmethacrylate, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, polyethylene and polypropylene glycol acrylate and methacrylate and mixtures thereof. Of the various monomers that can be used, hydroxyethylacrylate is most preferred.
The monomer or monomers are generally present in the composition in an amount in the range of from about 10% to about 90% by weight of the composition.
While various polymerization initiators can be used, azo polymerization initiators defined by the following formula are preferred:
R.sub.1 --N═N--R.sub.2
wherein: ##STR1##
Azo polymerization initiators within the scope of the above formula are temperature activated at various temperatures and are not activated by oxidation-reduction mechanisms. The term "activation temperature" is used herein to mean that temperature at which half the molar amount of a compound converts to free radicals in a period of 10 hours.
As is understood by those skilled in the art, a particular azo polymerization initiator can be selected for use in a polymeric epoxide composition of this invention which has an activation temperature equal to or slightly less than the temperature of the subterranean zone to be sealed. Further, since the azo compounds are not activated by oxidation-reduction mechanisms, the reducing metals commonly encountered in pumping equipment and tubular goods of wells do not cause premature gelation of the composition.
The azo polymerization initiators which are generally useful in accordance with this invention have activation temperatures ranging from about 111° F. to about 190° F. Examples of preferred such azo compounds are 2,2'-azobis (N,N'-dimethylene isobutyramidine) dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, and 2,2'-azobis [2-methyl-N-(2-hydroxyethyl) propionamide]. The activation temperatures of these initiators are 111° F., 133° F. and 187° F., respectively. The quantity of the azo initiator employed is generally an amount in the range of from about 0.01% to about 2% by weight of monomer in the composition.
The azo initiator utilized is dissolved in a small amount of water and the resulting solution is added to the composition.
The polymeric epoxide sealing compositions of this invention must have low viscosities whereby they readily flow into the pores of permeable subterranean zones. Generally, the sealing compositions have a selected viscosity in the range of from about 10 to about 90 centipoises. While various low viscosity epoxide containing liquids can be used in the compositions, preferred such liquids are selected from the group of diglycidyl ethers of 1,4-butanediol, neopentyl glycol and cyclohexane dimethanol. A suitable epoxide containing liquid comprised of the diglycidyl ether of 1,4-butanediol is commercially available from the Shell Chemical Company of Houston, Tex. under the trade name "HELOXY®67". This epoxide containing liquid has a viscosity at 25° C. in the range of from about 13 to about 18 centipoises, a molecular weight of 202 and a one gram equivalent of epoxide per about 120 to about 130 grams of the liquid. A suitable diglycidyl ether of neopentyl glycol is commercially available from Shell Chemical Company under the trade name "HELOXY®68". This epoxide containing liquid has a viscosity at 25° C. in the range of from about 13 to about 18 centipoises, a molecular weight of 216 and a one gram equivalent of epoxide per about 130 to about 140 grams of the liquid. A suitable diglycidyl ether of cyclohexanedimethanol is commercially available from Shell Chemical under the trade name "HELOXY®107". This epoxide containing liquid has a viscosity at 25° C. in the range of from about 55 to about 75 centipoises, a molecular weight of 256 and a one gram equivalent of epoxide per about 155 to about 165 grams of the liquid. The epoxide containing liquid utilized is generally included in the polymeric epoxide composition in an amount in the range of from about 10% to about 90% by weight of the composition.
A variety of hardening agents, including, but not limited to, aliphatic amines, aliphatic tertiary amines, aromatic amines, cycloaliphatic amines, heterocyclic amines, amido amines, polyamides, polyethylamines and carboxylic acid anhydrides can be utilized with the above described epoxide containing liquids. Of these, aliphatic amines, aromatic amines and carboxylic acid anhydrides are the most suitable.
Examples of aliphatic and aromatic amine hardening agents are triethylenetetraamine, ethylenediamine, N-cocoalkyltrimethylenediamine, isophoronediamine, N-aminoethylpiperazines, imidazoline, 1,2-diaminecyclohexane, diethyltoluenediamine and tris(dimethylaminomethylphenol). Examples of carboxylic acid anhydride hardening agents are methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, polyazelaic polyanhydride and phthalic anhydride. Of these, triethylenetetraamine, ethylenediamine, N-cocoalkyltrimethylenediamine, isophorone diamine, diethyltoluenediamine and dimethylaminomethylphenol are preferred, with isophorone diamine, diethyltoluenediamine and tris(dimethylaminomethylphenol) being the most preferred.
One or more of the above hardening agents can be utilized in a polymeric epoxide sealant composition of this invention. The hardening agent or mixture of hardening agents is generally included in the composition in an amount in the range of from about 25% to about 45% by weight of the epoxide containing liquid in the composition.
A solid filler material can be added to the polymeric epoxide compositions to provide a desired density and/or degree of rigidity to the compositions after they have polymerized and hardened. While a variety of filler materials which are well known to those skilled in the art can be utilized, preferred filler materials are ultra fine crystalline silica having an average particle size of about 5 microns, barite, clays, solid materials which hydrate in the presence of water such as hydraulic cements and pozzolan materials, and mixtures of such filler materials. Generally, the filler material used is added to the polymeric epoxide composition of this invention in an amount in the range of from about 100% to about 300% by weight of the composition.
Upon polymerization of the monomer or monomers used and hardening of the epoxide liquid or liquids used, the polymeric epoxide compositions are highly resilient and seal as well as improve the mechanical strengths of subterranean zones containing them. The components of the compositions can be varied in kind and amount to obtain desired properties such as density, durability, degree of rigidity etc. In addition, the polymeric epoxide compositions are highly adhesive whereby they readily bond to the surfaces of subterranean formation materials.
The methods of this invention for sealing a well bore penetrating a subterranean zone into which fluids contained in the well bore are lost or from which fluids undesirably flow into the well bore and for simultaneously improving the mechanical strength of the zone are comprised of the following steps. A polymerizable and hardenable polymeric epoxide composition of this invention having a selected viscosity at 25° C. in the range of from about 10 to about 90 centipoises is prepared comprised of a polymerizable monomer, a polymerization initiator, an epoxide containing liquid and a hardening agent. After the polymeric epoxide composition is prepared, it is placed by way of the well bore into the subterranean zone to be sealed. Thereafter, the polymeric epoxide composition is allowed to polymerize and harden to thereby seal the well bore and strengthen the subterranean zone.
As will now be understood, the polymerization of the monomer or monomers in the polymeric epoxide composition and the hardening of the epoxide liquid or liquids therein, are delayed for desired periods of time to allow extended penetration of the composition into the subterranean zone to be sealed. As mentioned, in addition to sealing the subterranean zone, the mechanical strength of the zone is increased whereby higher density fluids can be utilized in the well bore without fracturing the zone. Finally, the polymeric epoxide compositions of this invention are much less expensive than hardenable epoxy compositions which have been utilized heretofore.
In order to further illustrate the methods and compositions of this invention, the following examples are given.
EXAMPLE 1
A mixture of a hydroxyethylacrylate polymerizable monomer, a 2,2'-azobis (2-amidinopropane) dihydrochloride polymerization initiator dissolved in a small amount of water, an epoxide containing liquid comprised of the diglycidyl ether of 1,4-butanediol and a diethyltoluenediamine hardening agent was prepared. The mixture contained a 1:1 ratio of the polymerizable monomer and the epoxide containing liquid. The mixture also included microsand (powdered crystalline silica) added thereto in an amount of 150% by weight of the mixture. The mixture was allowed to cure at 140° F. for 72 hours.
A second mixture containing only hydroxyethylacrylate, 2,2'-azobis (2-amidinopropane) dihydrochloride dissolved in a small amount of water and microsand added thereto in an amount of 150% by weight of the mixture was prepared. This mixture was also allowed to cure at 140° F. for 72 hours.
A third mixture containing only an epoxide containing liquid comprised of the diglycidyl ether of 1,4-butanediol, a diethyltoluenediamine hardening agent and microsand added to the mixture in an amount of 150% by weight of the mixture was prepared and allowed to cure at 140° F. for 72 hours.
The three cured mixtures were tested for compressive strength in accordance with the test procedures set forth in API Specification for Materials and Testing for Well Cements, API Specification 10, 5th ed., Jul. 1, 1990. The results of these tests are set forth in Table I below.
TABLE I__________________________________________________________________________COMPRESSIVE STRENGTH TESTSComposition Commponents Polymerization Hardening.sup.4 agent, by Initiator.sup.2 by weight of Epoxide.sup.3 containing weight of epoxide Microsand, % bySampleMonomer.sup.1, % by weight monomer in the liquid, % by weight of containing liquid in weight of CompressiveNo of the composition composition the composition composition composition Strength,__________________________________________________________________________ psi1 50 0.25 50 33 150 20102 100 0.5 -- -- 150 4333 -- -- 100 33 150 10,300__________________________________________________________________________ .sup.1 Hydroxyethylacrylate .sup.2 2,2azobis(2-amidinopropane)dihydrochloride .sup.3 The diglycidyl ether of 1,4butanediol .sup.4 Diethyltoluenediamine
From Table I it can be seen that after polymerizing and hardening, the composition of this invention had good compressive strength.
EXAMPLE 2
A 1.75 inch diameter×2 inch long core was cut from Berea sandstone having a permeability of approximately 200 millidarcies, a compressive strength of 12,613 psi (at a confined pressure of 1,000 psi) and a tensile strength of 309 psi. The core was dried in a vacuum oven, and the outer cylinderical surface of the core was coated with an impermeable epoxy coating. After the epoxy coating had hardened and been dried in a vacuum oven for 24 hours, the core was placed in a standard API static fluid loss cell having a length of 5 inches. The cell was filled with a polymeric epoxide sealing composition of this invention and sealed. A pressure of 1,000 psi of nitrogen was applied to the cell and 10 milliliters of filtrate from the core was collected. A 1,000 psi pressure and a curing temperature of 140° F. was then applied to the cell for 72 hours after which the cured core was removed from the cell. The cured core was then cored to obtain a 1 inch diameter by 2 inches long sample which was used to determine the air permeability, compressive strength and tensile strength of the cured core.
The test process was repeated utilizing a polymeric composition which did not include an epoxide containing liquid or hardening agent. The results of these tests are given in Table II below.
TABLE II__________________________________________________________________________PERMEABILITY AND OTHER TESTSComposition Components Hardening.sup.4 Polymerization Epoxide.sup.3 agent, % by Initiator.sup.2, % by Containing weight of epoxideMonomer.sup.1, % weight of Liquid, % by containing liquid Tensile Young'sSampleby weight of the monomer in the weight of the in the Air Compressive Strength, Poisson's ModulusNo. composition composition composition composition Permeability, md Strength, psi psi Ratio × 10.sup.6,__________________________________________________________________________ psiUntreated-- -- -- -- 226.19 12,613 309 0.242339 1.680Core1 50 0.25 50 33 0.03 15,919 855 0.245023 1.8972 100 0.5 -- -- 9.5 13,398 490 0.134152 1.339__________________________________________________________________________ .sup.1 Hydroxyethylacrylate .sup.2 2,2azobis(2-amidinopropane)dihydrochloride .sup.3 The diglycidyl ether of 1,4butanediol .sup.4 Diethyltoluenediamine
From Table II it can be seen that the polymeric epoxide composition of this invention decreased the permeability of the core sample to near zero and increased the compressive and tensile strength of the sample.
Thus, the present invention is well adapted to carry out the objects and attain the features and advantages mentioned as well as those which are inherent therein. While numerous changes may be made by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended claims.
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The present invention relates to improved methods and compositions for sealing subterranean zones penetrated by well bores to reduce their permeabilities and increase their compressive strengths. The methods basically comprise the steps of introducing an aqueous sealing composition into a subterranean zone comprising a polymerizable monomer, a polymerization initiator, a hardenable epoxide containing liquid and a hardening agent, placing the sealing composition by way of the well bore into the subterranean zone and allowing the sealing composition to polymerize and harden whereby the well bore is sealed.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to wall construction, and more particularly to a method and apparatus for providing a connection between a pair of wall studs to provide a backing connector for anchoring wall mounted structures such as cabinets, handrails and grab bars.
2. Description of Prior Art
Historically, the framework of a light framed building wall was formed entirely of wood members, such as wood studs and top and bottom sills. In recent years, however, the use of metal studs has gained acceptance, especially in commercial buildings, but also in residential construction. Some designers prefer to use metal studs rather than wood studs. Galvanized steel studs can be considered stronger than wood in some respects, will not rot, and are not subject to damage by pests such as termites.
Metal studs are typically formed of sheet metal bent to encompass a cross sectional area having nominal dimensions of two inches by four inches. To conform to architectural plans and building code requirements, metal studs are formed of sheet metal bent into a generally C-shaped cross-section in which a relatively broad central web is flanked by a pair of narrower sides that are bent at right angles to the web. The web typically has a uniform nominal width of either four inches or 3⅝ inches. The sides of the C-shaped stud typically extend to a nominal distance of two inches from the web. To enhance structural rigidity to the flanges of the stud, the flanges are normally bent over into a plane parallel to and spaced from the plane of the web. These turned over edges of the sides thereby form marginal lips which are typically one quarter to one half inch in width. Conventionally, the metal studs are erected with the webs oriented on the same side in the same direction.
In building construction, there are certain situations which require the building studs to be braced or linked transversely to provide enhanced structural rigidity. The studs must be transversely bridged when they are over eight feet in length so that they provide adequate stability in a lateral direction within the wall which they support.
In certain instances, the metal studs require transverse backing between the studs in a building so as to provide structural support against forces acting normal to or parallel to the plane of the wall assembly. For example, structural backing must be provided between adjacent parallel studs to provide necessary structural stability for the installation of wall structures such as cabinets, hand rails and grab bars. Hand rails and grab bars may have to conform to requirements of the Americans with Disabilities Act, i.e., withstand 250 pounds of point load pressure outward and downward parallel to the plane of the wall. A common way to provide backing is to shape pieces of plywood between adjacent studs and use screw fasteners to attach these pieces to adjacent studs. The number and placement of backing plywood pieces is determined by how much of the framework needs backing.
The use of fire-stops, bridging and backing in construction trade is well known in the prior art, and there are a number of patents that teach especially made backing pieces, bridging members and blocking members that are formed from sheet metal for use with sheet metal studs. Construction Codes and Fire Codes require that these devices be positioned between metal studs to: (1) reinforce uniformly laterally spaced parallel metal studs; (2) discourage the spread of fire, smoke and gases within interior walls; and (3) anchor hand rails and grab bars to metal studs. Typically, drywall (also known as plasterboard, wallboard, gypsum board, sheetrock, or gyprock) panels cover the studs and backing and is attached thereto.
SUMMARY OF THE INVENTION
The present invention provides a connection between two metal studs that is easily erected and provides a solid facing into which fasteners can be anchored for securely attaching components to a hollow wall sheathed with sheet rock. The objects of this invention are achieved by providing a connection between standard metal studs with a separate backing connector designed to easily, quickly and securely connect to the studs when they are in place and to provide a member for anchoring into through the sheet rock between the studs.
The first wall stud of the connection has an elongated, vertically disposed, substantially planar web. The web has a given width and has an exterior surface on one side of the web and an interior surface on the opposite side of the web. The first wall stud is also formed with a substantially planar side member laterally connected to the web, the side member being disposed orthogonally to the web and running alongside the web, the side member extending from the interior surface side of the web and having an outer surface on one side of the side member and an interior surface on the opposite side of the side member. The first wall stud also has a substantially planar lip flange laterally connected to the side member opposite from the web, the lip flange being disposed parallel to the web and orthogonally to the side member, the lip flange running alongside the side member and being disposed on the interior surface side of the web. The lip flange has a selected width that is substantially narrower than the web. The lip flange has an interior surface that faces the interior surface of the web on one side of the lip flange and a facing surface on the opposite side of the lip flange.
The second wall stud of the connection is disposed in parallel relation to the first wall stud and is spaced a selected distance away from the first wall stud such that the first wall stud and the second wall stud are not in contact. Similar to the first wall stud, the second wall stud has an elongated, vertically disposed, substantially planar web, the web having a given width that is the same as the width of the web of the first wall stud. The web of the second wall stud has an exterior surface on one side of the web and an interior surface on the opposite side of the web. The second wall stud is also formed with a substantially planar side member laterally connected to the web of the second wall stud. The side member is disposed orthogonally to the web and runs alongside the web of the second wall stud. The side member extends from the interior surface side of the web and has an outer surface. The side member of the second wall stud also has a substantially planar lip flange laterally connected to the side member opposite from the web. The lip flange is disposed parallel to the web and orthogonally to the side member of the second wall stud. The lip flange runs alongside the side member and is disposed on the interior surface side of the web. The lip flange has a selected width that is substantially narrower than the web and is the same as the selected width of the lip flange of the first stud.
As is common in most stick-frame construction, the first wall stud is also disposed in relation to the second wall stud such that exterior surface of the web of the second wall stud is closest to the interior surface of the web of the first wall stud and the outer surfaces of the first and second side members of the wall studs are substantially parallel.
The backing connector of the connection is disposed substantially orthogonally to the first and second wall studs and connects the first wall stud to the second wall stud. The backing connector has a first elongated, substantially planar backing web having a longitudinal axis with a first end and a second end. The longitudinal axis is disposed substantially orthogonally to the elongated first and second wall studs with the first end of the backing connector being disposed adjacent the first wall stud and the second end of the backing connector being disposed adjacent the second wall stud. The backing web has an exterior surface on one side of the backing web and an interior surface on the opposite side of the backing web. The exterior surface of the backing web is substantially in alignment with the outer surfaces of the side members of the first and second wall studs.
The backing connector is also formed with a substantially planar upper flange laterally connected to the backing web, the upper flange being disposed at an angle to the backing web and running alongside and above the backing web. The upper flange extends from the interior surface side of the backing web a selected distance that is greater than the selected width of the lip flange of the first stud. The backing connector is also formed with a substantially planar lower flange laterally connected to the backing web, the lower flange being disposed at an angle to the backing web and running alongside and below the backing web. The lower flange extends from the interior surface side of the backing web a selected distance that is greater than the selected width of the lip flange of the first stud.
To make the connection to the first wall stud, the upper and lower flanges at the first end of the backing connector extend past the lip flange of the first stud towards the interior surface of the web of the first wall stud, and the upper and lower flanges are each formed with a notch where the upper and lower flanges receive the lip flange of the first wall stud, and a first end projecting tab if formed on the backing connector that is connected to the backing web at the first end of the backing web and extends generally parallel to the backing web. The first end projecting tab interfaces with a portion of the outer surface of the side member of the first wall stud. In the preferred embodiment, two such first end projecting tabs are provided near the upper and lower reinforcing flanges.
To make the connection to the second wall stud, the second end of the backing connector interfaces with portions of one or more of the exterior surface of the second wall stud or the outer surface of the side member of the second wall stud, but does not interface with or contact the lip flange of the second wall stud, and separate fasteners connect the second end of the backing connector to the second wall stud where the second end of the backing connector interfaces with the second wall stud.
To make a more secure connection between the backing connector and the first wall stud, the material of the upper and lower flanges is disposed on both sides of the lip flange of the first wall stud such that the lip flange of the first wall stud is disposed between material of the upper and lower flanges.
Also to make the connection more secure, the upper and lower flanges at the second end of the backing connector can extend to and make contact with the exterior surface of the second wall stud. In the preferred embodiment, a stabilizing flange is angularly attached to and formed from the material of both the upper and lower flanges respectively at the second end of the backing connector, and these stabilizing flanges interface with the exterior surface of the web of the second wall stud.
Also to make the connection more secure, the upper and lower flanges at the first end of the backing connector are formed with foot tabs that are disposed at an angle to the upper and lower flanges and interface with interior surface of the first side member.
It is also an object of the present invention to provide a backing connector that can be adjusted to span a variety of selected distances between the first and second studs. This is accomplished by forming the backing connector as two portions, an inner portion and an outer portion with the inner portion received within the outer portion such that the inner and outer portions slidingly engage with each other. In this form of the invention the upper and lower flanges at the second end of the backing connector are formed with reinforcing flanges attached to the upper and lower flanges opposite from the backing web, and the backing web at and near the second end of the connector has an inner part and an outer part that are in overlapping and interfacing engagement, and the upper and lower flanges at and near the second end of the backing connector have an inner part and an outer part that are in overlapping and interfacing engagement, and the reinforcing flanges of the upper and lower flanges at and near the second end of the backing connector have an inner part and an outer part that are in overlapping and interfacing engagement with each other.
In the preferred embodiment of the present invention, the entire length of both the upper flange and the lower flange are formed with the reinforcing flanges, as the reinforcing flanges add rigidity to the backing connector; however, the reinforcing flanges do not need to extend to the first end of the backing connector.
To further achieve the object of making a secure connection, a first end abutment flange is angularly joined to the first end of the backing web. The first end abutment flange interfaces with the facing surface of the lip flange of the first wall stud. Similarly, a second end abutment flange is angularly joined to the second end of the backing web and interfaces with the exterior surface of the web of the second wall stud.
Also to further achieve the object of making a secure connection, a second end projecting tab is connected to the backing web at the second end of the backing web and extends generally parallel to the backing web. The second end projecting tab interfaces with a portion of the outer surface of the side member of the second wall stud. In the preferred embodiment, two such second end projecting tabs are provided near the upper and lower flanges. The first and second end projecting tabs preferably extend less than half the distance across the side members of the wall studs, such that it is easy to install backing connectors at the same level across multiple pairs of studs.
In the preferred embodiment, and in order to make a more secure connection, fasteners also connect the first end of the backing connector to the first wall stud. The preferred fasteners are self-drilling, self-tapping metal screws. In the preferred embodiment, one fastener is driven through each of the first end projecting tabs into the side member of the first wall stud. Also, in the preferred embodiment, one fastener is driven through each of the stabilizing flanges into the web member of the second wall stud.
It is a further object of the present invention to provide a method of easily making a connection between a first wall stud and a second wall stud with a backing connector. The connection of the present invention is made by first positioning the notches of the upper and lower flanges at the first end of the backing connector so that they receive the lip flange of the first wall stud. Next, the second end of the backing connector is brought into engagement with the second wall stud by rotating the backing connector and by adjusting the relative engagement of the inner part and an outer part of the backing web, the inner part and outer part of the upper and lower flanges, and the inner part and outer part of the reinforcing flanges so that the backing connector is long enough to form an interfacing engagement with certain surfaces of the second wall stud. In the last step, fasteners are driven through selected members at the ends of the backing connector and into the first and second wall studs.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an upper front right perspective view of multiple connections made according to the present invention between a plurality of wall studs and the backing connector of the present invention, showing the same connector installed between wall stud pairs with differing spacing.
FIG. 2 is an upper front right perspective view of a backing connector of the present invention being installed between a pair of wall studs.
FIG. 3 is a lower rear left perspective view of the notches where the upper and lower flanges of the backing connector of the present invention showing the interface with the side member of a wall stud.
FIG. 4 is a front elevation view of the part of the backing connector of the present invention that has notches in its upper and lower flanges.
FIG. 5 is a back elevation view of the part of the backing connector shown in FIG. 4 .
FIG. 6 is a top plan view of the part of the backing connector shown in FIG. 4 .
FIG. 7 is a top plan cutaway view of the part of the backing connector shown in FIG. 4 and taken along line 7 - 7 .
FIG. 8 is a right end elevation view of the part of the backing connector shown in FIG. 4 .
FIG. 9 is a left end elevation view of the part of the backing connector shown in FIG. 4 .
FIG. 10 is a front elevation view of the part of the backing connector of the present invention that does not have notches in its upper and lower flanges.
FIG. 11 is a back elevation view of the part of the backing connector shown in FIG. 10 .
FIG. 12 is a top plan cutaway view of the part of the backing connector shown in FIG. 10 and taken along line 12 - 12 .
FIG. 13 is a top plan view of the part of the backing connector shown in FIG. 10 .
FIG. 14 is a left end elevation view of the part of the backing connector shown in FIG. 10 .
FIG. 15 is a right end elevation view of the part of the backing connector shown in FIG. 10 .
FIG. 16 is a front elevation view of the part of the whole backing connector of the present invention.
FIG. 17 is a top plan cutaway view of the part of the backing connector shown in FIG. 16 and taken along line 17 - 17 .
FIG. 18 is a top plan view of the part of the backing connector shown in FIG. 16 .
FIG. 19 is a top plan view of a connection made according to the present invention between a pair of wall studs and the backing connector of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
As shown in FIG. 1 , in the preferred embodiment, the drywall backing connection 1 of the present invention includes a first wall stud 2 having a first stud web 3 with a first vertical edge 4 , a first side flange or side member 5 extending from the first vertical edge 4 , the first side flange 5 having a second vertical edge 4 , and a lip flange 6 extending from the second vertical edge 4 . The elongated, vertically disposed, substantially planar web 3 has a given width and has an exterior surface 21 on one side of the web 3 and an interior surface 221 on the opposite side of the web 3 . The substantially planar side member 5 laterally connected to the web 3 is disposed orthogonally to the web 3 and runs alongside the web 3 . The side member 5 extends from the interior surface side 221 of the web and has an outer surface 12 on one side of the side member 5 and an interior surface 11 on the opposite side of the side member 5 . The substantially planar lip flange 6 is laterally connected to the side member 5 opposite from the web 3 . The lip flange 6 is disposed parallel to the web 3 and orthogonally to the side member 5 . The lip flange runs alongside the side member 5 and is disposed on the interior surface side 221 of the web 3 , such that lip flange 6 is closer to the second wall stud 2 than the web 3 of the first wall stud 2 , with the second wall stud being defined as the wall stud 2 to which the second end 13 of the backing connector 7 is attached. As shown in FIG. 1 , the wall studs 2 can serve as either the first wall stud 2 of a particular connection with a backing connector 7 or the second wall stud 2 of a different connection with a backing connector 7 . The lip flange 6 has a selected width that is substantially narrower than the web 3 , the lip flange 6 has an interior surface 222 that faces the interior surface 221 of the web 3 on one side of the lip flange 6 and a facing surface 22 on the opposite side of the lip flange 6 .
Similarly, in the preferred embodiment, a second wall stud 2 has a first stud web 3 with a first vertical edge 4 , a first side flange or side member 5 extending from the first vertical edge 4 , the first side flange 5 having a second vertical edge 4 , and a first lip flange 6 extending from the second vertical edge 4 . The second wall stud 2 is disposed in parallel relation to the first wall stud 2 and spaced a selected distance away from the first wall stud 2 such that the first wall stud 2 and the second wall stud 2 are not in contact. The elongated, vertically disposed, substantially planar web 3 has a given width that is the same as the width of the web 3 of the first wall stud 2 , the web 3 also has an exterior surface 21 on one side of the web 3 and an interior surface 221 on the opposite side of the web 3 . The substantially planar side member 5 laterally connected to the web 3 of the second wall stud 2 is disposed orthogonally to the web 3 and runs alongside the web 3 of the second wall stud 2 . The side member 5 extends from the interior surface side 221 of the web 3 and has an outer surface 12 on one side of the side member 5 and an interior surface 11 on the opposite side of the side member 5 . The substantially planar lip flange 6 is laterally connected to the side member 5 opposite from the web 3 . The lip flange 6 is disposed parallel to the web 3 and orthogonally to the side member 5 . The lip flange runs alongside the side member 5 and is disposed on the interior surface side 221 of the web 3 the lip flange. The lip flange 6 has a selected width that is substantially narrower than the web 3 , the lip flange 6 has an interior surface 222 that faces the interior surface 221 of the web 3 on one side of the lip flange 6 and a facing surface 22 on the opposite side of the lip flange 6 .
In any particular connection with a single selected backing connector 7 , connecting a first wall stud 2 and a second wall stud 2 , as shown in FIG. 2 , the first wall stud 2 is disposed such that exterior surface 21 of the web 3 of the second wall stud 2 is closest to the interior surface 221 of the web 3 of the first wall stud 2 and the outer surfaces 12 of the first and second side members 5 are substantially parallel.
As shown in FIG. 1 , in the preferred embodiment, the preferred variable-length, backing connector 7 , is formed with a backing web 8 , having a first longitudinal side edge 9 , a second longitudinal side edge 9 , and a first end 13 , and a second end 13 . In the preferred embodiment, the first and second longitudinal side edges 9 are parallel. An upper longitudinal flange 10 extends at an angle from the first longitudinal edge 9 . The upper longitudinal flange 10 has a first end 15 proximate the first end 13 of the first backing web 8 , and a second end 15 proximate the second end 13 of the backing web. A lower longitudinal flange 10 extends at an angle from the second longitudinal side edge 9 . The lower longitudinal flange 10 has a first end 15 proximate the first end 13 of the backing web 8 , and a second end 15 proximate the second end 13 of the backing web 8 . In the preferred embodiment, the upper and lower longitudinal flanges 10 are parallel.
The backing connector 7 is disposed substantially orthogonally to the first and second wall studs 2 and connects the first wall stud 2 to the second wall stud 2 . As mentioned, the backing connector 7 includes the first elongated, substantially planar backing web 8 . The backing web 8 has a longitudinal axis 300 with first and second ends 13 . The longitudinal axis 300 is disposed substantially orthogonally to the elongated first and second wall studs 2 with the first end 13 of the backing connector 7 being disposed adjacent the first wall stud 2 and the second end 13 of the backing connector 7 being disposed adjacent the second wall stud 2 . The backing web 8 has an exterior surface 301 on one side of the backing web 8 and an interior surface 302 on the opposite side of the backing web 8 . The exterior surface 301 of the backing web 8 is substantially in alignment with the outer surfaces 12 of the side members 5 of the first and second wall studs 2 .
As noted above the substantially planar upper flange 10 is laterally connected to the backing web 8 . The upper flange 10 is disposed at an angle, preferably a 90 degree angle, to the backing web 8 and runs alongside and above the backing web 8 . The upper flange 10 extends from the interior surface side 302 of the backing web 8 a selected distance that is greater than the selected width of the lip flange 6 of the first stud 2 . As also noted above, the planar lower flange 10 is laterally connected to the backing web 8 , the lower flange 10 being disposed at an angle, also preferably 90 degrees, to the backing web 8 and running alongside and below the backing web 8 . The longitudinal flange 10 extends from the interior surface side 302 of the backing web 8 a selected distance that is greater than the selected width of the lip flange 6 of the first stud 2 .
As shown in FIG. 3 , the upper and lower flanges 10 at the first end 13 of the backing connector 7 extend past the lip flange 6 of the first stud 2 towards the interior surface 221 of the web 3 of the first wall stud 2 , and the upper and lower flanges 10 are each formed with a notch 400 where the upper and lower flanges 10 receive the lip flange 3 of the first wall stud 2 .
As best shown in FIGS. 1 , 4 and 5 , the backing connector 7 is also formed with a first end projecting tab 18 that is connected to the backing web 8 at said first end 13 of the backing web 8 and extends generally parallel to the backing web 8 , the first end projecting tab 18 interfacing with a portion of the outer surface 12 of the side member 5 of the first wall stud 2 . In the preferred embodiment the backing connector 7 is formed with a pair of first end projecting tabs 18 near the upper and lower longitudinal flanges 10 .
In the preferred embodiment, the first ends of the upper and lower flanges 10 are formed with a first L-shaped end tabs 16 that extend over the first lip flange 6 of the first wall stud 2 .
As shown in FIGS. 1 and 2 , the backing connector 7 is fastened to the second wall stud 2 proximate the second web end 13 . The second end 13 of the backing connector 7 interfaces with portions of one or more of the exterior surface 21 of the second wall stud 2 or the outer surface 12 of the side member 5 of the second wall stud 2 , but does not interface with or contact the lip flange 6 of the second wall stud 2 . As shown in FIG. 2 , one or more fasteners 91 connect the second end 13 of the backing connector 7 to the second wall stud 2 where the second end 13 of the backing connector 7 interfaces with the second wall stud 2 .
As shown in FIG. 3 , material of the upper and lower flanges 10 is disposed on both sides of the lip flange 6 of the first wall stud 2 such that the lip flange 6 of the first wall stud 2 is disposed between the material of the upper and lower flanges 10 . Preferably, the notch 400 is provided with an orthogonally disposed to the longitudinal axis 300 of the backing member 7 abutment edge that contacts and can interface along the facing surface 22 of the lip flange 6 , and with an angled edge on the interior surface 222 of the lip flange 6 to allow the backing connector 7 to be easily swung into place over the lip flange 6 .
As shown in FIG. 19 , the upper and lower longitudinal flanges 10 at the second end 13 of the backing connector can extend to and make contact with the exterior surface 21 of the second wall stud 2 . In the preferred embodiment, a stabilizing flange 19 is angularly attached to and formed from the material of both the upper and lower longitudinal flanges 10 respectively at the second end 13 of the backing connector 7 , and these stabilizing flanges 19 interface with the exterior surface 21 of the web 3 of the second wall stud 2 . The stabilizing flanges 19 are preferably disposed orthogonally to the longitudinal flanges 10 .
As shown in FIGS. 2 and 3 , the upper and lower flanges 10 at the first end 13 of the backing connector 7 are formed with foot tabs 17 that are disposed at an angle, preferably a 90 degree angle, to the upper and lower flanges 10 and interface with the interior surface 11 of the first side member 5 .
As best shown in FIGS. 1 and 16 - 19 , the backing connector 7 can be adjusted to span a variety of selected distances between the first and second studs 2 . This is accomplished by forming the backing connector as two portions, an inner portion and an outer portion with the inner portion received within the outer portion such that the inner and outer portions slidingly engage with each other. In this form of the invention the upper and lower flanges 10 at the second end 13 of the backing connector 7 are formed with reinforcing flanges 20 attached to the upper and lower flanges 10 opposite from the backing web 8 , and the backing web 8 at and near the second end 13 of the connector 7 has an inner part 81 and an outer part 82 that are in overlapping and interfacing engagement, and the upper and lower flanges 10 at and near the second end 13 of the backing connector 7 have an inner part 101 and an outer part 102 that are in overlapping and interfacing engagement, and the reinforcing flanges 20 of the upper and lower flanges 10 at and near the second end 13 of the backing connector 7 have an inner part 201 and an outer part 202 that are in overlapping and interfacing engagement with each other.
In the preferred embodiment of the present invention, the entire length of both the upper flange 10 and the lower flange 10 are formed with the reinforcing flanges 20 , as the reinforcing flanges 20 add rigidity to the backing connector 7 ; however, the reinforcing flanges 20 do not need to extend to the first end 13 of the backing connector 7 .
As shown in FIGS. 2 , 3 , 10 and 14 , a first end abutment flange 14 is angularly joined to the first end 13 of the backing web 8 . The first end abutment flange 14 interfaces with the facing surface 22 of the lip flange 6 of the first wall stud 2 . Similarly, a second end abutment flange 14 is angularly joined to the second end 13 of the backing web 8 and interfaces with the exterior surface 21 of the web 3 of the second wall stud 2 . The abutment flanges 14 are preferably disposed orthogonally to the backing web 8 .
As shown in FIG. 1 , a second end projecting tab 18 is connected to the backing web 8 at the second end 13 of the backing web 8 and extends generally parallel to the backing web 8 . The second end projecting tab 18 interfaces with a portion of the outer surface 12 of the side member 5 of the second wall stud 2 . In the preferred embodiment, two such second end projecting tabs 18 are provided near the upper and lower flanges 10 . The first and second end projecting tabs preferably extend less than half the distance across the side member 5 of the wall studs 2 , such that it is easy to install backing connectors 7 at the same level across multiple pairs of studs 2 .
In the preferred embodiment, and in order to make a more secure connection, fasteners 91 also connect the first end 13 of the backing connector 7 to the first wall stud 2 . The preferred fasteners 91 are self-drilling, self-tapping metal screws. In the preferred embodiment, one fastener 91 is driven through each of the first end projecting tabs 18 into the side member 5 of the first wall stud 2 . Also, in the preferred embodiment, one fastener 91 is driven through each of the stabilizing flanges 19 into the web member 3 of the second wall stud 2 .
As best shown in FIG. 2 , the connection of the present invention is made by first positioning the notches 400 of the upper and lower flanges 10 at the first end 13 of the backing connector 7 so that they receive the lip flange 6 of the first wall stud 2 . Next, the second end 13 of the backing connector 7 is brought into engagement with the second wall stud 2 by rotating the backing connector 7 and by adjusting the relative engagement of the inner part 81 and an outer part 82 of the backing web, the inner part 101 and outer part 102 of the upper and lower flanges 10 , and the inner part 201 and outer part 202 of the reinforcing flanges 20 so that the backing connector 7 is long enough to form an interfacing engagement with certain surfaces of the second wall stud 2 . In the last step, fasteners 91 are driven through selected members, preferably in preformed fastener openings 90 , at the ends 13 of the backing connector 7 and into the first and second wall studs 2 .
The preferred backing connector 7 of the present invention is formed from two pieces of sheet metal on a progressive die with the inner part of the two pieces inserted into engagement with the outer part. As noted above, the longitudinal side edges 9 of the backing connector 7 are preferably parallel. The backing connector is preferably formed from a two generally rectangular blanks of sheet metal that allows the pieces to be cut on a progressive die with minimal waste. The parallel side edges 9 also allow the backing connector 7 to be installed at a horizontal level easily. The studs of the present invention are also preferably formed of sheet metal.
As shown in FIG. 1 , multiple backing connectors can be attached to side-by-side studs of varying distances between the studs.
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A connection between standard metal studs with a separate backing connector is provided. The backing connector has a planar backing web with lateral longitudinal flanges that receives the lip flange of a first wall stud and a projecting tab that interfaces with the side member of the first wall stud. The backing connector also has members that interface with and attach to selected portions of the surfaces of the second wall stud without engaging the lip flange of the second wall stud. The backing connector is adjustable in length.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Section 371 of International Application No. PCT/EP2013/069787, filed Sep. 24, 2013, which was published in the German language on Apr. 10, 2014 under International Publication No. WO 2014/053351 A1, which claims the benefit of U.S. Provisional Application No. 61/710,226, filed Oct. 5, 2012, the disclosures of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to the production of noble metal oxalate complexes. Hereinafter, noble metal oxalate complexes shall also be referred to as noble metal oxalates for reasons of simplicity. Specifically, the invention relates to the production of noble metal oxalate complexes from noble metal precursors and oxalic acid and/or oxalic acid salts.
[0003] The production of noble metal oxalate complexes from noble metal precursors and oxalic acid and/or oxalic acid salts has been known for a long time. The production of platinum oxalate complexes usually proceeds through the reaction of platinum oxide hydrate (platinum(IV)-hydroxoacid, dihydrogenhexahydroxoplatinate(IV), hydroxoplatinic acid) and oxalic acid at a temperature of 60° C. (K. Krogmann, P. Dodel, Chem. Ber. 99, 3408-3418 (1966)).
[0004] EP 0 254 935 A1 describes a method for the production of silver oxalate having a large particle diameter. According to this method, silver salt and oxalic acid or oxalic acid salts are reacted at a pH value of no more than 5. The reaction is carried out at a temperature from 0 to 80° C., preferably at a temperature from 40 to 60° C.
[0005] The production of noble metal oxalate complexes from noble metal precursors and oxalic acid and/or oxalic acid salts is an exothermic reaction, in which heat and CO 2 are produced. The temperature can increase above the decomposition point of the noble metal oxalate complexes in the course of the reaction, which simultaneously releases more CO 2 . In this context, see, for example, Sano, Isamu; Bulletin; 15, p. 196, “On the Catalytic Decomposition of Oxalic Acid by Colloidal Platinum” (1940), and Szabo, Z. G. and Biro-Sugar, E., Zeitschrift für Elektrochemie, vol. 50, no. 8, p. 869-874, “Kinetik der thermischen Zersetzung von Silberoxalat” (1956).
[0006] For safety reasons, when the reaction is carried out on a large scale, it is therefore necessary to take into consideration that the product must not be decomposed by heat that is produced during the reaction.
BRIEF SUMMARY OF THE INVENTION
[0007] It is therefore the object of the present invention to provide a method for the production of noble metal oxalate complexes that can be carried out on a large scale. Accordingly, the method enables the course of the reaction to be controlled. It is necessary that the amounts of gas and heat produced during the synthesis can be reliably guided away from the reactor.
[0008] These objectives are met by a method for the production of noble metal oxalate complexes which comprises reacting a noble metal precursor with oxalic acid and/or oxalic acid salt, wherein the product noble metal oxalate complexes are also added to the reaction as an auto-catalyst.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0009] The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.
[0010] In the drawing:
[0011] FIG. 1 is a graph of heat flow as a function of temperature for a platinum oxalate solution.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The invention provides a method for the production of noble metal oxalate complexes, in which noble metal precursors are reacted with oxalic acid and/or oxalic acid salts, and in which noble metal oxalate is introduced into the reaction mixture as an auto-catalyst.
[0013] According to the invention, noble metal precursors and oxalic acid and/or oxalic acid salts are used as reactants. Many starting substances are conceivable, whereby the noble metal precursor and oxalic acid and/or oxalic acid salt reactants are obviously different from the noble metal oxalate end-product.
[0014] The term “noble metal” includes, in particular, the classical noble metals Pt, Pd, Ir, Rh, Os, Ru, Ag, and Au, and also the semi-noble metal Re. Preferred noble metals include silver, palladium, and platinum; platinum is particularly preferred.
[0015] Examples of noble metal precursors include noble metal salts and noble metal oxide hydrates. Examples of noble metal salts include noble metal nitrates, noble metal acetates, and mixtures thereof. It is also conceivable to use mixtures of a noble metal oxide hydrate and noble metal salt or salts. However, noble metal oxide hydrate, in particular platinum oxide hydrate, also referred to as platinum(IV) hydroxoacid (see Gmelin, Verlag Chemie GmbH, Berlin p. 47-48 (1940)) has proven to be preferred. The salt which is used also depends on the type of noble metal. For example, silver oxalate can be produced from silver nitrate, and it is preferable to use platinum-(IV) hydroxoacid or any of the salts thereof, such as K 2 Pt(OH) 6 , Na 2 Pt(OH) 6 etc., as starting materials for platinum oxalate. As a matter of rule, the free acid is preferred.
[0016] Oxalic acid salts may include, for example, sodium oxalate, ammonium oxalate, potassium oxalate or mixtures thereof. However, it is also feasible to use a mixture of oxalic acid and one or more oxalic acid salt(s). As before, the preferred reactants depend on the type of noble metal. Accordingly, e.g., ammonium oxalate can be used to advantage for the production of silver oxalate. However, as a matter of rule, the use of free oxalic acid is particularly preferred. Accordingly, it is also preferable to use oxalic acid for the production of platinum oxalate.
[0017] According to the invention, a combination of noble metal oxide hydrate and oxalic acid reactants is particularly preferred because only carbon dioxide and water are produced in addition to the noble metal oxalate complexes.
[0018] It is particularly preferred to add the oxalic acid or oxalic acid salt at a suitable stoichiometric ratio. Referring to the production of platinum oxalate complexes, this means that 1.8 to 2.8 molar equivalents of oxalic acid or oxalic acid salt relative to platinum in the form of the platinum precursor are added. This reaction produces a mixture of different dioxalatoplatinic acids or platinum oxalate complexes. A detailed description of mixtures of this type is in K. Krogmann, P. Dodel, Chem. Ber. 99, pp. 3402-3407 and 3408-3418 (1966).
[0019] The form in which the oxalic acid and/or oxalic acid salt is added depends on the noble metal oxalate complex to be produced. Preferably, it is added in the form of an aqueous solution or as a solid. Oxalic acid is preferred and is preferably added as a solid in the form of oxalic acid dihydrate.
[0020] The reaction is carried out at a temperature below the decomposition temperature of the noble metal oxalate complexes. For defining the safety margin for the reaction temperature in the present case, a hazard evaluation needs to be considered which takes into account important parameters of process technology, parameters of equipment technology, and considerations and data of safety technology, such as, e.g., the decomposition temperature or decomposition range of the noble metal oxalate complexes. The reaction temperature may then be adjusted to come close to the decomposition temperature as a function of the existing data.
[0021] The reaction is therefore preferably performed at a temperature below the decomposition temperature of the noble metal oxalate complexes. In this context, the difference between reaction temperature and decomposition temperature should be at least 1° C., preferably at least 5° C. The decomposition temperature is defined to be the temperature at which decomposition starts, in which the start of decomposition is determined using long-term differential thermal analysis in glass ampules at a heating rate of 0.05 K/min in accordance with DIN 51007. Proven to be preferred for the reaction of noble metal precursors and oxalic acid and/or oxalic acid salts is a temperature range between 0° C. and 56° C., particularly preferably between 30° C. and 52° C., and even more particularly preferably between 35 ° C. and 45 ° C.
[0022] Referring, in particular, to platinum oxalate complexes already decomposing at a temperature of 57° C. (see FIG. 1 ), it is preferable to carry out the reaction at a temperature of up to 56° C., particularly preferably at up to 52° C., and even more particularly preferably at up to 45° C. The reaction is carried out above 0° C., preferably above 30° C., and particularly preferably at a temperature of 35° C. to 42° C.
[0023] According to the invention, the decomposition temperature of the noble metal oxalate complexes is determined by long-term differential thermal analysis (DTA) in accordance with DIN 51007 (June 1994). The determination can be done on solutions of noble metal oxalate complexes that correspond to the product solution, in a closed glass ampule at a heating rate of 0.05 K/min between 0° C. and a temperature above the measured peak trough (see FIG. 1 ). According to the invention, the decomposition temperature shall be understood to be the temperature when the first deviation (see FIG. 1 , 57° C.) of the measuring curve from the starting baseline curve is noted (5.2 DIN 51007).
[0024] In the present case, 2934.5 mg of a 10% by weight platinum oxalate solution in water were used. The measurement proceeded in glass ampules at a heating rate of 0.05 K/min. FIG. 1 shows the heat flow W/g as a function of the temperature between 2° C. and 83° C.
[0025] In the present description, temperature-equilibrate shall be understood to mean that the reaction mixture is set to a certain temperature. The temperature equilibration can be effected, e.g., with water.
[0026] It is advantageous to first produce an aqueous solution or suspension of noble metal oxide hydrate or noble metal salt. Referring to the production of platinum oxalate complexes, it is preferred to first produce an aqueous suspension of platinum oxide hydrate (H 2 [Pt(OH) 6 ] or platinum-(IV) hydroxoacid). It is preferable to produce a 5 to 25% by weight suspension, particularly preferably a 7-15% by weight suspension relative to platinum in water.
[0027] Surprisingly, it has been found that the introduction of small amounts of noble metal oxalate complexes into the reaction mixture has an auto-catalytic effect. The addition of noble metal oxalate complexes significantly shortens the induction period of the reaction (very slow starting phase of the reaction). This enables the course of the reaction to be controlled. Therefore, the added noble metal oxalate complexes are also referred to as auto-catalysts hereinafter. According to the invention, a small amount of auto-catalyst is added. Preferably, the amount of auto-catalyst to be added is 1×10 −4 to 5×10 −2 molar equivalents of noble metal relative to the noble metal in the noble metal precursor. Particularly preferably, the amount of auto-catalyst to be added is 5×10 −4 to 1×10 −2 molar equivalents of noble metal relative to the noble metal in the noble metal precursor, and particularly preferably the amount of auto-catalyst to be added is 5×10 −4 to 7×10 −3 molar equivalents of noble metal relative to the noble metal in the noble metal precursor. It is preferable to add the auto-catalyst in aqueous solution. Customary concentrations are 5-20% by weight, e.g. 8-15% by weight.
[0028] Expediently, the noble metal oxalate complexes corresponding to the product to be produced are used as auto-catalyst (in line with the meaning of the term, “auto-catalyst”). This means that platinum oxalate is used as an auto-catalyst for the production of platinum oxalate and silver oxalate is used as an auto-catalyst for the production of silver oxalate, etc.
[0029] The order in which the noble metal precursor, auto-catalyst, and oxalic acid and/or oxalic acid salt are added is less important. The auto-catalyst may be added to the reaction solution or suspension concurrently with the total amount of oxalic acid and/or oxalic acid salt, concurrently with part of the oxalic acid and/or oxalic acid salt, or before the addition of oxalic acid and/or oxalic acid salt. A solution or a suspension of noble metal precursor may be provided first or added later in this context.
[0030] If the noble metal precursor is provided first and the auto-catalyst and oxalic acid are added concurrently, the addition should be made at a temperature below the desired reaction temperature. The addition is preferably made at a temperature of up to 37° C., particularly preferably at up to 32° C. The reaction mixture thus formed is then heated up to the desired reaction temperature. The heating rate is then a function of when the reaction starts.
[0031] However, it has proven to be advantageous to first provide the noble metal precursor in solution or suspension, then add the auto-catalyst, and to add at least the major part of the oxalic acid or oxalic acid salt only after the reaction temperature is reached.
[0032] The oxalic acid or the oxalic acid salt may be added in one or more aliquots. The aliquots may be equal in size, or multiple aliquots differing in size may just as well be added. If the aliquots differ in size, it is advantageous to first add a larger aliquot and then add one or more smaller aliquots or progressively smaller aliquots. Accordingly, it has proven to be advantageous to first add an aliquot of 0.4 to 1.4 molar equivalents relative to platinum in the form of the platinum precursor and to subsequently add, e.g., multiple equal amounts of the remaining oxalic acid or the remaining oxalic acid salt. This can be done, for example, in a single further addition of e.g., 0.4 to 1.4 molar equivalents, in two further additions of, e.g., 0.2 to 0.9 molar equivalents, in three further additions of, e.g., 0.1 to 0.7 molar equivalents, in four further additions of, e.g., 0.1 to 0.6 molar equivalents, etc. However, it is just as conceivable to add the oxalic acid or the oxalic acid salt evenly and continuously.
[0033] It is advantageous to stir the solution or suspension during the reaction. In a preferred embodiment, the oxalic acid or the oxalic acid salt is added as a function of the stirring conditions, concentration of the solution or suspension, and reactor dimensions. As a matter of principle, the rate at which oxalic acid or oxalic acid salt can be added may be set quite well based on the production of CO 2 and on the temperature profile.
[0034] Noble metal oxalate complexes produced as specified above may advantageously be used as precursors for noble metal catalysts.
EXAMPLES
[0035] The following examples serve purposes of illustration and are not to be construed as to limit the invention.
Measuring Method and Analyses
[0036] NMR and UV spectroscopy were used in the qualitative analyses. The UV spectrum was measured at room temperature using a Specord® 200 UV spectrometer made by Analytic Jena AG and 1 cm cuvettes (QS Suprasil® quartz glass cuvettes made by Heraeus Quarzglas GmbH) over a measuring range from 190 nm-1,100 nm at a resolution of 2 nm. The nuclear resonance spectroscopic measurements were carried out using a Bruker Avance 400 MHz NMR spectrometer (Reference Example 1) and a Bruker Avance 600 MHz NMR spectrometer (Example, Reference Examples 2 and 3).
[0037] The platinum content was determined by gravimetry.
[0038] The reactants used were platinum (IV) hydroxoacid (H 2 [Pt(OH) 6 ]) from in-house production (wt (Pt): 55.51%), oxalic acid dihydrate for analysis EMSURE® ACS, ISO, Reag. Ph Eur made by Merck KGaA, art. no. 100495, and platinum oxalate from in-house production (wt (Pt): 11.72%).
Example 1
Production of Platinum Oxalate at 40° C., in the Presence of Auto-Catalyst, Oxalic Acid Added in 5 Aliquots
[0039] A total of 10 g Pt (50 mmol) in the form of 18.01 g H 2 [Pt(OH) 6 ] were placed in 54.29 ml demineralized water (“VEW”) in a 250 ml three-necked round flask. Then, 0.04 g Pt oxalate (0.24 mmol Pt) were added as an auto-catalyst at room temperature (23° C.) while stirring (250 U/min) with a magnetic stirrer. A pale-greenish suspension was thus produced.
[0040] Time: 0 min: The suspension was heated in a water bath from room temperature to 40° C. over the course of 20 minutes.
[0041] Time 20 min: As soon as the temperature of the suspension had reached 40° C., one of five equal aliquots of 2.568 g (20 mmol) oxalic acid dihydrate was added. Instantaneously gas production was observed, which lasted for a period of 60 minutes. A total of 270 ml CO 2 were captured.
[0042] Time 80 min: Once gas production ceased, another aliquot of 2.568 g (20 mmol) oxalic acid dihydrate was added. A total of 40 ml CO 2 were captured.
[0043] Time 140 min: Once gas production ceased, another aliquot of 2.568 g (20 mmol) oxalic acid dihydrate was added. The color of the solution changed from green to turquoise-blue after 10 min. A total of 300 ml CO 2 were captured over the course of 60 min.
[0044] Time 200 min: Once gas production ceased, another aliquot of 2.568 g (20 mmol) oxalic acid dihydrate was added. A total of 270 ml CO 2 were captured over the course of 60 min.
[0045] Time 260 min: Once gas production ceased, another aliquot of 2.568 g (20 mmol) oxalic acid dihydrate was added. A total of 300 ml CO 2 were captured over the course of 110 min. No further gas production was observed during 10 more minutes of stirring at 40° C.
[0046] Time 380 min: The heating system was switched off and the solution was stirred until room temperature was reached. The mixture was filtered through a 0.2 μm membrane filter (Sartorius filtration unit). Filtration was carried out within 30 minutes.
[0047] A total of 74.49 g of product having a Pt content of 13.40% by weight were obtained with the yield being 99.82% relative to platinum. 13 C-NMR (151 MHz, 299.6 K, DMSO-d 6 capillary): δ=168.70; 167.16 ppm. UV-VIS: 627 nm (A=0.399); 417 nm (0.415).
Reference Example 1
Production of Platinum Oxalate at 50° C.
[0048] A total of 10 g Pt (50 mmol) in the form of 18.01 g H 2 [Pt(OH) 6 ] were placed in 54.29 ml demineralized water (“VEW”) in a 250 ml three-necked round flask. Then, 12.93 g (100 mmol) oxalic acid dihydrate were added while stirring (250 U/min) with a magnetic stirrer. A milky, yellowish-white suspension was thus produced.
[0049] Time: 0 min: The suspension was heated in a water bath at a rate of approx. 1° C./10 min starting at 19° C.
[0050] Time 180 min: The solution started to turn greenish at a temperature of 35° C.
[0051] Time 210 min: The solution turned turquoise-blue at a temperature of 38° C.
[0052] Time 220 min: The solution turned deep-blue at a temperature of 39° C.
[0053] Time 230 min: The temperature of the solution reached 40° C. Gas production was for a period of 50 min, during which the temperature of the solution reached 45° C.
[0054] Time 350 min: The temperature reached 50° C. There was no longer any gas production.
[0055] Time 510 min: The heating system was switched off, the solution was stirred further until room temperature was reached. The mixture was filtered through a 0.2 μm membrane filter
[0056] (Sartorius filtration unit). Filtration was carried out within 90 minutes.
[0057] A total of 47.82 g of product having a Pt content of 20.75% by weight were obtained with the yield being 99.23% relative to platinum. 13 C-NMR (100.6 MHz, 303 K, DMSO-d 6 capillary): δ=168.43; 166.72 ppm. UV-VIS 664 nm (A=0.731); 417 nm (0.763).
Reference Example 2
Production of Platinum Oxalate at 40° C., No Auto-Catalyst
[0058] Reference Example 1 was repeated except that the solution was heated for a period of 210 minutes from 23° C. to a temperature of 40° C. The color of the solution turned greenish after 150 minutes at a temperature of 35° C. After 190 minutes, when the temperature was 37° C., the solution began to turn blueish, and after 230 minutes gas production was observed for a period of 65 minutes.
[0059] A total of 80.972 g of product having a Pt content of 12.25% by weight were obtained with the yield being 99.19% relative to platinum. 13 C-NMR (151 MHz, 298 K, DMSO-d 6 capillary): δ=168.16; 166.67 ppm. UV-VIS 641.05 nm (A=0.342); 417 nm (0.374).
Reference Example 3
Production of Platinum Oxalate at 40° C., No Auto-Catalyst, Oxalic Acid Added in 5 Aliquots
[0060] A total of 10 g Pt (50 mmol) in the form of 18.01 g H 2 [Pt(OH) 6 ] were placed in 54.29 ml demineralized water (“VEW”) in a 250 ml three-necked round flask.
[0061] Time 0 min: The suspension was heated in a water bath from 20° C. to 40° C. over the course of 40 minutes.
[0062] Time 40 min: As soon as the temperature of the suspension had reached 40° C., one of five equal aliquots of 2.568 g (20 mmol) oxalic acid dihydrate was added. Neither a color change nor the production of gas was observed. After another 60 minutes, another aliquot of 2.568 g (20 mmol) oxalic acid dihydrate was added. As before, neither a color change nor the production of gas was observed.
[0063] Time 160 min: Another 2.568 g (20 mmol) aliquot of oxalic acid dihydrate was added. Ten minutes later, the solution turned greenish. Another 30 minutes later (at 200 minutes), the color of the solution changed from green to turquoise-blue.
[0064] Time 220 min: Another 2.568 g (20 mmol) aliquot of oxalic acid dihydrate was added. Ten minutes later, gas production was observed.
[0065] Time 280 min: Another 2.568 g (20 mmol) aliquot of oxalic acid dihydrate was added. Gas production continued until the 300 minutes time point. No gas production was observed any longer after this time.
[0066] Time 330 min: The heating system was switched off. The solution was stirred further until room temperature was reached. The mixture was filtered through a 0.2 μm membrane filter (Sartorius filtration unit). Filtration was carried out within 30 minutes.
[0067] A total of 77.39 g of product having a Pt content of 12.85% by weight were obtained with the yield being 99.45% relative to platinum. 13 C-NMR (151 MHz, 299.6 K, DMSO-d 6 capillary): δ=168.16; 166.66 ppm. UV-VIS 664 nm (A=0.373); 417 nm (0.403).
[0068] It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.
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The production of noble metal oxalate complexes from noble metal precursors and oxalic acid and/or oxalic acid salts is an exothermic reaction, in which heat and CO 2 are produced, is described. The temperature can increase above the decomposition point of the noble metal oxalate complexes in the course of the reaction, which simultaneously releases more CO 2 . For safety reasons, when the reaction is carried out on a large scale, it is therefore necessary to take into consideration that the product must not be decomposed by heat that is produced during the reaction. Therefore, according to the invention, a method for the production of noble metal oxalate complexes is provided, in which the product noble metal oxalate complexes are added to the reaction mixture as an auto-catalyst.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to particulate polybutadiene crosslinked materials and a process of making the same. The particulate crosslinked product of the invention finds extensive application as blends with resinous materials used in machineries and electronics industries, as solid lubricating agents added to greases and lubricating oils, as anti-friction improvers for paints and inks and further as cosmetics blends.
2. Prior Art
Polybutadiene crosslinked particles are widely recognized for their high strength, high thermal resistance, low dielectric constant and low moisture-absorption characteristics, and are usually made available by mechanically pulverizing their initial massive crosslinked material.
However, such crosslinked particles are susceptible to discoloration upon exposure to ultraviolet rays and hence find limited commercial application. They are not suitable for outdoor application as they undergo abrupt discoloration from white to brown when exposed to sunlight. Mechanical pulverization of a massive or cloddish polybutadiene crosslinked material involves a difficulty in removing polymerization heat generated during its preparation and further in obtaining uniformly minute and regularly shaped particles at high yield. Emulsification crosslinking methods are also known and effective in so far as concerns the removal of polymerization heat, but not satisfactory in that the particles are liable to become coagulated or cohesive during crosslinking and fail to grow sufficiently minute.
SUMMARY OF THE INVENTION
It has now been found by the present inventors that polybutadiene crosslinked material in the form of a truly spherical particulate form can be obtained at high yield by subjecting a polybutadiene to crosslinking reaction with stirring in the presence of a silicone compound and surprisingly that the resulting crosslinked particles retain highly concentrated silicone chemically bonded to their surface layer whereby discoloration by ultraviolet rays is reduced to an absolute minimum as compared to conventional counterparts.
It is therefore a primary object of the present invention to provide a process of preparing a high yield of particulate polybutadiene crosslinked material which possesses excellent properties including high mechanical strength, high thermal resistance, low dielectric constant and low moisture-absorption, and in addition thereto, a substantial freedom of discoloration by ultraviolet radiation.
Another object of the invention is to provide particulate polybutadiene crosslinked material of the above mentioned character which further presents a substantially truly spherical and regularly shaped configuration and a relatively low particle size distribution.
These and other objects, features and advantages of the invention will appear manifest upon reading the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
The polybutadiene used in the invention may be obtained by subjecting a butadiene to one of many known polymerization reactions such as anionic polymerization using Na dispersant or organo-alkali metal catalyst, a radical polymerization (with organic peroxide catalyst), a cationic polymerization (with Friedel-Craft catalyst), and a coordination anionic polymerization (with Ziegler catalyst).
Generally, polybutadienes contain vinyl double bonds as well as main chain (trans and cis) double bonds. A polybutadiene eligible for the purpose of the invention contains usually more than 5 mol percent, preferably 10-100 mol percent, more preferably 30-100 mol percent of vinyl double bonds based on monomer unit and has a number average molecular weight usually in the range of 500-100,000 and preferably in the range of 1,000-20,000. The polybutadiene may be a butadiene homopolymer or a copolymer having monomers other than butadiene introduced into the polymer skeleton, in which instance the comonomers may be styrene and alpha-methylstyrene and is present in a unit amount of 20 mol percent or less, preferably 0-15 mol percent.
The polybutadiene may be modified, if necessary, with acids or peroxides to introduce hydroxide or carboxyl groups into the polymer. Such modified polymers include for example a polybutadiene added with maleic acid anhydride and a polymer having emulsified carbon-carbon double bonds, in which instance the reactive groups introduced into the polymer is present in an amount of usually 20 mol percent or less, preferably 0-15 mol percent based on butadiene unit.
The inventive product is produced by crosslinking the above described polybutadienes in the presence of a silicone compound according to a radical crosslinking, a cationic crosslinking or an anionic crosslinking process. In the case of radical crosslinking, the reaction can be initiated by some air dissolved in a liquid silicone compound, but more effectively by the use of a suitable radical initiator such as organic peroxides including methylethyl ketone peroxide, 1,1-bis(t-butyl peroxy)-3,3,5-trimethyl cyclohexane, t-butylhydroperoxide, dicumyl peroxide and 2,5-di(t-butyl peroxide)hexene-3, or aromatic hydrocarbons including 2,3-dimethyl-2,3-diphenyl butane and 2,3-diethyl-2,3-diethyl butane. These initiators may be used in combination and are used in an amount of usually 0.01-10 parts by weight, preferably 0.05-5 parts by weight per 100 weight parts of polybutadiene.
The radical crosslinking reaction is effected at a temperature of usually 100°-350° C., preferably 150°-320° C., more preferably 220°-300° C., though dependent upon decomposition temperature of the radical initiator used.
The term silicone compound as used herein designates a compound having a main chain consisting of repetitive units of siloxane bonds. Such a compound is eligible for the purpose of the invention if it is liquid at the above specified crosslinking temperature. Preferred examples of such compounds include dimethyl silicone, methylphenyl silicone, methyl trifluoropropyl silicone, methylhydrogene silicone and alkyl-modified silicone. Polyether-modified silicone, alcohol-modified silicone and carboxyl-modified silicone may be also exemplified.
According to an advantage of the invention, the particle size of a crosslinked particulate product to be obtained can be effectively controlled by the viscosity of the silicone compound which is in terms of dynamic viscosity at 25° C. usually 1-1,000,000 centistokes (cSt), preferably 10-100,000 cSt, more preferably 100-10,000 cSt. The above exemplified silicone compounds may be combined in use if necessary.
Any of the silicone compounds according to the invention is used in an amount of usually 1-100 parts by weight, preferably 4-20 parts by weight per 1 weight part of polybutadiene.
The crosslinking reaction contemplated hereunder is carried out for a time length of usually 5 minutes to 10 hours, preferably 10 minutes to 5 hours with stirring usually at 50-10,000 rpm, preferably 100-5,000 rpm.
There may be added certain polymers or monomers which are not detrimental to the results of the invention, examples of which polymers include polymethyl methacrylate and polystyrene. These polymers may be added in an amount of usually less than 20 parts by weight, preferably 0-15 parts by weight per 100 parts by weight of polybutadiene. Examples of the monomers that may be admixed include styrene, methyl methacrylate, 2-ethylhexyl acrylate, hexandiol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentacrythritol triacrylate, pentaerythritol trimethacrylate, triallyl isocyanurate and triallyl cyanurate. These monomers may be added in an amount of usually less than 20 parts by weight, preferably less than 15 parts by weight per 100 parts by weight of polybutadiene.
The particulate material resulting from the aforesaid crosslinking reaction comprises at least part of its surface region occupied by a reaction product of polymer and silicone compound. A surface layer of the crosslinked particulate material measuring about 20 angstroms in depth was examined by X-ray photoelectronic spectral analysis to reveal the presence of silicone compound in an amount of generally more than 20 weight %, preferably more 40 weight %, more preferably more than 60 weight % of the total surface layer.
The particle size of the crosslinked material ranges usually between 0.01 and 1,000 microns, preferably between 0.02 and 500 microns, more preferably between 0.05 and 200 microns. Less than 0.01 micron particle sizes would lead to secondary coagulation of the particles. Conversely, larger particle sizes than 1,000 microns would fail in uniform distribution of the particles when admixed with other materials.
The invention will be further described by way of the following examples.
INVENTIVE EXAMPLE 1
To 100 parts by weight of liquid polybutadiene having a number average molecular weight of 2,000 and 65 mol percent of vinyl double bonds (tradenamed Nisseki Polybutadiene B-2000 manufactured by Nippon Petrochemicals Co., Ltd.) were added 1.0 parts by weight of each of 2,5-di(t-butylperoxy)hexene-3 and 2,3-dimethyl-2,3-diphenyl butane which were uniformly dissolved. 10 grams of the resulting admixture or starting crosslinking material together with 190 grams of dimethyl silicone having a dynamic viscosity of 1,000 cSt at 25° C. (tradenamed KF-96 manufactured by Shinetsu Chemicals Co., Ltd.) were charged into a 500 ml reactor equipped with stirrer. The reactor temperature was gradually raised from room temperature to 290° C. with a stirring speed held at 500 rpm and maintained at 290° C. for three consecutive hours to effect crosslinking of the admixture. The reaction liquid was removed from the reactor and found to show a dispersion of particles. The liquid was centrifugally processed to recover the particles which were thereafter washed with xylene and filtered. The resulting white crosslinked particles were thus recovered at a yield of 81 weight % based on the starting crosslinking material. The particles when observed by a scanning type electron microscope presented a truly spherical form having an average size of about 5 μm.
A surface layer measuring about 20 angstroms deep of the crosslinked particulate product was analyzed by X-ray photoelectron spectral method (XPS) to reveal the presence of a silicone compound concentration corresponding in terms of dimethyl silicone to about 91 weight % of the total surface layer measured.
The particulate product was further exposed through an alumina sheet to 160 mW/cm radiation by high-pressure mercury lamp, with the results shown in Table 1.
INVENTIVE EXAMPLE 2
The procedure of Inventive Example 1 was followed with the exception that methylphenyl silicone (tradenamed KF-54 manufactured by Shinetsu Chemicals Co., Ltd.) having a dynamic viscosity of 400 cSt at 25° C. was used in place of dimethyl silicone. There was obtained a white spherical particulate crosslinked product having a particle size of 11 μm and at a yield of 78 weight % based on the starting crosslinking material. Analysis of the crosslinked product showed a silicone compound concentration in its surface layer corresponding in terms of methylphenyl silicone to about 79 weight % of the total surface layer measured. The results of ultraviolet radiation test are shown in Table 1.
INVENTIVE EXAMPLE 3
To 100 parts by weight of liquid polybutadiene having a number average molecular weight of 3,000 and 65 mol percent of vinyl double bonds (tradenamed Nisseki Polybutadiene B-3000 manufactured by Nippon Petrochemicals Co., Ltd.) were added 1.0 parts by weight of each of 2,5-di(t-butylperoxy)hexene-3 and 2,3-dimethyl-2,3-diphenyl butane which were uniformly dissolved. 20 grams of the resulting admixture or starting crosslinking material together with 180 grams of methyltrifluoropropyl silicone having a dynamic viscosity of 10,000 cSt at 25° C. (tradenamed FL-100 manufactured by Shinetsu Chemicals Co., Ltd.) were charged into a 500 ml reactor equipped with stirrer. The reactor temperature was gradually raised from room temperature to 280° C. with a stirring speed held at 500 rpm and maintained at 280° C. for three consecutive hours to effect crosslinking of the admixture. The reaction liquid was removed from the reactor and was centrifugally processed to recover the particles which were thereafter washed with xylene and filtered. There was obtained a white spherical crosslinked particulate product at a yield of 84 weight % based on the starting crosslinking material. The particles when observed by a scanning type electron microscope presented a truly spherical form having an average size of about 10 μm.
Analysis showed the presence of a silicone compound concentration corresponding in terms of methyltrifluoropropyl silicone to about 93 weight % of the total surface layer measured.
The particulate product was tested as in Inventive Example 1 by ultraviolet radiation with the results shown in Table 1.
COMPARATIVE EXAMPLE 1
The starting crosslinking material used in Inventive Example 1 was alone charged into a brass mold and then transferred to and stored in a constant temperature bath at 290° C. for three consecutive hours. There was obtained a sheet of crosslinked resin, which was thereafter pulverized by a shock-type ultrafine grinder to an average particle size of 42 μm. The resulting particulate product was further classified thereby producing a white irregularly shaped particulate material having an average particle size of 23 μm. The yield of the thus classified particles was 16%. Ultraviolet radiation test as in Inventive Example 1 was conducted with the results shown in Table 1.
TABLE 1______________________________________ Color change of particles Yield before after (weight) radiation radiation______________________________________Inventive Example 1 81 white whiteInventive Example 2 79 white whiteInventive Example 3 84 white whiteComparative Example 1 16 white dark brown______________________________________
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A particulate polybutadiene crosslinked material is disclosed along with a process of making the same. The particulate material has a substantially spherical, uniformly shaped configuration and comprises at least part of its surface layer occupied by a reaction product of polybutadiene and a silicone compound.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to German Patent Application No. 10347333.5, filed on Oct. 11, 2003, the entire contents of which are hereby incorporated herein in its entirety.
BACKGROUND OF THE INVENTION
[0002] The invention initially relates to a method for the gentle conveyance of sensitive adhesives such as dispersion adhesives and/or abrasive media, whereby the adhesive or the medium is conveyed from a pressurized material vessel to an applicator such as a spray gun.
[0003] From the prior art, methods are known for applying dispersion adhesives or the like to the material to be bonded via an applicator, such as a spray gun. The main fields of application for dispersion adhesives are to be found in the wood-processing industry, the packaging industry and in the manufacture of foil- or textile-laminated moldings. Furthermore, it is also known how dispersion adhesives or the like can be fed, for example to a spray gun, which is also known from utility model DE 297 14 302 U1, the entire contents of which are hereby incorporated herein in its entirety, via a pressurized material tank. Such a pressurized material vessel is known from DE 100 62 993 A1, the entire contents of which are hereby incorporated herein in its entirety, for example.
[0004] The invention is based on the problem of how to improve a method for the gentle conveyance of sensitive adhesives or the like.
SUMMARY OF THE INVENTION
[0005] The problem is solved by intermittently refilling the pressurized material vessel from a supply vessel intermittently, applying negative and positive pressure, as a result of which a method is established which is characterized by gentle conveyance of sensitive adhesives, such as dispersion adhesives and/or abrasive media, whereby the process-assured handling of the adhesives or other media is assured in the application of such abrasive or corrosive media. An element here is also the fact that the method can be performed without using a mechanically-acting pump. The preferred embodiment is where the refilling is accomplished by generating negative pressure in the pressurized material vessel, and simultaneously forcing a valve in a connecting pipe between the pressurized material vessel and the supply vessel into an open position. The valve can be a slide valve or the like. However, there could also be a design where the valve in this connection can even take the form of a non-return valve. An alternative method specifies that the refilling is performed, in an arrangement with the supply vessel above the pressurized material vessel, by means of positive pressure acting on the supply vessel in the form of potential energy and atmospheric pressure after a valve in a connecting pipe between the pressurized material vessel and the supply vessel has been forced into an open position.
[0006] There can also be two pressurized material tanks and one of the pressurized material tanks is refilled without the positive pressure discharge of the other pressurized material tank having to be interrupted. In such a case, the two pressurized material tanks would again be connected to one another via a pipe which can be shut off with a valve. If one of the pressurized material tanks is being refilled because of negative pressure, the valve in the connecting pipe is closed. Then the other pressurized material tank could also be refilled in turn from the refilled pressurized material tank without any interruption, because of positive pressure.
[0007] The above methods can also be applied in combination. For example, in addition to the effect of potential energy, pressure may be applied in the supply vessel and/or negative pressure may be generated in the pressurized material vessel. Whilst when the pressurized material vessel is being operated at positive pressure a realistic pressure level should be approximately 5 to 8 bar, the specified negative pressure can be 0.5 bar, for example. In addition, the 0.5 bar stated may even be sufficient as positive pressure acting or applied in the supply vessel. Since in such a case, in particular, the rate of refilling dependent on that pressure is heavily dependent, higher pressures can also be used.
[0008] The invention also relates to an arrangement for a pressurized material vessel and a supply vessel for conveying sensitive adhesives such as dispersion adhesives and/or abrasive media to an applicator such as a spray gun. In order to develop a generic arrangement which is advantageous for use, it is proposed that the pressurized material vessel and the supply vessel be connected to one another via a pipe which can be shut off with a valve and that it be possible for the adhesive and/or the medium to be conveyed from the supply vessel into the pressurized material vessel solely by applying pressure. This application of pressure can take place by gravity, for example. For this purpose, the supply vessel is positioned at a suitable height in relation to the pressurized material vessel. Another preferred embodiment is where negative pressure can be generated in the pressurized material vessel in order to convey material out of the supply vessel, whereby positive pressure either exists or can be generated in the supply vessel by potential energy and/or increasing the pressure. The valve mentioned in the pipe between the supply vessel and the pressurized material vessel may, within the meaning of the invention, also be a non-return valve which opens automatically upon generation of negative pressure in the pressurized material vessel or upon a pressure increase in the supply vessel, permitting passage of the medium in order to fill the pressurized material vessel. Furthermore, it is also proposed that the pressurized material vessel be allocated a level measuring device which, in a favorable manner, continuously measures the level of the medium inside the pressurized material vessel, whereby, as necessary, negative pressure is generated in the latter in order to convey material from the supply vessel to the pressurized material vessel and the valve mentioned is opened. Another possible embodiment is where the measuring device is an ultrasonic measuring device. A preferred embodiment is where the measuring device takes the form of a vibrating fork measuring device. Such electronically controlled measuring devices provide the user with fundamental certainty for operation of his installation.
[0009] These and other features, advantages and objects of the present invention will be further understood and appreciated by those skilled in the art by reference to the following specification, claims and appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a side schematic view of a system for conveying adhesives embodying the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0011] Below an embodiment is explained in greater detail referring to the diagram of an arrangement according to the invention shown in FIG. 1 , which only represents an example.
[0012] The diagram in FIG. 1 shows one possible arrangement A for the gentle conveyance of sensitive adhesives, particularly dispersion adhesives and/or abrasive media, which, for the sake of simplicity, are not illustrated here.
[0013] Arrangement A consists of an approximately silo-shaped supply vessel 1 , which is connected to a pressurized material vessel 3 via a connecting pipe 2 . In addition, the pressurized material vessel 3 is connected to a spray gun 5 , constituting an applicator, via discharge pipe 4 . The spray gun 5 is known from utility model DE 297 14 302 U1 mentioned at the outset so it will not be described in any further detail here.
[0014] Furthermore, an electronically regulated controller 6 is a constituent part of arrangement A, whereby controller 6 in the illustrated example of arrangement A monitors three task methods within this arrangement A. On the one hand, controller 6 acts upon a pressure pipe 7 , which is connected to the pressurized material vessel 3 . On the other hand, an electronic line 8 is proposed which is connected to the level measuring device 9 positioned on pressurized material vessel 3 . There is also a control line 10 , by which it is possible to control a valve 11 positioned in connecting pipe 2 between supply vessel 1 and pressurized material vessel 3 .
[0015] Pressure pipe 7 is also used for subjecting the pressurized material vessel to negative pressure. Alternatively, a separate negative pressure pipe, which is not shown on the diagram, can also be provided.
[0016] Discharge pipe 4 , passing through cover 3 ′ of pressurized material vessel 3 with a seal, projects into the bottom area of pressurized material vessel 3 , maintaining a distance from the bottom. Pressure pipe 7 , which also passes through cover 3 ′ with a seal, ends at a short distance below cover 3 ′, whereby the latter seals off pressurized material vessel 3 .
[0017] Furthermore, cover 3 ′ supports measuring device 9 , which, penetrating cover 3 ′, dips like a probe into pressurized material vessel 3 , which has an explosion-proof seal.
[0018] One end of the connecting pipe mentioned, 2 , also penetrates cover 3 ′ of pressurized material vessel 3 with a seal.
[0019] Supply vessel 1 , the size of which is many times larger than pressurized material vessel 3 , supplies a very large quantity of application medium. Whilst material vessel 3 can be placed directly in the working area, supply vessel 1 can, for example, be positioned at a distance from pressurized material vessel 3 , for example in a supply vessel building.
[0020] The volume of the application medium inside pressurized material vessel 3 is monitored by measuring device 9 . The latter can take the form of an ultrasonic measuring device but also a vibrating fork measuring device. If a preset threshold level is detected on measuring device 9 because the level of the application medium has dropped, a negative pressure is generated inside the pressurized material vessel, using controller 6 and pressure pipe 7 . Accordingly, using controller 6 and control pipe 10 , valve 11 is opened out of the position which is closed in normal operation when applying the medium with spray gun 5 , after which the supply medium, subject to negative pressure, can flow out of supply vessel 1 into material vessel 3 until measuring device 9 detects an appropriate level in material vessel 3 .
[0021] The pumpless transfer of medium from supply vessel 1 into pressurized material vessel 3 is also supported by the atmospheric pressure on the application medium kept in supply vessel 1 and by its potential energy, so inside pressurized material vessel 3 a relatively low negative pressure of 0.5 bar, for example, is sufficient. Alternatively, or in addition, positive pressure can also be generated in supply vessel 1 via a facility not illustrated.
[0022] When the preset level in pressurized material vessel 3 has been reached, valve 11 is closed, after which a positive pressure of approximately 5 to 8 bar, preferably monitored by controller 6 , is again generated in pressurized material vessel 3 in order to apply the medium via spray gun 5 .
[0023] Valve 11 , proposed in the arrangement illustrated, may take the form of a slide valve. However, there could also be a solution in which the valve is provided by a non-return valve, which is kept in the closed position by positive pressure being exerted during material application operations and is shifted to the open position only on account of the negative pressure generated for refilling in pressurized material vessel 3 , and possibly on account of the potential energy of the application medium in supply vessel 1 acting on the non-return valve.
[0024] The intermittent supply of adhesive, which is sensitive in conveyance, and/or the abrasive medium, triggered by applying negative or positive pressure as described above, acts gently on the functional components.
[0025] The above description is considered that of the preferred embodiments only. Modification of the invention will occur to those skilled in the art and to those who make or use the invention. Therefore, it is understood that the embodiments shown in the drawings and described above are merely for illustrative purposes and not intended to limit the scope of the invention, which is defined by the following claims as interpreted according to the principles of patent law, including the doctrine of equivalents.
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An arrangement for conveying adhesives to an applicator comprising a pressurized material vessel and a supply vessel, wherein the pressurized material vessel and the supply vessel are connected to one another by a pipe, which can be shut off by a valve and wherein the adhesive can be conveyed from the supply vessel into the pressurized material vessel solely by exertion of pressure.
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BACKGROUND OF THE INVENTION
The general process for modifying iron, and in particular producing nodular cast iron, (i.e., cast iron comprising nodular or spheroidal graphitic inclusions) comprises in its broadest aspect supplying to molten grey iron a relatively minor amount of magnesium (based on the weight of the cast iron to be treated). Such magnesium additions preferentially lowers the sulfur and oxygen content of molten cast iron compositions, and, if sufficient magnesium is added, such treatment has the effect of producing spheroidal graphite rather than a flake graphite form.
Considerable problems have been associated with the introduction of elemental magnesium to a bath or exposed stream of molten iron. Ladle additions of magnesium to a molten iron bath have been largely avoided because the comparatively low boiling point of magnesium and its high degree of reactivity with oxygen and low density (relative to the density of the molten cast iron) causes substantial and expensive magnesium losses resulting from flash off at the surface of the molten bath. The loss is usually indicated by a violent pyrotechnic display and is accompanied by a violent reaction causing splashing of molten iron; this latter factor, along with the pyrotechnic display, constitute a serious threat to the welfare of personnel and equipment, especially in commercial operations wherein the amount of iron to be treated and the amount of magnesium metal required is generally great.
Efforts to reduce pyrotechnics and splashing have usually comprised adding the nodularizing agent to an enclosed treating ladle or enclosed reservoir stationed in the mold and through which the metal must ultimately flow. A modification to the ladle addition approach has used a tubular device to introduce solid addition agents, such as magnesium, below the surface of the molten metal; the magnesium is added in the form of a fine grain suspension in a gaseous carrier. Similar to this approach is the sub-surface injection of a mixture of powdered carbon and elemental magnesium, or the use of a tiltable reaction ladle with magnesium stored in one region thereof and caused to react under a certain vapor pressure. A commercial ladle approach, is the dropping of powdered additives of magnesium through a chute that enters a conical cavity in a stream of molten iron flowing through an aperture in the bottom of a storage chamber for molten metal; this is commonly referred to as the T-nock process. There is a vast number of other published arrangements for introducing magnesium during the pouring of molten iron into a ladle or while it is in the ladle.
In all of the above enclosed pouring ladle approaches, the results are unsatisfactory because of essentailly three problems, the most important of which is that the metal must be superheated to accommodate the considerable loss in heat from reladling and pouring. The superheat destroys growth sites and thus requires post inoculation to improve the distribution of the graphite nodules; inoculation has never achieved totally satisfactory homogeneity and magnesium recovery is relatively low leading to high costs.
The other two problems comprise dross build-up in the pouring vessel and the fading of the reacted magnesium before solidification. Dross on the ladle refractories create magnesium reaction products (sulfides, oxides); this can lead to excessive pouring unit downtime as a result of inductor channel clogging, loss of vessel volume, and pouring orifice restrictions. Magnesium and post inoculant fade are time dependent phenomenon. In general, the iron must be poured within 15 minutes of the time of treatment. If this cannot be done and if corrective actions are not taken, low nodularity of carbidic castings are likely to result.
Thus the prior art has turned to treating the molten iron after it leaves the mechanical pouring unit or ladle. One general approach to this post treatment is that which treats the molten metal as it flows through the casting mold or just prior to its entrance into the mold cavity. A notable example of stream treatment employs a reaction chamber embedded in the sand mold, thus forming a part of the runner system. A charge of magnesium bearing material is added to the reaction chamber in advance of pouring. Nodularization is accomplished by the reaction of this magnesium bearing material with the molten metal flowing through the reaction chamber. Several disadvantages are associated with this process including increased casting inspection, the ratio of the poured weight of metal to the cleaned weight of metal increases, there must be closer metallurgical control, an investment in unique runner and gating systems, and usually a closely sized magnesium ferrosilicon alloy is required since the molten metal has a difficult time in flowing around each magnesium particle. As to the increased casting inspection, this becomes a significant disadvantage. Each mold is treated individually. The conventional method of checking each treated quantity of metal for nodularizing content and for chill is impractical. A fail safe method of adding the magnesium alloy and of checking the produced castings has yet to be developed to make this approach successful.
Earlier attempts at stream treatment used a filter element placed at the mouth of this mold gating system; the filter had a predetermined porous magnesium matrix through which the molten iron was poured. Alternately, a consumable pouring sprue containing sponge iron impregnated with magnesium, both of which were reacted at a predetermined rate of consumption. In still another approach, an exposed stream was poured into a mold and an exposed stream of magnesium additive was projected against the stream for mixing and chemical reaction. These earlier attempts at stream treatment were, of course, unsatisfactory because they did not provide a controlled rate of solution; this is a function of alloy form and composition, treatment temperature, system heat, type and time of exposure to iron (the solvent) and oxygen available.
Whether the commercial practice has been stream treatment or ladle treatment, it has been carried out in batches; typically, up to several tons of molten iron is nodularized in a treating or holding ladle, then reladled into several pouring ladles, and then finally poured into a mold with post inoculating agents added to the pouring stream during transfer from treating ladle to the pouring ladle.
SUMMARY OF THE INVENTION
The primary object of this invention is to provide an improved method and apparatus, as well as the resulting product, for treating and manufacturing nodular cast iron, all characterized by better process control, lessened quality efforts (as judged by the uniformity of the resulting product) and lower material costs.
Another object of this invention is to provide a method and apparatus for nodularizing cast iron which is relatively independent of time variations for treating the molten iron.
Still another object is to provide a method of modifying cast iron which utilizes a constant predetermined pour rate and facilitates automatic continuous pouring requiring little or no operator control.
Particular features pursuant to the above objects comprise: (a) the use of an inclined trough having the aperture of an outlet controllable to selectively develop a pool of molten iron without interrupting flow therethrough, a modifying agent is injected into the pool and/or stream to provide turbulant flow and mixing as a result of the chemical reaction and time dwell therein; (b) the pool is built-up and dissipated in stages to provide for an initial quick fill and a trailing flushing flow; (c) the modifying agent may include a postinoculant or a desulphurizing material, such as magnesium ferrosilicon, effective to carry out a significant desulphurization simultaneous with nodularization; (d) the superheat temperature of the treated molten stream is considerably lower (about 100°-150° F.) than prior art methods; (e) the refractory chamber is effective to reduce gaseous emissions from the nodularization treatment significantly, thereby minimizing the need for special anti-pollution equipment; (f) since the stream treating equipment is small and exterior to the mold, it can be changed to treat a variety of different sized streams at different rates and back-to-back by merely changing either the reaction chamber or changing the pouring cup and exit openings, such choice depending on the design of the particular system; (g) the treated stream is directed immediately to a mold cavity and preferably a plurality of flasks containing a number of mold cavities, at a constant time factor; and (h) the resulting cast product is characterized by a unique absence of carbides and dross, and has a nodule distribution count of at least 400 per square millimeter in a 1/2 inch section.
SUMMARY OF THE DRAWINGS
FIG. 1 is a perspective view of an apparatus embodying the principality of this invention for stream treating molten iron;
FIGS. 2 and 3 are each substantially sectional views taken, respectively, along lines 2--2 and 3--3 of FIG. 1;
FIG. 4 is a composite of views depicting steps in the control of a pool of molten iron within a reaction chamber through which the stream flows;
FIG. 5 is a graphical illustration of the preferred range of carbon and silicon useful to characterize base iron as the starting material for this invention; and
FIGS. 6 and 7 are microphotographs, respectively 100× and 50× of the solidification structure of castings resulting from the practice of this invention.
DETAILED DESCRIPTION
APPARATUS
Turning first to FIGS. 1-3, there is depicted an apparatus which is particularly effective in carrying out the method of this invention and which contains novel structural features for stream treatment of molten iron. The apparatus 10 comprises means 11 defining an inclined flow course of refractory elements to conduct and define a stream of molten iron. The course consists of a receiving cup or basin 12 and a conduit 13; the cup has tapered interior walls 12a arranged to receive a predetermined continuous input or discrete charge of molten iron 25. The cup has an outlet opening 16 located at the lower most region which also serves as the inlet to adjoining structure; the size of opening 16 may effectively determine the maximum flow rate through the course but more predominantly the controlled outlet aperture of treating chamber will serve this function, as will be described. In place of the receiving cup, another conduit may be substituted to receive the iron. In any event, the inclined flow course is capable of delivering a stream of iron along a path at a predetermined flow rate influenced principally by gravity; the flow rate is changeable by primarily changing the size of opening 17 which may entail substituting a different cup 12 having a different sized opening 16 and/or adjusting the incline of the adjoining structure.
A refractory lined receptacle 14 is interposed in said flow course and has a closed interior reaction or expansion chamber 15; the receptacle has an open side abutting cup 12 in a sealing manner and utilizes opening 16 as an inlet. The receptacle 14 has an outlet 17 connecting with said conduit 13 and provides for egress of molten iron. Interior side walls 14a and 14b of the receptacle are inclined with respect to a central bifurcating plane; the walls 14a and 14b form a trough 18 substantially along the entire length of said receptacle and have bottom 18a of the trough inclined at an angle 19 with respect to a horizontal plane.
An apparatus means 20 is arranged atop the receptacle 14 for injecting a predetermined and continuous supply of modifying agent 53 into the chamber 15 of said receptacle by way of a conduit 22 extending through an opening 21 in the receptacle roof. Means 20 may be comprised of any suitable control apparatus, such as a vibrator 27 supported on structure 28 and effective to deliver a predetermined quantity of particulate material, preferably in the form of sized pellets, from a bin containing a supply 23 of said pellets.
The outlet 17 is controllable by means 30, which may take the form of a slidable gate operable by a suitable mechanical or electronic element 31. There must be at least one aperture control for either of said inlet or outlet (17 or 18). By adjusting the position of said gate relative to the opening 17, a pool 32 of molten iron may be built-up or dissipated in said chamber 15. The apertures of openings 16 and 17 are preferably designed to be of generally equal area and thus, when unobstructed, a maximum fast flow with a minimum diameter stream can be expected through chamber 15. By traversing the gate across opening 17, a differential between said apertures may be established promoting the development of said pool and in effect daming a portion of the flow therethrough.
The function of the slidable gate is twofold; (a) it must contact the stream surface to prevent the modification agent from floating out of the reaction chamber, (b) restrain the stream flow to increase residing time in the chamber. It is conceivable that if a series of gates are arranged to skim and control flow in a highly elongated chamber, the need for a pool becomes less critical.
An optical control 35 is employed to regulate the operation of injector means 20; control 35 has an optical sensor 36 aimed along a sensing path 37 to detect the presence of molten iron in said cup 12 at about a station 38. Station 38 should be adjacent the upper portion of said cup and remote from the trough 18. The control 35 is connected and arranged to electrically activate or deactivate vibrator 27 which in turn establishes the introduction of the modifying agent. When or if the charge of molten metal recedes below the station 38, the control 35, of course, deactivates the vibrator 27 and thereby stops any further injection of the modifying agent. Thus, the terminal portion of said flow residing between said receptacle 14 and station 38 will not receive direct injection of the modifying agent but will be chemically reacted by virtue of mixing with the residual iron in the flow course or in the pool 32.
The reacted molten metal is immediately directed by means 48 from conduit 13 to a plurality of molding flasks (42, 43, 44) each containing a molding cavity (45, 46, 47) for solidifying the casting. No special runner or gating system 49 is required in the molding set-up and the entire apparatus may be operated by automatic pouring equipment (not shown). Highly controlled and automated operation is not possible on a continuous basis with apparatus or methods known to the art and yet achieve the cost savings and quality castings of this invention.
METHOD
A preferred method aspect of this invention is as follows:
(a) A charge of base iron, having a chemistry equivalent to grey cast iron, is heated to a temperature in the range of 2500°-2700° F. Ductile or grey iron of one type considered pertinent to the present method can best be defined as that having carbon and silicon within the shaded area of the graph of FIG. 5. This type of composition of grey iron should have essentially between 3.5 and 3.7% by weight, total carbon and between 2.0 and 2.75 silicon (but as much as 3.0% ). Variable end limits between these ranges, depicted by lines 61 and 62, are best defined by lines 60 and 63. Line 60 is the result of the equation where total carbon plus 1/3 silicon equals 4.55; line 63 is the result of the equation where total carbon plus 1/7 silicon is equal to 3.9. However, certain iron types may be used which have a chemistry employing a greater silicon content; thus, the problems noted on the graph of FIG. 5 are only for the iron type there selected.
(b) An inclined flow course is provided; an inclined trough is interposed in the flow course having an inlet and an outlet for the trough disposed at the lower most apex of the trough and interconnecting with the flow course. The course is enclosed and particularly the trough is enclosed so that any gaseous emissions are trapped eliminating need for special anti-pollution equipment. For example, magnesium vapor will be released and will quickly condense on the tapered walls of the trough. The inlet and outlet can be arranged to have equal areas or apertures, one of which is controllable in size by way of a slidable gate thereacross; more preferably, the outlet can be sized somewhat smaller. As shown in FIG. 3, it has been deemed preferable to control the aperture of the outlet to provide a differential between the amount of flow making an ingress as compared to the flow making an egress from the trough. The length of the trough for the preferred embodiment should be about 30 inches, and the volume of the trough (defined by inclined side walls) should provide for expansion of the molten iron when reacted with a modifying agent. Such volume can be about one-third cubic foot. To insure a proper flow rate of the molten iron through said trough, it is inclined at an angle 19 which preferably is about 5° with respect to a horizontal plane. This incline, of course, is designed with the molten iron flow under no back pressure other than that which is produced by the column of molten iron in the receiving cup 12. If additional back pressure is provided, the incline and flow rate can be adjusted accordingly. In addition, a non-oxidizing atmosphere is preferably maintained within the flow course to prevent any unwanted oxidation of the molten iron.
(c) A stream of molten ductile iron is established and passed along said incline course and through said trough; the stream is controlled to have a flow rate of typically about 10 lbs. of molten iron per second which conforms to manufacturing reality, although a more preferable flow rate would be about 5 lbs. per second.
(d) As the molten grey iron passes through said trough, a modifying agent, preferably in the form of magnesium ferrosilicon operative as a nodularizing agent, is injected at a predetermined rate onto the stream for reaction therewith. A vibrating mechanism which may be used when the agent is in a particulate or lump form; the agent 53 will be urged to spill onto and through a feeding conduit 22 for deposit at a location on the stream in the upper region of the trough. For magnesium ferrosilicon, it is added at a rate and in an amount to achieve approximately 0.04-0.055% magnesium in the final casting; 0.0004-0.0006 lbs. (0.18-0.25 grams) of magnesium is dissolved for each pound of molten iron. Magnesium, being the critical modifying agent, can be introduced in other forms such as by a solid magnesium rod advanced so that the tip thereof progressively contacts the molten stream, or the magnesium may be added in the form of pure vapor. When the magnesium in particulate compound form, it is important that the lump size not be too great so as to prevent a graduated and controlled feed and should not be too small as to prevent good reaction with the molten stream; the minimum size should not be less than 750 microns.
(e) One of the main features of this invention is the flexibility of adjusting the injection rate of the modifying agent so as to match the flow rate of the stream passing through the reaction chamber of the trough and to adjust the pouring rate to fill the mold cavities at a required interval. Accordingly, the flow through said trough or reaction chamber is adjusted to provide a staged build-up and dissipating of a pool therein of sufficient quantity to provide for turbulency and thorough mixing of the modifying agent. Improved dissolvement of the agent in the molten iron is established so that at least 90% of the magnesium is recovered in the casting.
Referring to FIG. 4, the initial stage (a) permits the molten iron supplied to the receiving cup 12 from a heating ladle or furnace 51 to flow through the chamber 15 at a fast rate with no pool build-up; gate 30 is raised so that the inlet and outlet 17 apertures being maintained at generally equal size. The injection means 20 is triggered to introduce the modifying agent 53 simultaneous with the introduction of molten iron 50 to the receiving cup as sensed by the photoelectric means 35. Accordingly, the nodularizing agent, in the form of magnesium ferrosilicon pellets will be released to contact the earliest portions of the stream. However, since there is fast flow and little dwell time within the trough, total nodularization or reaction of the modifying agent and the iron will not take place in the trough. Nonetheless, the iron must migrate through the runner and gating system before reaching the mold cavity; in so doing it has been predetermined that the initial flow of the stream will totally reach outside the trough but prior to entry into the mold cavity. (b) As soon as the gate 30 can be progressively lowered to restrict the outlet 17, a pool 32 of molten iron is established in the trough which should have a sufficient depth to allow thorough reaction and turbulency 54 of the molten iron therein. This may preferably be at least 3 times the normal dimension of the stream flow. The top surface 40 of the molten pool will be built-up to such an extent that it may reach to the roof of the enclosed chamber. The entire surface of the pool will not be calm and smooth during the injecting phase of treatment since the contact of the magnesium therewith will result in immediate pyrotechnics and reactions rendering the evolution of gases 52. (c) In this stage, the gate 30 is progressively raised to cause the pool to dissipate even though further molten iron is maintained in the reception cup and even though the modifying agent is continued to be injected. The same reactions and evolution of gases, of course, continue to take place with slightly less mixing due to the receding pool. However, this stage is arranged so that it will be close to the trailing end of the charge or stream even though the surface 56 of the charge is still above the sensor 35. The pool is caused to dissipate as quickly as possible. (d) Finally, in this stage, the pool has been fully dissipated; the inlet and outlet are maintained at identical apertures or their full uncovered aperture thereby causing a rapid flow 59 straight through the trough. This occurs almost simultaneous with the receding of the molten iron in the reception cup below that at which the optical eye is trained, causing the injection of the modifying agent to be stopped. Thus, the trailing end of the stream flows through the trough without contact by additional injection of the modifying agent. However, since the very trailing end of the stream will fundamentally be solidified in the gating system of the mold arrangement, the unreacted or poorly reacted iron will be discarded. The rapid flow in this stage is important since it allows for flushing of the trough carrying away any impurities or slag that are retained on the surface of the pool, such impurities solidifying in the runner or gating system.
(f) The reacted stream is directed into a plurality of flasks (42, 43, 44) each containing preferably a tree-like arrangement of numerous castings interconnected by runner and gating systems in each mold. The plurality of flasks are arranged as close as possible to the reaction chamber or trough so that the dwell time, once the magnesium has reacted with the ductile iron, is limited to less than 5 seconds. The actual flow rate into each of the molds, of course, will be variable to some degree as dictated by the type of runner and gating system and the number of molds utilized. Nonetheless, this invention permits unprecedented, quick control of reaction and casting. If the dwell time between reaction and solidification is excessive, the nodularizing effect of magnesium will diminish causing a substantial nodule degeneration in the eventual casting.
Unprecedented cost reductions result from this continuous nodularization method for cast iron. With older techniques of nodularizing in a pouring ladle, several disadvantages resulted. Superheating was required which lead to a reduction in the number of growth sites for subsequent nodularization; post inoculation was thereby required to improve the distribution and homogeneity of the nodular cast iron, all of this resulting in higher costs. When the prior art turned to reacting magnesium in an enclosed chamber within the mold itself, a very important disadvantage resulted. There was complete lack of control or monitoring of the unviewable chamber; operators could never be quite confident that every portion of the iron charge was nodularized. Operators thus used excessive amounts of nodularizing agent to provide a margin of saftey and this again, of course, resulted in additional cost increases. The elimination of any baghouse or emission control equipment is an important advantage of the instant system. The need for special runners or gating is eliminated, such as that required in a system where the reaction chamber is enclosed in the molding flask.
The present inventive method is preferably operated with a low sulfur content in the iron charge (0.01-0.015%). However, this system is uniquely adaptable to disulfurization, to a limited degree, in the reaction chamber. Accordingly, additional desulfurizing agents may be added along with the magnesium to obtain a sulfur content of less than 0.01%. The ability to desulfurize in a local reaction chamber, immediately upstream of the mold, is unknown to the art and can lead to further significant cast reduction in the total iron treating method.
SAMPLES
Initial experimental research tests demonstrated the importance of the control of the molten flow through an inclined trough and the importance of the pool volume with respect to obtaining a full nodularizing action in stream treatment.
In a first research sample, the trough was arranged to have no pool build-up during treatment; the flow through the inlet and outlet of the trough was relatively rapid. Starting materials comprised for 42 lbs. of pig iron, 7 lbs. of pure iron, 500 grams of ferrosilicon, 160 grams of ferro manganese and 210 grams of magnesium ferrosilicon (Mg was 6% of additive). The pour temperature was 2650° F. and a nitrogen atmosphere was contained in the reaction chamber. Vibrator action was maintained for four seconds during the pour. The castings showed very good nodularization when analyzed at the middle of the pour (taken from the outlet of the chamber). However, when analyzed at initial stage of the pour, the nodularity was very poor due to inadequate reaction.
In a second research sample, the treating system was arranged to fill a plurality of molds, carried on a long cart, rolled under the outlet of the reaction chamber. Again, there was no pool build-up during stream treatment. The starting materials for the treatment included 58.2 lbs. of pig iron, 10 lbs. of pure iron, 714 grams of ferrosilicon, 228 grams of ferro manganese, and 300 grams of magnesium ferrosilicon (Mg was 6% of additive). The vibrator was operated over a 7 second interval which provided for more adequate addition of the modifying agents. The first mold poured showed poor nodularity due to inadequate magnesium reaction, there being no build-up of a pool in the trough of the treating chamber. The second casting in the second flask showed fair to good nodularity but exhibited an inserve chill. The last casting showed excellent nodularity.
A third research sample was arranged to provide a shallow pool in the treating chamber. Starting materials were similar to that in the second sample. The pour temperature was 2680° F., there was no nitrogen contained in the reaction chamber, and pouring time took 10 seconds. The castings showed only 30% nodularity, indicating that some of the reaction between the magnesium and iron took place outside the treating chamber. Part of the problem of this particular sample arose from the inadequate location of an optical power cell to begin and stop the addition of the modifying agent.
A fourth research sample was made with starting materials similar to that in the second sample except that the magnesium ferrosilicon was adjusted to provide 5% magnesium and about 0.5 Ce in the additions. Pouring temperature was 2660° F. and the pouring time took 16 seconds. A significant and deep pool was built-up in the treating trough. The nodularity of the casting was excellent and nearly 100%. The optical power cell was aimed at a different location to insure that the injection of the modifying agent was more appropriately timed with the flow of iron through the trough; the trailing portion of the stream through the trough was not accompanied by simultaneous injection causing residual reaction of the magnesium in the pool to complete a nodularizing reaction for the trailing portion.
PRODUCT
Utilizing the stream treatment development taught herein, a new product is created having a solidification structure as illustrated in FIGS. 6 and 7. The casting microstructure is characterized by a nodular distribution at a count of at least 400 per square millimeter for a 1/2 inch section, the nodules can be and are predominately of the type I shape (spherical) by at least 90%, and there is a high degree of homogeneity. There is a definite and observable absence of dross or slag in the microstructure and a definite absence of carbides. The chemistry of the casting accompanying such microstructure consists essentially of about 3.5 carbon, 2 1/2% silicon, the ratio between carbon and silicon being about 7:5 the sulfur content being less than 0.01%, about 0.6 Mn, and the remainder being substantially iron. The magnesium content of the nodularized cast iron is about 0.004.
A zoned casting can be made from a single pour according to this invention. This is facilitated by the ability to control the stream treatment of the molten iron so that a predetermined portion may be nodularized and a predetermined portion not nodularized. Accordingly, a casting may be provided which has a specific volume, such as a head or a hub of a casting, containing nodularized cast iron with the remaining volume of the casting being of ductile or grey cast iron depending on the application and design.
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A method and apparatus for producing modified grey iron, and particularly nodular cast iron, is disclosed. The apparatus comprises refractory elements including an inclined flow course for continuous reception of molten grey iron, a V-shaped inclined receptacle interposed in said course into which a predetermined supply of modifying agent, such as magnesium, is injected to react with said iron, and means for controlling the egress of iron from the receptacle in order to sequentially stage the build-up and dissipation of a pool of iron in said receptacle facilitating chemical reactions and thorough mixing for attaining and improving the homogeneity of the modified iron elements. The product and compositon uniquely is characterized by about 3.5 carbon, by weight, 2.5% silicon, 0.2-0.9% Mn sulfur no greater than 0.015%, the remainder being essentially iron; the composition is devoid of carbide and dross or slag and has a graphite nodule count of at least 400 per square millimeter in a 1/2 inch section.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention deals with a control device for a yarn or thread of a textile machine having a traction member connected to the yarn, with the traction member being connectable by a coupling assembly with a lifting device, and with the coupling assembly being controlled by a piezoelectric switching member. Such a control device is for instance suited for controlling a single yarn or thread, however also for a Jacquard- or dobby loom of a weaving- or knitting machine.
2. Description of the Prior Art
Numerous control devices for the thread of a textile machine are known, thus the DE-OS 21 30 502 describes for instance a control arrangement of the above-named type in a Jacquard machine for textile machines. The Jacquard machine contains a plurality of traction members as well as a lifting device for raising or lowering traction members selected according to the pattern. A coupling arrangement serves for selecting the traction members in accordance with the pattern. A piezoelectric switching member controls the coupling assembly. However herein it is disadvantageous, that the build-up of the device is extraordinarily complicated and that the piezoelectric switching member serves only as a substitute organ, which controls the drive means which themselves cause the coupling or uncoupling to happen. Herein it is additionally impossible to monitor the operational state of the coupling arrangement.
SUMMARY OF THE INVENTION
It is the object of the invention to design a control device of the type described above in such a way that the mentioned disadvantages are eliminated.
The object of the invention is achieved by providing a control device of the previously mentioned type the coupling assembly of which comprises a coupling link pin reciprocating between neutral and engaged positions, with two piezoelectric switching members being associated with the link pin and acting alternately as actuators and sensors having two piezoelectric switching members serve alternately as an actuator and a sensor and by having them move the coupling link pin to and fro between a neutral position and a coupling engaged position, there results an extraordinarily simple apparatus, since the piezoelectric switching members serve directly for controlling and for driving of the link pin and do not require any additional driving means. Since the piezoelectric switching members serve alternately not only as actuator rather also as sensor, they serve at the same time for monitoring the state of the coupling. Thus a control device results which incorporates an extremely simple build-up with simultaneous simple control and the greatest degree of security or safety.
BRIEF DESCRIPTION OF THE DRAWING
Embodiment examples of the subject in the invention are described with particularity in the following with the help of the drawings. It is shown on:
FIG. 1 A control device for controlling the warp thread of a weaving machine, partially in section and in diagrammatic illustration and in front view transversely to the longitudinal direction of the warp thread or warp yarn;
FIG. 2 the control device in FIG. 1 in section along the line II--II;
FIGS. 3a to 3c the functional mode of the control device in FIG. 1 in different shift positions of the link pin in diagrammatic presentation;
FIG. 4 a control device with two traction members according to the double lift principle for controlling a warp thread of a weaving machine analogously to the apparatus in FIG. 1, in front view transversely to the longitudinal direction of the warp thread;
FIG. 5 control device with group-like disposition of traction members and assigned thereto link pins and electrical actuation, shown diagrammatically;
FIG. 6 control apparatus consisting of several modularly structured control devices viewed from the top;
FIG. 7 the control device in FIG. 6 sectioned along the line VII--VII, shown diagrammatically;
FIG. 8 mode of operation of the device in FIGS. 6 and 7 shown diagrammatically.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1, 2, 3a, 3b and 3c show a first embodiment example of the invented control device 2 at a weaving machine 4. The weaving machine shown only diagrammatically contains warp yarns 6, which can be brought into a high position 6a or a low position 6b by the control device 2 for forming an open shed 8. A filling or weft yarn 10 is shot through the open shed 8 and is beat up at the edge 14 by a weaving reed 12. The cloth or tissue 16 thus produced is drawn off by a cloth or tissue take-off device 18.
The control device 2 contains a stationary block 20, in which a traction member 22 is guided so as to be able to move upwards and downwards. The traction member 22 configured in a laminar fashion is connected at its bottom end to a heddle 26 through a connector element 24, for instance a traction cord, with the heddle 26 containing a heddle eye 28 through which the warp yarn 6 is guided. The heddle 26 and with it also the traction member 22 are preloaded in a downward direction by a return spring 30. A lifting device 32 with lifting knives 34 disposed on both sides of the laminations cooperates with a drive cam 36 disposed at the traction member 22. The design of the drive of the lifting device 32 and the lifting knives 34 is sufficiently known so that it does not need to be described in detail here. The traction member 22 is preloaded in a downward direction by the return spring 30, this means it is preloaded in the low position 6b of the warp yarn 6. In order to bring the warp thread 6 into the high position 6a and to hold it there, the lifting knives 34 lift the lifting member 22 by means of the drive cam 36 to such an extent until the high position 6a of the warp yarn 6 is reached. A coupling arrangement 38 serves for retaining the traction member 22 in the raised position or for release of same, so that the traction member 22 can follow the lowering of the lifting knife under the action of the return spring.
The coupling assembly 38 comprises a link pin 40 supported on both sides of the traction member 22 in the block 20 so as to be displaceable in a reciprocating manner. The link pin 40 comprises a narrow guidance segment 42 engaging into a longitudinal slot 44 of the traction member and permitting the upward and downward motion of the traction member with simultaneous guidance of same. Furthermore the link pin comprises a wide link segment 46 which can snap into a coupling bore 48 in the traction member and in such a position can retain the guide member in the assumed position corresponding to the high position of the warp yarn 6.
Two piezoelectric switching members 50, 52 disposed on the block 20 on both sides of the link pin and which cooact with the ends of the link pin serve for creating the reciprocating motion meaning for controlling the link pin. The piezoelectric switching members 50, 52 serve alternately as actuator and as sensor.
The functional mode of the link pin and the switching members 50, 52 is explained in even more detail with the help of FIG. 1 but in particular by the diagrams on FIGS. 3a to 3c. If the switching members 50, 52 do not carry any current, the link pin 40 assumes the basic position shown in FIG. 3a, where the guidance segment 42 engages into the longitudinal slot 44 of the traction member 22. Herein the link pin contacts a switching member 52 and exerts a certain pressure on this switching member, which thereby functions as a sensor and sends a current pulse to an electronic control unit, which has not been depicted in detail here, thus indicating the position assumed by the link pin at this time. In order to shift the link pin, current is applied to a respective one of the switching members, for instance the right hand switching member 52 FIG. 3a, wherein the piezoelectric switching member bends or assumes a curved position and herein displaces the link pin from the right hand position into the left hand position, so that the wide pin segment 46 of the link pin snaps into the coupling bore 48 of the traction member 22 thus preventing further movement of the traction member. In the course of this shifting process the link pin is pressed against the other switching member 50 as is evident from FIG. 3b and it produces a control current there, which again indicates the assumed position of the link pin to the electronic control device not shown in detail here. The thus assumed position of the link pin where the traction member 22 is arrested in the high position is maintained until another control pulse causes the left hand switching member 50 to press the link pin back into the initial position as this is evident from FIG. 3c, in which the narrow guidance segment 42 again cooperates with the longitudinal slot 44 in the traction member. The piezoelectric switching members 50, 52 thus act alternately on the one hand as actuators causing displacement of the link pin and on the other hand as sensors which indicate the correct assumed position of the link pin to the electronic control device.
FIG. 4 shows the refinement of the control device in FIGS. 1 to 3 at the example of a double lift apparatus, as it is for instance described in the U.S. Pat. No. 3,835,894. In this control device there exist two lifting members 22a, 22b as well as a lifting device 32a with two pairs of lifting knives 34a and 34b acting one against the other. The lifting members 22a and 22b are connected with each other by a connecting cable 54 guided over a reversing roller 56. The bearing fork 60 is supported on the axis 58 of the reversing roller 56, with a flexible connector element 24 being fastened thereto, thus establishing the connection to the heddle 26 and with this to the warp thread 6. The mode of operation of the double lifting system is known and the control is performed analogously to the example in FIGS. 1 to 3c.
As is evident from FIG. 5, one or several coupling arrangements 38 and appropriate traction members 22 can be combined into a modular unit 62, which can be connected by connector means 64, for instance dovetail connections, with corresponding modular units 62, 62a, 62b, 62c, 62d. The individual switching members 50, 52 are connected to wires 66, 68 or 70, 72 which end at contact points 74, 76 or 78, 80 which cooperate with corresponding contact points of modular units 62, 62a, 62b, 62c, 62d connected therewith. The wires 66, 68, 70, 72 constitute a matrix for controlling the switching members 50, 52.
FIGS. 6 to 8 show a control device which is built up horizontally from modular units 62 of the control arrangement. A stationary coupling arrangement 84 and two coupling arrangements 86, 88 which can be moved up and down and are part of the lifting device are assigned in vertical direction to a traction member 82. The coupling arrangements 86, 88 are formed similar to the coupling arrangement 38 in FIG. 1. Each control arrangement of the control device functions in the same way as the control arrangement of FIG. 4, with the lifting knives 92, 94 corresponding to the lifting knives 34a and 34b of FIG. 4. The lifting knives 92 and 94 are respectively associated with the coupling arrangements 86, 88 which act on the traction member 82 that corresponds to the traction members 22a, 22b of FIG. 4. The row of the stationary coupling devices 84 constitute thus a stationary knife 90 and the row of the first mobile coupling devices 86 constitute an upper lifting knife 92 with the lift H 1 , and the second coupling devices 88 constitute a lower lifting knife 94 with the lift H 2 all of the lifting device 96. The upper lifting knife 92 and the lower lifting knife 94 of the lifting device 96 operate in a push-pull manner. The traction member 82 comprises, apart from the longitudinal slot 98, three coupling bores or recesses 100, 102, 104, which are allocated respectively to the lowermost position of the lifting knives 92, 94 or to the stationary knife 90. Furthermore the traction member 82 has a fourth coupling bore 106, which cooperates with the coupling arrangement 84 of the stationary knife 90 in the lifted position of the traction member, as this is evident from FIG. 8. FIG. 8 shows following one another operational phases from a to h where respectively activated coupling devices are shown in a shaded manner in FIG. 8.
FIG. 8a shows the traction member 82 in the basic position, in which the traction member is held in the low position by means of a return spring which has not been shown in detail here and which is similar to the spring 30 shown in FIG. 1. In the drive phase shown in FIG. 8b the coupling arrangement 84 of the stationary knife 90 is activated and retains the traction member 82 in the low position, while the upper lifting knife 92 and the lower lifting knife 94 move away from each other into the farthest position from each other, as shown in FIG. 86. According to FIG. 8c the stationary coupling arrangement 84 of the stationary knife 90 is disengaged and the coupling arrangement 88 of the lower lifting knife 94 is activated whereupon the movement of the lifting knives 92, 94 oriented against one another starts until they have reached the adjustment shown in FIG. 8d and the traction member 82 is in the lifted position. Thereupon the coupling arrangement 88 of the lower lifting knife 94 is released and the stationary coupling arrangement 84 of the stationary knife 90 is activated according to FIG. 8e, so that the traction member 82 is retained in the top shed position. The upper lifting knife 92 and the lower lifting knife 94 move away from each other from a position of FIG. 8e into the position shown in FIG. 8f, in which the stationary coupling arrangement 84 of the stationary knife 90 is disengaged and the traction member 82 is coupled with the coupling arrangement 86 of the upper lifting knife 92. Thereupon the lifting knives 92, 94 move against one another from the position of FIG. 8f into the position of FIG. 8g, and the traction member 82 is again lowered into the bottom shed position according to FIG. 8g. There the coupling arrangement 86 of the upper lifting knife 92 is disengaged and the stationary coupling 84 of the stationary knife 90 is activated, as shown in FIG. 8h, in order to hold the traction member 82 in the lower position, whereupon the lifting knives 92, 94 can again be moved away from each other from the position of FIG. 8h into the position of FIG. 8b.
Because of the horizontal subdivision of the knives into modular units, the control device can also be divided into individual blocks in vertical direction, wherein the electric lines are disposed in a matrix-like manner; this permits to reduce the quantity of the inlets and outlets of the control electronics to an acceptable and realizable quantity as is evident from FIG. 5. Since the individual modular units are interconnected by electric contacts, the individual modular units and partial blocks can be easily separated from each other, so that every unit and every block can be removed or replaced without removing the other blocks or units. Due to the modular units it is possible to combine different systems according to the width of the textile machine and the quantity of the warp threads.
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A traction member (22) is connected to a yarn (6) which is to be controlled. A coupling assembly (38) serves for coupling the traction member (22) to a lifting device (32). A coupling assembly (38) contains a link pin (40), which can reciprocate between a neutral position and a coupling engaged position, with two piezoelectric switching members (50, 52) which function respectively alternately as actuator and sensor being allocated to said link pin 40. This results not only in a particularly simple coupling construction, rather also in a monitoring of the switching function of the coupling, wherein switching errors and switching malfunctions can be avoided.
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BACKGROUND OF THE INVENTION
This invention relates generally to color masking and specifically to such systems which employ the multiplication capabilities of electro-optical imaging devices to achieve in real-time that which is usually a relatively time consuming process.
Color copying has become increasingly important in recent years because of changes in public acceptance of, and demand for, color information. The pressures created by these demands have resulted in numerous technological advances in the color reproduction arts, among which is that set forth in the instant disclosure.
Due to the inability of readily available and economic dyes to adequately reflect colors, it is necessary that some compensation or color correction be made to reduce the amount of specific pigments in specific areas -- a compensation which is most often accomplished by the process known as color masking. Many color masking techniques are known in the art as, for example, those described in The Focal Encyclopedia of Photography, Vol. II, pp. 921-927, W. & J. Mackay & Co., Ltd., Chatham, England, 1965, or by Yule in Principles of Color Reproduction, John Wiley & Sons, Inc., New York, 1967. These techniques include the well known photographic process of masking color separation negatives or positives, with other negatives or positives to vary the density of the specific color components.
Additional related techniques include the use of electronic color scanners which simultaneously or individually produce color separations. These devices scan the subject along very narrow lines using a small light beam and, through lenses and electronic gear obtain all of the information needed to separate colors and make such corrections as are necessary.
As mentioned above, the instant invention employs a broad class of imaging members which record optical images by an imagewise distribution of photo-generated voltages or current acting upon a voltage or current-alterable recording medium. Typically, in these members, imagewise activating radiation incident on a photoconductor allows charge carriers to move in an external electric field. These charge carriers interact with a voltage or current-sensitive member which in turn modulates light.
U.S. Pat. No. 2,896,507 describes an imaging member which includes a photoconductive layer on an elastically deformable layer sandwiched between a pair of electrodes, one of which is a thin metallic layer overlying the deformable layer. In operation, imagewise activating radiation is directed upon the member and an electrical field is established across the photoconductive and deformable layers thus causing these layers to deform in image configuration. The member is described as being capable of functioning as an image intensifier since the deformation image may then be read out with a high intensity light source and a Schlieren-type optical system.
Recently, a major advance in the art was made by Sheridon who disclosed the Ruticon (derived from the Greek words "rutis" for wrinkle and "icon" for image) family of imaging member wherein the voltage sensitive light modulating recording medium comprises a deformable elastomer layer and a photoconductive material may be provided as a separate layer or incorporated in the elastomer layer. For a detailed description of the Ruticon devices, see IEEE Transactions On Electron Devices, September 1972, and U.S. Pat. No. 3,716,359. Various different embodiments for establishing an electric field across the elastomer layer are described.
Sheridon discloses (U.S. Pat. No. 3,716,359) several embodiments of electro-optical imaging members and several variations upon ther useful application. The instant invention employs these members in a novel fashion to achieve results comparable to prior art color masking techniques.
SUMMARY OF THE INVENTION
It is therefore an object of this invention to provide a novel color masking system which is both simple and sensitive, without the complexities of the prior art.
It is a further object of this invention to provide a novel color masking system which employs optical recorders to achieve in real time that which the prior art has been able to accomplish only through multiple-step, or other time consuming processes.
It is a still further object of this invention to provide a color masking system which advantageously employs the image multiplication capabilities of electro-optical recorders.
It is an even still further object of this invention to provide a reusable color masking system with the real-time capability of multiplying the transmittance of the positive of an original color component with the negative of another.
These and other objects are accomplished by providing a method of real-time color masking wherein pairs of color filters are inserted at specific locations in the optical paths of an electro-optical image multiplication system to thereby produce a modulated radiation pattern representative of the product of the reflectance of the positive of one color component and the negative of other color components of the original.
BRIEF DESCRIPTION OF THE DRAWINGS
The advantages of this invention will become apparent upon consideration of the following detailed disclosure of the invention, especially when taken in conjunction with the accompanying drawings wherein:
FIG. 1 is a partially schematic, partially cross-sectional view of an optical recorder suitable for use in the instant invention.
FIG. 2 is a schematic representation of the basic multiplication concept used in the instant invention.
FIG. 3 is a schematic representation of a preferred embodiment of the inventive system.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As explained in the above-described U.S. Pat. No. 3,716,359 and publications, Ruticon imaging members can be made to store images and/or to display them in real-time. Furthermore, the image output sense can be either positive or negative, depending upon a simple change in Schlieren system geometry. These properties can be advantageously employed to produce a real-time color masking system which compensates for non-ideal inks or dyes. All of the embodiments and materials described in the Sheridon patent are suitable for use in this invention and are intended to be encompassed herein.
The term "real-time" as used in relation to the disclosed invention means basically that response times (process periods) are minimal or substantially instantaneous. This is contrary to operations which require minutes or hours for completion.
Referring now to FIG. 1, an exemplary imaging member from the Ruticon family is shown. Many modifications of the elements are known in the art, but generally imaging member 1 is comprised of a substrate 6 which is a transparent non-conductive layer having thereon a conductive transparent layer 5. Layer 4 is a photoconductive material which will allow the passage of more electrical charges into those regions which are exposed to light. Elastomer 3 may be of a class of elastomeric solid materials including both natural, such as natural rubbers and synthetic polymers which have rubber-like characteristics, i.e., elastic, and include materials such as styrene-butadiene, poly-butadiene, neoprene, butyl, polyisoprene, nitrile and ethylene propylene rubbers.
A thin continuous conductive layer 2 is placed on the surface of the elastomer, and is flexible enough to follow the deformations of the elastomer. In a preferred embodiment, this layer is highly reflective.
Power supply 7 provides DC voltages of one polarity to form a deformation image on the surface of the elastomer. The polarity required depends primarily upon the nature of the photoconductor. Power supply 7 must be capable of being turned off to erase the image, or undergo a shift in polarity to more rapidly erase the image. Supply 7 may also be AC or a combination AC and DC. The external electrical circuit may also include suitable switching means (not shown). Also not shown is an optional floodlight which may facilitate image erasure.
This type of image recorder can be read out using Schlieren optics. The positive image will be produced by diffracted light (higher orders), and the negative image will be produced by the undiffracted light (zero order).
When I p , the positive image, and I n , the negative image, are normalized in such a fashion that they are between zero and one, then I p = 1 - I n . This is a property that will be used in the masking process herein described.
FIG. 2 demonstrates the basic image multiplication principle used in the instant invention. Two images, in register with each other, are formed with quasi-collimated light on the two sides of the imaging member 1. For purposes of illustration, the "masking" image, the image that exposes the photoconductor and produces a phase image on the imaging member 1, is referred to as I 1 , the "original" image, the image formed on the opposite side of the imaging member, is referred to as I o and the "read-out" image, the image produced by conventional Schlieren optics from only the zero diffracted order of light reflected from the imaging member, is referred to as I R . Note that in the figure, 8 is a source of original input and 9 is a conventional beam splitter which separates the original into the two images I 1 and I o . Member 9 may also be a dichroic filter which separates the original image into two color separation images.
The read-out image is equivalent to the product of the positive original image I o and the negative of the masking image, that is, I R = I o (1 - I 1 ), as needed for masking. This result is obtained by using the image recorder property that the zero order readout gives an image that is 1 minus the image which exposes the photoconductor, i.e., the masking image. For simplicity it is assumed that the positive image of the image recorder is identical with the image which exposes it. The contrast of the positive (and negative) image can be controlled by adjusting the imaging member voltage and/or adding some of the higher diffracted orders to the zero order, and/or by adding some uniform light exposure, and/or by choosing the proper photoconductive material, and/or any of the methods known by those of skill in the art.
Referring now to FIG. 3, a preferred embodiment of the instant invention, which by way of illustration provides yellow toned exposure, will be discussed. The two imaging members 10 and 11 used in this illustration are of the same structure as shown in FIG. 1. The colored original is illuminated with white light at image source 8 and separated into two identical images by beam splitter 9. b
One of these two images, I g , is directed through green light filter 12 to address imaging member 10. The other image I b , is directed through blue filter 13 and then to imaging member 11. Imaging member 10 is illuminated with collimated actinic light, I A , and by a Schlieren-type optical system (not shown), the image produced by the zero diffraction order (proportional to (1-I g ), that is the negative image, is projected onto imaging member 11 in register with I b . The image produced by the higher diffracted orders, I m , reflected from member 11 is again equal to I b (1 - I g ).
In practice the output images from the two imaging members 10 and 11 have a different contrast than the input images. The contrast can be controlled by any of the methods set forth above to achieve the required masking properties.
Inasmuch as I M is the masking image representative of a color component of the original, it is a useful end product in itself. However, it should be appreciated that this image will normally be projected onto a photosensitive recording medium through a halftoning screen or system to recreate at least a portion of the original. Apparatus to perform the recreation process can take many forms, for example, one masked image can be used to expose a photoconductor the image upon which is then toned with a pigment and transferred to a receiver. A second masked image can then be used to create a different color pigment image on the receiver. These steps may be repeated until the desired color combination is achieved. Single or multiple photosensitive recording mediums may be used depending upon machine requirements. The halftoning process may be further used, in conjunction with the masking process described to improve the quality of the final color copy.
Furthermore, when masking by more than one of the other colors is required or when the image storage properties of the electro-optical imaging device is used, the concept can be extended to utilize three or more different imaging devices (one for each color). The different sequential exposures to reproduce all colors can be achieved by either mechanically interchanging the color filters, or the imaging devices, and holding the other optical components fixed. In particular, when the storage properties of the image recorder are utilized, as few as three recorders are needed to perform the complete color separation and masking by more than one color for all three colors.
It will be understood that various other changes of the details, materials, steps, arrangements of parts and uses which have been herein described and illustrated in order to explain the nature of the invention will occur to and may be made by those skilled in the art, upon a reading of this disclosure, and such changes are intended to be included within the principles and scope of this invention.
For example, the invention is not limited to the Ruticon family of image recorders, but rather includes devices such as liquid crystals.
Furthermore, by using the nonlinear characteristics of the image recorder, highlight and shadow masking can also be achieved. This is a very desirable capability, allowing control of final copy detail content.
Also, it should be noted that masking by more than one color, as mentioned above, may be achieved by directing a third image from element 9 of FIG. 3 through a red filter onto a third image recorder. The readout from the third recorder then becomes I A .
Even still further it is possible to use the structure of FIG. 2 to achieve single color masking of a transparency. Different color filters are merely inserted into the two outputs of member 9 to produce a masked readout at I R .
Finally, it should be realized that the embodiment of FIG. 3 can be used to produce different color masking by merely changing the two filters 12 and 13.
Although specific components proportions and process steps have been stated in the above description of preferred embodiments of the invention, other suitable materials, proportions and process steps, as listed herein, may be used with satisfactory results and varying degrees of quality. In addition other materials which exist presently or may be discovered may be added to materials used herein to synergize, enhance or otherwise modify their properties.
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A method of real-time color masking is disclosed wherein pairs of color filters are inserted at specific locations in the optical paths of an electro-optical image multiplication system to thereby produce a modulated radiation pattern representative of the product of the reflectance of the positive of one color component and the negative of other color components of the original.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel compounds having anti-hyperlipidemic activity and to processes for their production, and more particularly, is converned with novel triterpenyl esters of organic acids [except triterpenyl esters of ferulic acid (4-hydroxy-3-methoxycinnamic acid) and of monobasic and dibasic saturated fatty acids] having excellent anti-hyperlipidemic activity and low toxicity and with processes for the production of these esters.
The invention further relates to anti-atherosclerotic and hypolipidemic agents which contain the above-mentioned novel compounds and the known compounds (i.e. cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of ferulic acid, or monobasic saturated fatty acids, and cyclobranol).
More specifically, the present invention relates to excellently active and low toxic agents for treatment of hyperlipidemia or hyperlipoproteinemia, that is, safety and novel hypolipidemic and antiatherosclerotic agents which contain triterpenyl esters of organic acids, preferably, cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of organic acids including esters from triterpenyl alcohols and ferulic acid or monobasic saturated C 4 ˜C 20 fatty acids, and cyclobranol alone, as respective active ingredients.
2. Description of the Prior Art
It is well known that hyperlipidemia or hyperlipoproteinemia is one of the most serious factors causing atherosclerosic, a form of arteriosclerosis, especially coronary heart disease. Miller and Miller (G. J. Miller and N. E. Miller, Lancet Jan. 4, p. 16 (1975)) have observed a negative correlation between the concentration of high density lipoprotein choresterol (hereinafter referred to as HDL-C) in blood plasma and the cholesterol pool in the body, and no correlation between either the concentration of total cholesterol (hereinafter referred to as TC) for the concentration of other lipoproteins, and the cholesterol pool, and therefrom proposed the theory that the reduction of cholesterol clearance from the arteries caused by a decrease in the HDL-C concentration in blood promotes arteriosclerosis. Since the proposal of this theory, a number of epidemiological studies (e.g. T. Gordon et al., Am. J. Med., 62. 707 (1977)) have proved the presence of a reverse correlation between the onset of ischemic heart disease and the concentration of HDL-C, and comfirmed that a decrease in the HDL-C concentration in blood is one of the most serious factors causing ischemic heart disease regardless of the presence or absence of an anti-hyperlipidemic agent.
It has so far been known that phytosterols reduce the content of cholesterol in serum. For example, a mixture of β-sitosterol and dihydro-β-sitosterol (supplied by Lilly Co., U.S.A. under the tradename of Cytellin) and a mixture of soysterol, phytosterol, and tocopherol (supplied by Morishita Pharaceutical Co., Ltd. Japan, under the trandename of Moristerol) are on the market as anti-hyperlipedemic agents.
On the other hand, the following is reported on triterpenyl alcohols.
Japanese Patent Application Laid-Open No. 18617/1982 describes that when a phytosterol (1 part) was used jointly with a cycloartenol or 24-methylenecycloartanol (0.01-0.1 part), a stronger action of lowering serum cholesterol than that of phytosterol singly was exhibited by synergism.
Japanese Patent Application Laid-Open No. 116415/1983 also describes that a considerably stronger action depressing serum cholesterol due to synergistic effect was observed in the case of joint use of a phytosterol (100 parts) with cycloartenol, 24-methylencycloartanol, or cyclolandenol (1-20 parts, particularly about 5 parts) than in the case of single use of the phytosterol. In particular, cycloartenol has synergistic effect on the serum cholesterol lowering action of phytosterol, while 24-methylenecycloartanol and cyclolandenol have weaker effect than that of cycloartenol.
Japanese Patent Application Laid-Open No. 27824/1984 reports that when 1% of cycloartenol or 24-methylenecycloartanol was added to a diet containing 0.5% of cholesterol, the respective percentages of TC lowering were 13.7% and 10.2% based on a control with high cholesterol diet (calculated by the present inventors from the data shown in Table 2 of the above patent Laid-Open Gazette).
However, these three patent applications described none of triglyceride (hereinafter referred to as TG), total phospholipid (hereinafter referred to as PL), HDL-C, atherogenic index [(TC - HDL-C)/(HDL-C), hereinafter referred to as AI: some Japanese medical scientists designate the AI as cholesterol ratio or arteriosclerosis index], and lipid peroxide (hereinafter referred to as LPO), though reporting on the action of TC lowering in serum.
From the fact that cycloartenol, 24-methylenecyclo artanol, and cyclolaudenol, alone or in combination with a phytosterol, depressed TC in serum, it is not obvious that these triterpenyl alcohols have also the action of lowering the other items of serum lipids TG, PL, and LPO which are important for treating or diagnosing hyperlipidemic conditions, and that these alcohols have the effect of increasing HDL-C, which is currently considered as particularly significant for treating hyperlipidemia, and in addition the effect of lowering AI. It is impossible to predict such overall pharmacological activity from analogy.
The γ-orizanol on the market today in Japan as a therapeutic agent for treating whiplash syndrome (head or cervical damage) is not composed of a single component but mixtures of various phytosteryl and triterpenyl esters of ferulic acid. An example of the γ-organol is composed of campesteryl (14%), stigmasteryl (1%), β-sitosteryl (4%), cycloartanyl (2%), cycloartenyl (35%), and 24-methylenecycloartonyl (44%) esters of ferulic acid but little cyclobranyl ester of ferulic acid.
Recently the following report on the influence of γ-orizanol upon cholesterol metabolism in hyperlipidemic rats was published by F. Kuzuya et al. (Geriatric Medicine 18, pp 519-524 (1980)). According to the report; TC was explicitly depressed in rats fed with a high cholesterol diet containing 0.1, 0.5, and 1% of γ-orizanol, as compared with TC in control rats fed with the same diet but containing no γ-orizanol, while the degree of the lowering depended on the dosage; the degree of TC lowering was greater than that of PL and comparable to that of HDL-C depression; γ-orizanol showed no activity an AI, but a tendency to increasing TG and the distinct action lowering LPO.
According to K. Mitani et al. [Domyaku Koka, 11, No. 2, June, pp 411-416 (1983)], the serum TC values in rats fed with a high chloresterol diet with 0.5, 1.0, and 2.0% of γ-orizanol were lower by 8.1, 23.4, and 30.9%, respectively, than control rats fed with the same diet but containing no γ-orizanol, while no significant depression was observed in the serum TG and PL values.
According to the study of the influence on hyperlipidemia of hypothalamic obesity rats, by S. Inoue et al. [Domyaku Koka, 11, No. 2, June, pp 417-428 (1983)]γ-orizanol exhibited the action of lowering TC but not TG in blood and no effect on PL and HDL-C in blood.
As regards organic acids, R. D. Sharma [Atherosclerosis, 37, pp. 463-468 (1980)] describes; that in rats fed with a high cholesterol diet containing 0.2% of an organic acid, TC level was lowered significantly by 10.8% when the acid was ferulic acid, and by 9.4% when the acid was p-coumaric acid, based on TC level in control rats fed with the same diet but containing none of such organic acids; that the degree of TG level lowering was 18.7% with ferulic acid and 19.8% with p-coumaric acid, but these values were not significant; that the PL level lowering was scarcely observed with both the acids; and that no decrease of TC, TG, or PL level was shown with vanillic acid, caffeic acid, or cinnamic acid.
Although an organic acid was not used singly, the following reports on the anti-hyperlipidemic effect of α-methylcinnamic acid derivatives was presented. K. Takashima et al. [Biochemical Pharmacology, 27, 2631 (1978)] describe the antihyperlipidemic effect of α-mono-p-myristyloxy-α'-methylcinnamoyl glycerol. T. Watanabe et al. [Journal of Medicinal Chemistry, 23, 50 (1980)] describe in detail synthetic methods of p-alkoxycinnamic acids, p-alkoxy-α-methylcinnamic acids wherein the alkyl moiety in the alkoxy substrituent is 2-propenyl, C 8 -C 18 alkyl, or phenyl; o-, p-, and m- myristyloxycinnamic acids; m-methoxy-p-alkoxy-α-methylcinnamic acids wherein the alkyl moiety of the alkoxy substituent is C 12 or C 14 alkyl; p-alkoxycinnamates, and p-alkoxyl-α-methylcinnamates wherein the alkyl moiety of the alkoxy substituent is 2-propenyl, methyl, butyl, or C 8 -C 18 alkyl and the alcohlic residue of the ester is chloroethyl, metharyloxyethyl, monoglyceride residue, diglyceride residue, etc; and anti-hyperlipidemic activities of these compounds. T. Watanabe et al described also a process for producing p-alkoxy-α-methylcinnamic acids wherein the alkyl moiety of the alkoxy is C 8 -C 16 alkyl) (Japanese Patent Publication No. 45582/1976). T. Ota et al. (Japanese patent application Laid-Open No. 80370/1982) describes α-methyl-p-pyridyloxycinnamic and α-methyl-p-pyridylalkyloxycinnamic acids and (C 1 -C 3 alkyl) esters thereof, processes for producing these compounds, and anti-hyperlipidemic compositions containing these compounds.
Recently, Grill, H. et al. [Japanese patent application Laid-Open No. 25953/1985); DE, App. No. 3326164.4 (1983, July, 20)] desribe p-aloxybenzoic acid derivatives such as N-carboxymethyl-4-(2-hydroxy-4-phenylbutoxy) benzamide and 4-[4-(4'-tert-butylphenyl)-2-oxobutoxy] benzoic acid, processes for producing these derivatives, and anti-hyperlipidemic compositions containing these derivatives.
Also, in the past, attempts have been made to lower the levels of cholesterol, phospholipids, an triglycerides in the blood by the oral feeding of various substances which have been generally referred to in the art as hypalipidemic agents or hypocholesteremic adjuvants. Several synthetic hypolipidemic agents are now available, namely, clofibrate, D-thyroxine, cholestyramine, and various nicotinic acid-derivatives.
The development of agents capable of reducing elevated blood lipids and of favorably altering blood-lipoprotein patterns is considered by medical authorities to be extremely important for the treatment and prevention of atherosclerosis.
The present inventors tested the known compounds cycloartenol, 24-methylenecycloartanol, and cyclobranol to ascertain the anti-hyperlipidemic effect thereof. The tests were carried out according to method A (male Wistar strain rats weighing initially 100±1 g were fed for 2 weeks with the diet limited to 10 g/day for each animal but with water given ad libitum) and method B (male Wistar strain rats weighing initially 100±1 g were fed for 4 weeks with the diet and water given ad libitum). Details of these test methods will be described later. Results of these tests shown in Tables 1 and 2 (method A) and Tables 15 and 16 (method B) were as follows: The hypolipidemic effects according to both methods were fundamentally identical. The decrease of TC in serum was observed in the both group given a hyperlipidemic diet containing cycloartenol and given a hyperlipidemic diet containing cyclobranol, at significance levels (P<0.05 according to method A, P<0.01 according to method B), as compared with that in the control group given only a hyperlipidemic diet. The TC lowering due to 24-methylenecycloartanol was slight and not significant according to method A but significant (p<0.05) according to method B). As to HDL-C; cycloartenol depressed it at significant levels (p<0.05 according to method A, p<0.01 according to method B), 24-methylenecycloartanol lowered it slightly with both method so it was not significant. On the contrary, cyclobranol showed a tendency to increasing HDL-C according to both methods though these increases were not significant. Needless to say, HDL-C level is desired to increase significantly, as shown in the foregoing literature.
One of the purposes of the invention is to develop a hypolipidemic agent which significantly lowers TC and increases HDL-C in serum. As stated above, it was confirmed that one of the triterpenyl alcohols, for instance, cycloartanol, cyclobranol, or 24-methylenecycloartanol singly depress TC level in serum significantly. However, no increase in HDL-C content was ascertained in the present inventors' test for hypolipidemic effect according to either methods A or B.
As to AI, cycloartenol and cyclobranol showed tendencies to decrease it according to method A, while 24-methylenecycloartanol showed only a slight tendency to increase. According to method B, the three triterpenyl alcohols showed tendencies to decrease AI. As to TG, PL, and LPO, no significant change was shown with these triterpenyl alcohols according to both methods.
Comparing these three triterpenyl alcohols, cyclobranol tended to lower TC, AI, TG, PL, and LPO but to increase HDL-C, and consequently it was different in the action from cycloartenol and 24-methylenecycloartanol. That is, it has proved that cyclobranol is superior to cycloartenol and 24-methylenecyloartanol in hypolipidemic effect.
Thus, the present inventors have studied aiming at the production of an hypolipidemic agent which will decrease the TC, PL, and TG, contents in serum while the HDL-C content is increased, furthermore an agent which lower AI and LPO contents simultaneously. So our studies have been concentrated on the development of a hypolipidemic agent which has distinctly greater effect in at least 2-3 of 6 items noted above than known triterpenyl alcohols and γ-orizanol. As a result, we discovered a number of novel triterpenyl esters of organic acids having excellent hypolipidemic activity. Further we found that each of the three known triterpenyl esters of ferulic acid, certain esters of monobasic saturated fatty acids, and cyclobranol have high hypolipidemic activity singly. It is difficult to predict these facts from properties of each of the known triterpenyl alcohols, organic acids, and γ-orizanol.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide novel triterpenyl esters of organic acids except triterpenyl esters of ferulic acid (4-hydroxy-3-methoxycinnamic acid), and of monobasic and dibasic saturated fatty acids. More particularly, the novel triterpenyl esters of organic acids are organic esters derived from the following alcohols: cycloartenol 24-methylenecycloartanol, lanosterol, lanostenol agnosterol, cyclosadol (3β-hydroxy-24-methylene-9, 19-cyclo-9β-lanosta-23-ene), dihydroagnosterol, cyclolaudenol, cycloartanol, cycloeucalenol, euphol, butyrospermol, tirucallol, euphorbol and dammerradienol, except esters of ferulic acid, and monobasic and dibasic saturated fatty acids.
Of these esters, preferred are those derived from cycloartenol, 24-methylenecycloartanol, and cyclobranol. Favorable organic acids for the esters are; cinnamic acid, benzoic acid, and α-(C 1 -C 4 alkyl) cinnamic acid wherein one substituent group on the benzene ring is selected from amino, nitro, hydroxyl, C 2 -C 5 acylamino, C 1 -C 4 alkoxy, and C 2 -C 6 alkylcarboxyl groups; cinnamic acid, benzoic acid, and α-(C 1 -C 4 alkyl) cinnamic acid wherein two substituent groups on the benzene ring are selected from these pairs hydroxyl and C 1 -C 4 alkoxy, hydroxyl and C 2 -C 6 alkylcarboxyl, C 1 -C 4 alkoxy and C 2 -C 6 alkylcarboxyl, C 1 -C 4 alkoxy and nitro, C 1 -C 4 alkoxy and amino, C 1 -C 4 alkoxy and C 2 -C 5 acylamino, two C 1 -C 4 alkoxy, two C 2 -C 6 alkylcarboxyl, and two hydroxyl groups; nicotinic acid; and unsaturared fatty acids such as linoleic acid, linolenic acid, arachidonic acid, and eicosapentaenoic acid.
It is another object of the present invention to provide processes for the production of the above-mentioned esters of organic acids.
It is still another object of the present invention to provide a hypolipridemic agent which significantly depresses TC and increases HDL-C in serum.
It is still further object of the present invention to provide a pharmaceutical composition for treating hyperlipidemia, comprising a pharmaceutical carrier and an effective amount of cyclobranol or a triterpenyl ester of organic acid other than dibasic saturated fatty acid.
It is still further object of the present invention to provide a method of treating hyperlipidemia comprising administering to a patient in need of such treatment, a therapeutically effective amount of cyclobranol or a triterpenyl ester of organic acid other than dibasic saturated fatty acid.
According to one aspect of the present invention, there is provided a triterpenyl ester of organic acid other than triterpenyl esters of ferulic acid and of monobasic and dibasic saturated fatty acids.
According to another aspect of the present invention, there is provided a process for producing a triterpenyl ester of organic acid ester other than esters of ferulic acid and of monobasic and dibasic saturated fatty acids, which comprises the reaction of a triterpenyl alcohol with an acid halide of the corresponding organic acid.
According to still another aspect of the present invention, there is provided a pharmaceutical composition for treatment of hyperlipidemia comprising a pharmaceutical carrier and an effective amount of a triterpenyl ester of organic acid other than triterpenyl esters of dibasic saturated fatty acids.
According to still another aspect of the present invention, there is provided a phermaceutical composition for treating hyperlipidemia which comprises a pharmaceutical carrier and an effective amount of cyclobranol as an active ingredient.
According to still another aspect of the present invention, there is provided a method of treating hyperlipidemia comprising administrating to a patient in need of such treatment, a therapentically effective amount of cyclobranol, or of a triterpenyl ester of organic acid other than dibasic saturated fatty acid.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The novel compounds of the present invention are, in general, white crystalline solids having characteristic melting points and specific rotation, and stable compounds which, as can be seen from later examples of preparation, that those are not hydrolyzed at all even heated at 60°-70° C. for 3 hours in a strongly acidic aqueous solution of pH 0.5-1.5 with stirring.
Structural formulae of three preferred triterpenyl compounds are shown below. ##STR1##
When R is H in the general formulae Ia, Ib, and Ic, formula Ia represents cycloartenol, formula Ib 24-methylenecycloartanol, and formula Ic cyclobranol. These three triterpenyl alcohols are publicly known.
In the present invention, R of formulae Ia, Ib, and Ic herein represents a residue of the above-mentioned various monobasic organic acids. The following general formulae II and IIIa-IIId represent the compounds of the present invention which have, in the molecule, one of these organic acid residues except nicotinic acid, linoleic acid, linolenic acid, arachidonic acid, and eicosanpentaenoic acid residues. ##STR2##
In formula II, R 1 denotes α,β-unsaturated carbonyl group (--CH═CH--CO--), carbonyl group (--CO--), or α-(C 1 -C 4 alkyl) α,β-unsaturated carbonyl group (--CH═CR 3 --CO--), and R 2 denotes amino (--NH 2 ), acylamino (--NHCOR 3 ), nitro (--NO 2 ), hydroxyl (--OH), C 1 -C 4 alkoxy (--OR 3 ), or C 2 -C 6 alkylcarboxyl (--OCOR 4 ). R 3 is C 1 -C 4 alkyl, i.e. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and R 4 is C 1 -C 5 alkyl, that is, any of the above alkyls denoted by R 3 and of the C 5 alkyls, i.e. pentyl iso-pentyl, sec-pentyl, 3-pentyl, and tert-pentyl.
General formula (II) represents any of the triterpenyl esters of cinnamic acid, benzoic acid, and α-(C 1 -C 4 alkyl) cinnamic acid which have the substituent R 2 on the ortho-, meta-, or para- position of the benzene ring. ##STR3##
In general formulae IIIa-d, R 1 , R 3 , and R 4 are as defined above.
The compound of general formula IIIa is a triterpenyl ester of cinnamic acid, benzoic acid, or α-(C 1 -C 4 alkyl)cinnamic acid each having, on the benzene ring, two different substituents OH and OR 3 groups, or OH and OCOR 4 groups. The compound of general formula IIIb is the same ester but the acid residue of which has on the benzene ring, two different substituents OR 3 and OCOR 4 groups, OR 3 and NO 2 groups, OR 3 and NH 2 groupos, or OR 3 and NHCOR 3 groups.
Referring to the compounds of formula IIIa or IIIb, detailed description is given below.
The compound of formula IIIa, when an OH group is attached to the benzene ring at the o-position (2-position), is an ester having an OR 3 or OCOR 4 group at the 3-, 4-, 5- or 6-position. When an OH group is attached to the benzene ring at the m-position (3-position), the compound is an ester having an OR 3 or OCOR 4 group at the 2-, 4-, 5-or 6-position. When an OH group is attached to the benzene ring at the p-position (4-position), the compound is an ester having an OR 3 or OCOR 4 group at the 2- or 3-position (hereinafter these compounds are referred to as compounds of formula IIIa). Such bond-structures of the compounds of formula IIIa are shown by the following general formulae IIIa 1 -IIIa 10 : ##STR4##
In formulae IIIa1-IIIa10, R 1 , R 3 , and R 4 are as defined above.
The compound of general formula IIIb is a triterpenyl ester of cinnamic acid, benzoic acid, or α-(C 1 -C 4 alkyl) cinnamic acid each having, on the benzene ring, two different groups, i.e. an OR 3 group, in place of the OH group of the compounds of formula IIIa, and any of OCOR 4 , NO 2 , NH 2 , and NHCOR 3 groups. Consequently, the compound of formula IIIb1 shown below is a compound resulting from the substitution of an OR 3 group for the OH group of the compound of formula IIIa1 and the substitution of an OCOR 4 , NO 2 , H 2 , or NHCOR 3 group for the OR 3 or OCOR 4 group of the compound of formula IIIa1.
The compounds of the following formulae IIIb2-IIIb10 have similar bond-structures. In these formulae, X denotes OCOR 4 , NO 2 , NH 2 , or NHCOR 3 group. ##STR5##
In formulae IIIb1-IIIb10, R 1 and R 3 are as defined above.
The compound of general formula IIIc and the compound of general formula IIId are triterpenyl esters of cinnamic acid, benzoic acid, or α-(C 1 -C 4 alkyl) cinnamic acid having, on the benzene ring, two OH groups and two OR 3 groups, respectively. That is, the compound of formula IIIc has two OH groups at the 2- and 3-positions, 2- and 4-positions, 2- and 5-positions, 2- and 6-positions, 3- and 4-positions, or 3- and 5-positions, that is, the following six bond-structures are present for the compounds of formula IIIc. ##STR6##
The compound of formula IIId has two OR 3 groups in place of the two OH groups of the compound of formula IIIc, thus including six compounds of formulae IIId1-IIId6 similarly to formulae IIIc1-IIIc6.
In the next place, the process for producing the compound of the invention is described.
The aforementioned γ-orizanol is a suitable raw material for cycloartenol, 24-methylenecycloartanol, and cyclobranol. The γ-orizanol, as stated before, is not a single compound but a mixture of various steryl and triterpenyl esters of ferulic acid. The mixture, for example, is composed of campesteryl (14%), stigmasteryl (1%), β-sitosteryl (4%), cycloartanyl (2%), cycloartenyl (35%), and of 24-methylenecycloartanyl (44%) esters of ferulic acid. With reference to the method of Endo et al. (Yukagaku, 18, pp. 63-67 (1969)), γ-orizanol was recrystallized repeatedly by using acetone-methanol (methanol content 2-7%), acetone, and ethyl acetate to give cycloartenyl ester of ferulic acid, which was then saponified to separate cycloartenol, m.p. 101°-102° C., specific rotation [α] D 21 .5 +49.7° (c 1.01, CHCl 3 ). This cycloartenol, on gas chromatography, gave a single peak.
Method for isolating 24-methylenecycloartanol
According to the above method of Endo et al., crystals obtained from the mother liquor after separating cycloartenol from γ-orizanol were acetylated with phridine-acetic anhydride, the acetylated product was recrystallized repeatedly by using chloroform-ethyl acetate-ethanol (4:3:2) and then deacetylated, and the product was recrystallized from acetone-methanol to give 24-methylenecycloartanyl ester of ferulic acid, which was then saponified to isolate 24-methylenecycloartanol, m.p. 123°-124° C., specific rotation [α] D 24 +48.1° (c 1.00, CHCl 3 ). This substance, on gas chromatography, gave a single peak.
Method for isolating cyclobranol
γ-Orizanol (1.1 Kg, cyclobranol content 0%) was dissolved in acetone (8 l). After dissolution of iodine (40 g) therein, the mixture was heated for 1.5 hours under reflux. The mixture was then allowed to cool, a 10% aqueous solution (500 ml) of sodium thiosulfate was added, the mixture was stirred for 30 minutes, and further water (550 ml) was added. The formed crystals were filtered, washed with a 2% aqueous solution (700 ml) of sodium thiosulfate and then with water (4 l), and dried to give a γ-orizanol (1 Kg), which was found by gas chromatography to contain about 23% cyclobranol. This crystalline product (1 Kg) was suspended in a 4% ethanolic KOH solution, and the suspension was heated for 3 hours under reflux. After cooling the resulting mixture, the precipitated potassium salt of γ-orizanol was filtered, and suspended in methanol (8 l), and the suspension was refluxed for 2 hours. After cooling the resulting mixture, the precipitated yellow crystals were filtered and dried to give the potassium salt of a γ-orizanol (260 g). This crystalline product was treated similarly with 3% and 2% ethanolic KOH solutions to give yellow crystals (130 g). This product was found to contain 88% cyclobranol. Further this yellow crystalline product (130 g) was saponified in a 2N ethanolic KOH solution (2.6 l), and the residue was extracted with chloroform (1.2 l). The extract was dried and evaporated under reduced pressure to give crude cyclobranol (80 g, 88% purity), which was then recrystallized 3 times from acetone (1.6 l), thus giving crystalline cyclobranol (28 g), m.p. 165°-166° C., specific rotation [α] D 25 +47.0° (C 1.00, CHCl 3 ). This cyclobranol, on gas chromatography, gave a single peak.
The triterpenyl esters of organic acids according to the present invention can be readily obtained by known methods of esterification from the above defined alcohols and organic acids. That is, the ester can be prepared by the esterification of the organic acid and the triterpenyl alcohol through dehydration in the presence of a catalyst such as sulfuric acid, p-toluenesulfonic acid, or boron trifluoride (BF 3 ), the reaction of the anhydride of the organic acid with the triterpenyl alcohol in the presence of a catalyst such as sulfuric acid or zinc chloride, or the reaction of a halide of the organic acid (the corresponding acyl halide; hereinafter referred to as organic acid halide), with the triterpenyl alcohol. Of these methods, the most favorable is the method of reacting the organic acid halide with the triterpenyl alcohol. That is, when the starting organic acid is a monobasic acid such as nicotinic acid, linoleic acid, linolenic acid, arachidonic acid, eicosanpentaenoic acid, C 6 ˜Cl 14 saturated fatty acids, or an organic acid corresponding to an ester of formula II, IIIB, or IIId, i.e. a mono- or di-substituted cinnamic, benzoic, or α-(C 1 -C 4 alkyl) cinnamic acid having; one substituent selected from NO 2 , OR 3 , OCOR 4 , and NHCOR 3 groups (formula II); two different substituents OR.sub. group and any of OCOR 4 , NO 2 , NH 2 , and NHCOR 3 groups (formula IIIb); or two OR 3 groups (formula IIId); on the benzene ring; the intended triterpenyl esters of organic acid can be obtained with ease and in a high yield by converting the COOH group of the starting organic acid with a halogenating reagent into the CO-halogen group, followed by esterifying the resulting acid halide with the triterpenyl alcohol in the presence of a dehydrohalogenating agent in a solvent at a temperature of 10° to 100° C. Favorable halogenating reagents for this purpose are thionyl chloride, sulfuryl chloride, phosphorus pentachloride, phosphorus oxychloride, benzoyl chloride, phthaloyl chloride, hydrogen chloride, and hydrogen bromide. Suitable dehydrohalogenating agents for use in the esterification are pyridine, quinoline, trimethylamine, triethylamine, tripropylamine, tributylamine, magnesium, and dimethylaniline.
When the starting organic acid is one corresponding to an ester of formula II, IIIa, or IIIc [i.e. a mono- or di-substituted cinnamic, benzoic, or α-(C 1 -C 4 alkyl) cinnamic acid having one substituent OH or NH 2 group (formula II), two different substituents OH and OR 3 groups or OH and OCOR 4 groups (formula IIIa), or two OH groups (formula IIIc), on the benzene ring], the acylated derivative of triterpenyl esters of organic acids can be obtained with ease and in a high yield by acylating the OH or NH 2 group of the organic acid in advance, followed by halogenation and esterification of the resulting acid as stated above. Then each ester of formula II, IIIa, or IIIc having OH or NH 2 group on the benzene ring can be prepared by deacylating the above acylated derivative, that is, by heating it in a concentrated aqueous solution of ammonia, caustic alkali (NaOH or KOH), or inorganic acid (HCl, H 2 SO 4 , or H 3 PO 4 ).
The acylation can be readily accomplished by using an acylating agent such as an acid anhydride or acid halide of such a lower fatty acid as acetic acid, propionic acid, butyric acid or caproic acid.
Further an ester of formula II or IIIb having one substituent NH 2 group or two different substituents NH 2 and OR 3 groups or NH 2 and OCOR 4 groups on the benzene ring can be prepared by reducing the corresponding triterpenyl esters of substituted cinnamic, benzoic, or α-(C 1 -C 4 alkyl) cinnamic acid having one NO 2 group, NO 2 and OR 3 groups, or NO 2 and OCOR 4 groups, on the benzene ring of the acid portion, with iron (or zinc) and acid (HCl, H 2 SO 4 , or acetic acid), or with tin (or tin chloride) and conc. H 2 SO 4 to convert the NO 2 group selectively into NH 2 group. This reduction method using metal and acid is best suited since the unsaturated group present in the triterpenyl alcohol portion is not reduced.
The acylation of the above amino derivatives in the usual manner gives readily the corresponding esters of the invention having one NHCOR 3 group or two groups of NHCOR 3 and either OR 3 or OCOR 4 on the benzene ring of the acid portion.
Pharmacological action
In the next place, detailed description is given on the results of pharmacological tests of compounds according to the present invention for toxicity and anti-hyperlipidemic activity.
Acute toxicity test
Acute toxicity tests were conducted using 5 male ddy strain mice (30±2 g) and 5 male Wistar strain rats (100±2 g) for each compound by oral administration.
Examples of the compounds according to the present invention subjected to the acute toxicity tests were as follows:
Example 29, Cycloartenyl ester of 4-hydroxy-3-methoxybenzoic acid,
Example 37, Cyclobranyl ester of 4-hydroxy-3-methoxybenzoic acid,
Example 86, 24-Methylenecycloartanyl ester of 4-hydroxy-3-methoxybenzoic acid,
Example 60, Cycloartenyl ester of 3-ethoxy-4-hydroxybenzoic acid,
Example 62, Cyclobranyl ester of 3-ethoxy-4-hydroxybenzoic acid,
Example 74, Cycloartenyl ester of 4-hydroxy-4-propoxycinnamic acid,
Example 71, Cyclobranyl ester of 3-ethoxy-4-hydroxycinnamic acid,
Example 27, Cycloartenyl ester of 3,4-dihydroxybenzoic acid,
Example 39, Cyclobranyl ester of 3,4-dihydroxybenzoic acid,
Example 83, 24-Methylenecycloartanyl ester of p-acetoxycinnamic acid,
Example 2, Cycloartenyl ester of 3,4-dihydroxycinnamic acid,
Example 32, Cyclobranyl ester of 3,4-dihydroxycinnamic acid,
Example 82, 24-Methylenecycloartanyl ester of 3,4-dihydroxycinnamic acid,
Example 8, Cycloartenyl ester of o-hydroxybenzoic acid,
Example 41, Cyclobranyl ester of o-hydroxybenzoic acid,
Example 72, 24-Methylenecycloartanyl ester of 4-acetoxy-3-ethoxycinnamic acid,
Example 10, Cycloartenyl ester of p-hydroxybenzoic acid,
Example 58, Cyclobranyl ester of p-hydroxybenzoic acid,
Example 13, Cycloartenyl ester of o-methoxybenzoic acid,
Example 14, Cycloartenyl ester of p-methoxybenzoic acid,
Example 24, Cycloartenyl ester of nicotinic acid,
Example 50, Cyclobranyl ester of nicotinic acid,
Example 20, Cycloartenyl ester of p-acetamidobenzoic acid,
Example 19, Cycloartenyl ester of p-aminobenzoic acid,
Example 43, Cyclobranyl ester of p-aminobenzoic acid,
Example 100, 24-Methylenecyloartanyl ester of m-aminobenzoic acid,
Example 25, Cycloartenyl ester of linoleic acid,
Example 51, Cyclobranyl ester of linoleic acid,
Example 93, 24-Methylenecyloartanyl ester of linoleic acid,
Example 12, Cycloartenyl ester of m-hydroxybenzoic acid,
Example 54, Cyclobranyl ester of m-hydroxybenzoic acid,
Example 16, Cycloartenyl ester of o-nitrobenzoic acid,
Example 47, Cyclobranyl ester of o-aminobenzoic acid,
Example 23, Cycloartenyl ester of m-aminobenzoic acid,
Example 49, Cyclobranyl ester of m-aminobenzoic acid,
Example 100-1, Cycloartenyl ester of 4-hydroxy-3-methoxycinnamic acid (another name: cycloartenyl ester of ferulic acid),
Example 100-2, Cyclobranyl ester of 4-hydroxy-3-methoxycinnamic acid,
Example 100-3, 24-Methylenecycloartanyl ester of 4-hydroxy-3-methoxycinnamic acid,
Example 101, Cycloartenyl ester of p-nitrocinnamic acid,
Example 102, Cycloartenyl ester of p-aminocinnamic acid,
Example 104, Cyclobranyl ester of p-aminocinnamic acid,
Example 108, Cycloartenyl ester of m-aminocinnamic acid,
Example 112, 24-Methylenecyloartanyl ester of m-aminocinnamic acid,
Example 114, Cycloartenyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid,
Example 116, Cyclobranyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid,
Example 118, 24-Methylenecycloartanyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid,
Example 120, Cycloartenyl ester of 4-hydroxy-3-methoxy-α-ethylcinnamic acid,
Example 140, Cyclobranyl ester of 3-ethoxy-4-hydroxy-α-methylcinnamic acid,
Example 130, Cycloartenyl ester of 4-hydroxy-α-ethylcinnamic acid,
Example 146, Cycloartenyl ester of 4-hydroxy-3-propoxy-α-methylcinnamic acid,
Example 167, Cycloartenyl ester of 4-amino-3-methoxybenzoic acid,
Example 173, Cyclobranyl ester of 5-amino-2-methoxybenzoic acid,
Example 189, Cycloartenyl ester of 4-amino-3-methoxy-α-methylcinnamic acid,
Example 177, Cycloartenyl ester of 4-amino-3-methoxycinnamic acid,
Example 205, Cycloartenyl ester of p-amino-α-methylcinnamic acid,
Example 183, Cycloartenyl ester of 5-amino-2-ethoxycinnamic acid,
Example 212, Cyclobranyl ester of m-amino-α-methylcinnamic acid,
Example 191, 24-Methylenecycloartanyl ester of 4-amino-3-methoxy-α-methylcinnamic acid,
Example 197, 24-Methylenecycloartanyl ester of 5-amino-2-propoxy-α-methylcinnamic acid,
Example 171, Cycloartenyl ester of 5-amino-2-methoxybenzoic acid,
Example 170, Cycloartenyl ester of 2-methoxy-5-nitrobenzoic acid,
Example 178, Cyclobranyl ester of 4-amino-3-methoxycinnamic acid,
EXAMPLE 195, Cycloartenyl ester of 5-amino-2-propoxy-α-methylcinnamic acid,
EXAMPLE 213, 24-Methylenecycloartanyl ester of m-amino-α-methylcinnamic acid,
EXAMPLE 113, Cycloartenyl ester of 3-methoxy-4-propionyloxy-α-methylcinnamic acid,
EXAMPLE 117, 24-Methylenecycloartanyl ester of 3-methoxy-4-propionyloxy-α-methylcinnamic acid.
The above 66 compounds of esters, and as control drugs, cycloartenol, 24-methylenecycloartanol, cyclobranol, and γ-orizanol were given forcibly to the above-mentioned mice and rats by means of a throat explorer rod in doses of 0.1 to 5 g/Kg for mice and 2 to 6 g/Kg for rats. During the test, the temperature of the animal room was kept at 22° to 23 ° C. After administration, the animals were observed for 2 weeks. With these doses none of the animals died. During the observation, no symptom of toxicosis appeared and no difference in behavior as well as in body weight was found between the animals given the test and the normal animals not given the compound. In the inspection conducted after 2-week observation, no macroscopic lesion was found in any part of main organs. Thus the compound of the invention has very low toxicity, so that the LD 50 value could not determined.
Pharmacological test method A for anti-hyper lipidemic activity (the term "method A" is used in the present specification)
Male Wistar strain rats (100±lg, each 10 rats were formed into a group) were used as test animals. Diet for the control group was prepared by thorough mixing of 20% casein, 62.5% glucose, 10% hydrogenated coconut oil, 2% agar powder, 4% vitamin-containing salt mixture, 1% cholesterol, and 0.5% cholic acid (this composition is described by Fukushima et al, in "Yakugaku Zassi", 89, No. 6, pp. 857-862 (1962)). Diet for the test groups was prepared by good mixing of 1% each of cycloartenol, 24-methylenecycloartanol, and cyclobranol with the control group's diet. Each rat was kept in a cage at a constant temperature of 23±1° C. and a constant R.H. of 55±5% for 2 weeks, during which 10 g/day of the prescribed was given. Finally the rats were fasted from food except water for 16 hours (from 4 p.m. of the 14th test day to 8 a.m. of the 15th test day), and under anesthesia with pentbarbital sodium (tradename: Nembutal), blood was taken from each rat through the descending abdominal arota. Then, TC, HDL-C, TG, PL, and LPO in the serum were measured in the manner that will be described below.
Pharmacological test method B for anti-hyperlipidemic acitivity (the term "method B" was used in the present specification)
Male Wistar strain rats (100±1 g, each 8 rats were formed into a group except that the control group fed with a hyperlipidemic diet was formed of 16 rats) were used as test animals. A powdery diet (CE-2, supplied by Clea Japan, Inc.) was used as ordinary diet. The hyperlipidemic diet was prepared by fortifying the ordinary diet with cholesterol (1%) and cholic acid (0.5%). Each test compound (1%) for administration was admixed with the hyperlipidemic diet. Each two rats were kept in a cage and given the prescribed diet and water ad libitum. Thus the rats were fed for 4 weeks at a constant temperature of 23±1° C. and a constant R.H. of 55±5%. Finally, the rats were fasted from food except water for 16 hours (from 4 p.m. of the 28th test day to 8 a.m. of the 29th test day), and under anesthesia with pentbarbital sodium (tradename: Nembutal), blood was taken from each rat through the descending abdominal arota. Then, TC, HDL-C, TG, PL, and LPO in the serum were measured in the following manner.
Method for determination of serum TC
A TC kit-K (supplied by Nippon Shoji Kaisha, Ltd.) was used. The principle of this determination is as follows: The ester of cholesterol in the serum is hydrolyzed with cholesterol-ester hydrolase into free cholesterol and fatty acids. All the free cholesterol is oxidized with cholesterol oxydase to form Δ 4 -cholestenone and hydrogen peroxide. Phenol and 4-aminoantipyrin are oxidatively condensed together by the formed hydrogen peroxide and peroxydase. The produced red quinone coloring matter is measured by colorimetry for absorbance at 500 nm using a spectrophotometer, thereby determining the TC:
Preparation of color-developing liquid:
Color-developing reagent: One bial (components: cholesterol esterase 25,000μ, cholesterol oxydase 25μ, peroxydase 3,554μ, 4-aminoantipyrin 20 mg)
Buffer solution: 100 ml of the solution contains phenol (33.3 mg), potassium dihydrogenphosphate (489.9 mg), and anhydrous disodium hydrogenphosphate (908.5 mg) in purified water.
Standard solution: 100 ml of the solution contains cholesterol (300 mg).
A solution of one bial of the above color-developing reagent in 160 ml of the buffer solution is referred to as color-developing liquid.
The color-developing liquid (3.0 ml) is well mixed with the sample serum (0.02 ml). The mixture once heated at 37° C. for 15 minutes, is measured for absorbance at 500 nm with a spectrophotometer. The found absorbance is denoted by EA. On the other hand, the color-developing liquid (3.0 ml) is well mixed with the standard solution. The mixture is treated and measured for absorbance at 500 nm in the same manner as the above. This found absorbance is denoted by ES. Both EA and ES are determined with reference to the value of the blank test conducted using the color-developing liquid (3.0 ml) alone. ##EQU1##
Method for determination of serum HDL-C
An HDL-C kit-N (supplied by Nippon Shoji Kaisha, Ltd.) was used. Ultra-high density lipoprotein (VLDL) and lo density lipoprotein (LDL) in the serum is precipitated by the action of heparin. The precipitate is separated by centrifugation. High density lipoprotein (HDL) is dissolved in the separated supernatant. Esters of cholesterol in this fraction is hydrolyzed with cholesterol-ester hydrolase into free cholesterol and fatty acids. All the free cholesterol is oxidized with cholesterol oxydase to form Δ 4 -cholestenone and hydrogen peroxide. Phenol and 4-aminoantipyrine are oxidatively condensed together by the formed hydrogen peroxide and peroxydase. The produced red quinone coloring matter is measured by colorimetry for absorbance at 500 nm using a spectrophotometer, thereby determining the HDL-C.
Method for determination of serum PL
A PL kit-K (supplied by Nippon Shoji Kaisha, Ltd.) was used for the determination. Lecithin, sphingomyelin, and lysolecithin are decomposed by phospholipase D into choline and phosphatidic acid, N-acylsphingosyl phosphate, or lysophosphatidic acid, respectively. The resulting choline is quantitatively decomposed by choline oxydase into hydrogen peroxide and betaine. With this hydrogen peroxide, and aid of peroxydase, phenol and 4-aminoantipyrin are condensed into red quinone pigment, then the absorbance at 500 nm of which is measured with a spectrophotometer, thereby determining the PL.
Method for determination of serum TG
Serum TG level was determined by means of a triglyceride test kit (supplied by Wako Pure Chemical Industries, Ltd.) in which acetylacetone is used for a reagent, in the following manner: Serum proteins are precipitated, when isopropyl alcohol and the sample serum are mixed. Thereby serum lipids and sacchalides are extracted into the isopropyl alcohol layer. An adsorbent is added to the isopropyl alcohol solution to adsorb coloration-interferring materials. After centrifugation of the mixture, potassium hydroxide is added to a portion of the supernatant, thereby saponifying the triglyceride to liberate glycerol. Then the pH of the mixture is adjusted to 6 by adding a buffer solution, and a sodium metaperiodate solution is added to oxidize the glycerol into formic acid (1 mole from mole of gylcerol) and formaldehyde (2 moles from mole of glycerol). The resulting form aldehyde is allowed to react with acetylacetone and with the ammonia in the buffer solution, forming a cyclic compound 3,5-diacetyl-1,4-dihydrobutidine. This yellow pigment is determined by measuring the absorbance at 410 nm with a spectrophotometer, thus determining the TG content.
Method for determination of serum LPO
A lipoperoxide test kit (supplied by Wako Pure Chemical Industries, Ltd.) according to the Yagi's thiobarbituric acid method [K. Yagi, Biochem. Med. 15, p 212 (1976), Vitamin 49, p 403 (1975)] was used for this determination. Physiological saline (1.0 ml) is added to the sample serum (0.05 ml) and the mixture is stirred gently. After centrifugation (3,000 r.p.m., 10 minutes) of the mixture, 1/12N-H 2 SO 4 (4.0 ml) is added and well mixed with the supernatant (0.5 ml). A 10% aqueous phosphotungstic acid solution (0.5 ml) is added thereto and the mixture is stirred well, allowed to stand for 5 minutes, and centrifuged at 3,000 r.p.m. for 10 minutes. The resulting precipitate is suspended thoroughly in a mixture of 1/12 NH 2 SO 4 (2.0 ml) and a 10% aqueous phosphotungstic acid solution by means of a mixer. The suspension is then centrifuged at 3000 r.p.m. for 10 minutes, then the obtained precipitate is suspended in distilled water (4.0 ml) by means of a mixer. Then a TBA reagent (1.0 ml; 50% acetic acid solution containing thiobarbituric acid) is well mixed with the suspension. The mixture is charged in a centrifuge tube, and heated in a boiling water bath for 60 minutes with a glass ball placed on the top of the tube. After 5-minute cooling of the tube in a running water, butanol (5.0 ml) is added to the mixture, and well mixed for 20 seconds by means of a mixer with the tube being stoppered, thereby extracting the reaction product in the butanol. The mixture is centrifuged at 3000 r.p.m. for 10 minutes. The butanol layer is measured for fluorescence. After adjustment of the zero point by a blank test, the fluorescence intensity (F) of 0.1 ml of a standard solution (1,1,3,3-tetraethoxypropane 5 n mole/ml) and that of the sample (f) are measured at 553 nm with an excitation wavelength of 515 nm. That is, in this method, the product of the reaction of LPO with thiobarbituric acid is identical with that of malondialdehyde with thiobarbituric acid. Accordingly, the LPO concentration is determined as the amount of malondialdehyde in 1 ml of the serum. The standard solution is a 5n mole/ml aqueous solution of 1,1,3,3-tetraethoxypropane, which is converted quantitatively into malondialdehyde. Since 0.1 ml of the standard solution is used in this method, the quantity of 1,1,3,3-tetraethoxypropane used is 0.5 n mole. Consequently the LPO content is calculated according to the following equation: ##EQU2##
Results of phamacological tests for hypolipidemic activity
The hypolipidemic action of typical compounds among the present invention on serum lipids and on serum lipid hydroperoxide are described below. The compound selected here are the same as selected in the description of the acute toxicity. The tests were carried according to the above methods wherein rats were fed with high cholesterol diet.
Results of the tests for hypolipidemic activities of cycloartenol, cyclobranol, and 24-methylenecycloartanol, which are used as control drugs, are shown in Tables 1 and 2 (according to method A) and Tables 15 and 16 (according to method B). Effects of these compounds were described already.
Hypolipidemic effects of compounds of the present invention, tested according to method A are shown in Tables 3 to 14, 23, and 24. The effects of compounds according to the present invention and those of cycloartenol, cyclobranol, 24-methylenecycloartanol, and γ-orizanol as control drugs, with method B are shown in Tables 17 to 20. Tables 17 to 20 indicate that TC, PL, and LPO of the normal diet feeding group (denoted by N) were depressed at high significance levels (p<0.001, marked with ***) without exception while the HDL-C was raised at high significance levels (p<0.001), in contrast with those of the control group fed with the hyperlipidemic diet (denoted by C). On the TG in N tendency to depress was shown in C, but this difference between values of TG in N and C was not significant.
Hypolipidemic effects of improving serum lipids' components were clearly observed in the groups given the hyperlipidemic diet containing each of compounds according to the present invention, or each of the control drugs, as compared with those in the group given the hyperlipidemic diet only. In particular, compounds according to the present invention brought about distinctly better effects on two or more serum lipids components of TC, HDL-C, PL, and LPO than did the control compounds.
According to method A, the TC level were changed by compounds of the present invention as follows: The compound of Example 49 depressed the TC levels at a high significance level (p<0.001). The compounds of Examples 37, 62, 71, 27, 39, 8, 41, 10, 58, 13, 14, 19, 43, 100, 25, 51, 93, 100-1, 100-2, 101, 105, and 109 depressed the TC levels at medium significance levels. The compounds of Examples 29, 86, 60, 74, 83, 32, 72, 24, 50, 20, 12, 16, and 23 depressed the TC levels at low significance levels (p<0.05). The compounds of Examples 2, 82, and 47 didn't depress the TC significantly, but tended to depress apparently.
According to method B, the TC levels were 5 depressed by the control drugs, i.e. the three triterpenyl alcohols and γ-orizanol, at medium significance levels (p<0.01), as compared with the TC levels in the control group given the hyperlipidemic diet only. In contrast, the compounds of Examples 114, 116, 118, 189, 205, 212, 191, 197, 171, 178, 195, and 213 depressed the TC levels at high significance levels (p<0.001). The compounds of Examples 120, 140, 130, 146, 167, 173, 177, 183, 170, 113 and 117 depressed the TC levels at medium significance levels (p<0.01).
The HLD-C contents, according to method A, were affected by compounds of the invention as follows: The compound of Example 8 raised the HLD-C contents at a high significance level (p<0.001), the compounds of Examples 37, 62, and 39 at medium significance levels (p<0.01), and the compounds of Examples 71, 27, 83, 41, 51, 100-1, 105, and 109 at low significance levels (p <0.05). The compounds of Examples 86, 74, 10, 12, 47, and 49 scarcely varied or slight depressed the HLD-C contents while the compounds of other Examples showed tendencies to raise them but insignificantly.
According to method B, effects of test compounds on the HLD-C were as follows: The control drug cycloartenol caused the depression at a significance level (p<0.01), while the other control drugs cyclobranol, 24-methylenecycloartanol, and γ-orizanol showed tendencies to the raise or the depression but insignificantly. In contrast, the compounds of Examples 114, 116, 118, 140, 146, 167, 173, 189, 177, 205, 212, and 213 raised HDL-C levels at high significance levels (p<0.001) and the compounds of Examples 120, 130, 183, 191, 197, 171, 178, 195, 113, and 117 increased at significance levels (p<0.01). The compound of Example 170 caused the rise at a low significance level (p<0.05). In particular, the compounds of Examples 116, 118, 140, 167, 173, 170, 178, 195, and 213 caused remarkable rises in the HDL-C contents in comparison with that in the group given the normal diet.
As to the AI, all the compounds tended evidently to depress the AI levels without exception according to method A or B.
The TG, according to method A, was not depressed at the significance level but unvaried or slightly depressed by any compound tested, except that the depression was caused by the compound of Example 49 at a medium significance level (p<0.01) and by the compounds of Examples 100-1, 100-2, and 101 at low significance levels (p<0.05). According to method B, compounds of the present invention as well as control drugs showed tendencies to slight or some degree depression of the TG but insignificantly.
As to the PL, according to method A, the compounds of Examples 62, 71, 27, 39, 8, 41, 72, 24, 50, 20, 19, 43, 25, 51, 93, 49, and 100-2 depressed the PL levels at significance levels (p<0.001), the compounds of Examples 29, 37, 60, 74, 83, 58, 13, 14, 100, and 101 at significance levels (p<0.01), and the compounds of Examples 86, 32, 10, 23, 100-1, 105, and 109 at significance levels (p<0.05). The compounds of Examples 2, 82, 12, 16 and 47 showed apparent tendencies to the depression but insignificantly.
According to method B, the control drugs showed tendencies to slight depression of the PL but insignificantly. In contrast, the compounds of Examples 114, 116, 118, 140, 146, 171, 195, and 213 depressed the PL levels at significance levels (p<0.001), the compounds of Examples 120, 130, 189, 205, 212, 191, 197, 170, 178, 113, and 117 at significance levels (p<0.01), and the compounds of Examples 167, 173, 177, and 183 at significance levels (p<0.05).
As to LPO, according to method A, the compounds of Examples 10, 58, 13, 14, 19, 43, 100, 25, 51, 93, 101, 102, 104, and 112 depressed the LPO levels at significance levels (p<0.001), the compound of Example 50 at a significance level, and the compounds of Examples 29, 37, 60, 62, 71, 24, 12, 16, 47, 23, and 49 at significance levels (p<0.05). Other compounds of the invention showed distinct tendencies to the depression but insignificantly. According to method B, the control drug γ-orizanol depressed the LPO at a significance level (p<0.01) and the control drugs triterpenyl alcohols showed apparent tendencies to the depression but insignificantly. In contrast, the compounds of Examples 114, 116, 118, 120, 140, 130, 146, 189, 205, 212, 183, 191, 197, 171, 178, 195, and 213 depressed the LPO at significance levels (p<0.001) and the compounds of Examples 167, 173, 177, 170, 113, and 117 at significance levels (p<0.01).
As described above, most of the compounds according to the present invention, in the tests according to method A or B, tended obviously to raise the HDL-C contents and depress the TC, AI, PL, and LPO levels. In comparison with effects obtained by the administration of the free triterpenyl alcohols alone, it is evident that these hypolipidemic activities of the compounds of the invention are synergistic effects.
Increases of the body weights of rats used for the hypolipidemic activity tests according to method B are shown in Tables 21 and 22. These tables shows that the body weights of the rats given the normal diet were increased at significance levels (p<0.001) as compared with those of the control group rats given the hyperlipidemic diet. The group of rats given the hyperlipidemic diet containing each of typical compounds according to the present invention and the groups of rats given the hyperlipidemic diet containing each of the control drugs showed slight increases in body weight but insignificantly, as compared with the control group of rats given the hyperlipidemic diet alone.
TABLE 1__________________________________________________________________________TC HDL-C TG PL LPOSample mg/dl SD mg/dl SD AI mg/dl mg/dl SD n mol/ml SD__________________________________________________________________________C 205.1 ±27.4 81.5 ±10.1 1.517 34.3 ±4.8 173.6 ±11.0 2.27 ±0.381 173.5* ±32.1 72.0* ±9.4 1.410 38.0 ±5.2 173.7 ±12.1 2.03 ±0.232 168.0* ±30.4 90.3 ±9.3 0.860 30.6 ±4.9 168.2 ±10.8 1.98 ±0.273 200.1 ±33.5 76.8 ±8.9 1.605 33.3 ±6.5 167.0 ±13.0 2.40 ±0.25__________________________________________________________________________ [Notes In Sample column, C: Serum of the control group of 10 rats given the hyperlipidemic diet in Tables 1 to 24. 1: Serum of the group of 10 rats given the hyperlipidemic diet containing 1% of cycloartenol as a control drug in Tables 1 to 2. 2: Serum of the group of 10 rats given the hyperlipidemic diet containing 1% of cyclobranol as a control drug in Tables 1 to 2. 3: Serum of the group of 10 rats given the hyperlipidemic diet containing 1% of 24methylenecyloartanol as a control drug in Tables 1 to 2. Mark*: Signicicance level (p < 0.05) SD: Standard deviation. These notations are applied to the following tables.
TABLE 2__________________________________________________________________________TC HDL-C AI TG PL LPO Diff. % of Diff. % of Diff. % of Diff % of Diff. % of Diff. % ofSample mg/dl diff. mg/dl diff. mg/dl diff. mg/dl diff. mg/dl diff. n mol/ml diff.__________________________________________________________________________1 -31.6 -15.4 -9.5 -11.6 -1.107 -7.1 +3.7 +10.9 +0.1 +0.06 -0.24 -10.62 -37.1 -18.1 +8.8 +10.8 -0.657 -43.3 -3.7 -10.9 -5.4 -3.1 -0.29 -12.83 -5.0 -2.4 -4.7 -5.8 +0.088 +5.8 -1.0 -2.9 -6.6 -3.8 +0.13 +5.8__________________________________________________________________________ [Notes "Diff." means the difference between QQc and "% of diff." means (QQc) × 100/Qc, wherein Q: Concentration of the component lipid in the sample serum, Qc: Concentration of the component lipid in the serum of the control group. These notations apply in the following tables.
TABLE 3__________________________________________________________________________Sample TC HDL-C TG PL LPO(Example No.) mg/dl SD mg/dl SD AI mg/dl SD mg/dl SD nmol/ml SD__________________________________________________________________________C 192.6 ±24.3 96.2 ±8.2 1.002 33.2 ±8.1 180.9 ±14.7 2.33 ±0.3529 162.7* ±23.4 101.0 ±8.2 0.611 32.7 ±8.5 160.6** ±14.9 1.95* ±0.3037 161.2** ±22.8 110.4** ±9.4 0.460 31.0 ±7.8 155.4** ±14.7 1.91* ±0.3286 165.6* ±25.0 91.9 ±9.7 0.802 33.1 ±8.3 163.2* ±17.2 2.06 ±0.2860 164.9* ±24.0 102.5 ±9.2 0.609 32.8 ±8.8 161.4** ±15.2 1.98* ±0.3362 159.5** ±23.2 108.2** ±9.3 0.474 32.0 ±9.2 156.5*** ±13.8 1.94* ±0.3274 165.1* ±23.3 92.4 ±8.9 0.787 33.1 ±7.4 162.1** ±14.5 2.09 ±0.3371 161.4** ±23.6 106.0* ±9.4 0.523 32.9 ±8.3 157.7*** ±15.6 1.96* ±0.30__________________________________________________________________________ [Notes Mark**: Significance level (p < 0.01) ***: Significance level (p < 0.001) Example No.: Serum of the group of 10 rats given the hyperipidemic diet containing 1% of compounds of example number each in Tables 3 to 24. These notations apply in the following tables.
TABLE 4__________________________________________________________________________ TC HDL-C AI TG PL LPOSample Diff. % of Diff. % of % of Diff. % of Diff. % of Diff. % of(Example No.) mg/dl diff. mg/dl diff. Diff. diff. mg/dl diff. mg/dl diff. nmol/ml diff.__________________________________________________________________________29 -29.9 -15.5 +4.8 +5.0 -0.391 -39.0 -0.5 -1.5 -20.3 -11.2 -0.38 -16.337 -31.4 -16.3 +14.2 +14.8 -0.542 -54.1 -2.2 -6.6 -25.5 -14.1 -0.42 -18.086 -27.0 -14.0 -4.3 -4.5 -0.200 -20.0 -0.1 -0.3 -17.7 -9.8 -0.27 -11.660 -27.7 14.4 +6.3 +6.5 -0.393 -39.2 -0.4 -1.2 -19.5 -10.8 -0.35 -15.062 -33.1 17.2 +12.0 +12.5 -0.528 -52.7 -1.2 -3.6 -24.4 -13.5 -0.39 -16.874 -27.5 14.3 -3.8 -4.0 -0.215 -21.5 -0.1 -0.3 -18.8 -10.4 -0.24 -10.471 -31.2 16.2 +9.8 +10.2 -0.479 -47.8 -0.9 -2.8 -23.2 -12.8 -0.37 -15.9__________________________________________________________________________
TABLE 5__________________________________________________________________________Sample TC HDL-C TG PL LPO(Example No.) mg/dl SD mg/dl SD AI mg/dl SD mg/dl SD nmol/ml SD__________________________________________________________________________C 217.1 ±25.2 80.9 ±10.2 1.684 42.8 ±6.4 179.7 ±10.9 2.31 ±0.4027 186.1** ±22.7 95.2* ±12.3 0.955 40.4 ±5.7 160.3*** ±11.0 1.99 ±0.3839 176.9** ±23.3 98.1** ±11.4 0.803 39.8 ±7.2 155.1*** ±12.2 1.99 ±0.3583 192.1* ±23.1 93.3* ±10.8 1.059 41.1 ±6.5 162.1** ±9.7 2.02 ±0.27 2 194.5 ±23.1 89.2 ±10.7 1.180 41.3 ±7.1 170.2 ±10.3 2.05 ±0.3432 190.4* ±23.2 89.2 ±11.2 1.135 40.7 ±5.5 168.2* ±11.4 2.06 ±0.2982 195.8 ±25.0 87.9 ±11.3 1.228 42.3 ±5.3 173.9 ±12.7 2.08 ±0.29 8 177.8** ±24.5 101.1*** ±10.8 0.759 41.3 ±6.6 148.8*** ±11.8 2.01 ±0.2941 175.6** ±23.8 92.9* ±10.6 0.890 41.5 ±6.3 156.7*** ±10.9 2.01 ±0.3572 186.5* ±22.7 89.2 ±10.2 1.091 41.8 ±6.1 160.3*** ±9.8 2.07 ±0.44__________________________________________________________________________
TABLE 6__________________________________________________________________________ TC HDL-C AI TG PL LPOSample Diff. % of Diff. % of % of Diff. % of Diff. % of Diff. % of(Example No.) mg/dl diff. mg/dl diff. Diff. diff. mg/dl diff. mg/dl diff. nmol/ml diff.__________________________________________________________________________27 -31.0 -14.3 +14.3 +17.7 -0.729 -43.3 -2.4 -5.5 -19.4 -10.8 -0.32 -14.039 -40.2 -18.5 +17.2 +21.2 -0.881 -52.3 -3.0 -6.9 -24.6 -13.7 -0.32 -14.083 -25.0 -11.5 +12.4 +15.3 -0.625 -37.1 -1.7 -4.0 -17.6 -9.8 -0.29 -12.7 2 -22.6 -10.4 +8.3 +10.2 -0.504 -29.9 -1.5 -3.5 -9.0 -5.0 -0.26 -11.232 -26.7 -12.3 `+8.3 +10.2 - 0.549 -32.6 -2.1 -4.8 -11.5 -6.4 -0.25 -10.782 -21.3 -9.8 +7.0 +8.7 -0.456 -27.1 -0.5 -1.2 -5.8 -3.2 -0.23 -9.8 8 -39.3 -18.1 +20.2 +25.0 -0.925 -54.9 -1.5 -3.5 -30.9 -17.2 -0.30 -13.041 -41.5 19.1 +12.0 +14.8 -0.794 -47.1 -1.3 -3.0 -23.0 -12.8 -0.30 -13.072 -30.6 -14.1 +8.3 +10.2 -0.593 -35.2 -1.0 -2.4 -19.4 -10.8 -0.24 -10.4__________________________________________________________________________
TABLE 7__________________________________________________________________________Sample TC HDL-C TG PL LPO(Example No.) mg/dl SD mg/dl SD AI mg/dl SD mg/dl SD nmol/ml SD__________________________________________________________________________C 166.6 ±14.1 60.2 ±8.5 1.767 27.2 ±4.2 136.7 ±12.0 2.53 ±0.3110 146.5** ±15.3 57.6 ±9.4 1.543 27.3 ±4.1 123.3* ±11.9 1.73*** ±0.2458 143.7** ±17.9 62.0 ±9.6 1.318 26.8 ±4.0 121.3** ±11.8 1.82*** ±0.1313 144.5** ±16.8 60.5 ±8.6 1.388 26.2 ±3.8 122.8** ±12.7 1.94*** ±0.2514 145.8** ±15.2 64.1 ±9.2 1.275 25.4 ±3.1 120.9** ±11.3 1.81*** ±0.18__________________________________________________________________________
TABLE 8__________________________________________________________________________ TC HDL-C AI TG PL LPOSample Diff. % of Diff. % of % of Diff. % of Diff. % of Diff. % of(Example No.) mg/dl diff. mg/dl diff. DIff. diff. mg/dl diff. mg/dl diff. nmol/ml diff.__________________________________________________________________________10 -20.1 -12.1 -2.6 -4.3 -0.224 -12.7 +0.1 +0.4 -13.4 -9.8 -0.80 -31.658 -22.9 -13.7 +1.8 +3.0 -0.449 -25.4 -0.4 -1.5 -15.4 -11.3 -0.71 -28.113 -22.1 -13.3 +0.3 +0.5 -0.379 -21.4 -1.0 -3.7 -13.9 -10.2 -0.59 -23.314 -20.8 -12.5 +3.9 +6.5 -0.492 -27.8 -1.8 -6.6 -15.8 -11.6 -0.72 -28.5__________________________________________________________________________
TABLE 9__________________________________________________________________________Sample TC HDL-C TG PL LPO(Example No.) mg/dl SD mg/dl SD AI mg/dl SD mg/dl SD nmol/ml SD__________________________________________________________________________C 192.2 ±24.0 86.5 ±9.7 1.232 36.3 ±5.3 172.6 ±10.5 2.24 ±0.2624 164.3* ±23.1 94.0 ±9.8 0.748 34.7 ±6.4 133.8*** ±10.1 1.93* ±0.3050 162.4* ±22.4 95.7 ±10.4 0.697 34.7 ±5.1 138.8*** ±11.3 1.87** ±0.3120 168.8* ±24.5 90.4 ±10.8 0.867 35.2 ±5.8 143.3*** ±11.4 2.02 ±0.3519 156.1** ±24.5 91.9 ±9.4 0.699 31.6 ±5.6 153.6*** ±10.2 1.63*** ±0.2143 157.4** ±23.6 91.9 ±9.6 0.713 33.3 ±6.4 146.0*** ±10.1 1.54*** ±0.24100 159.1** ±22.6 90.1 ±10.3 0.766 34.3 ±6.2 155.6** ±11.4 1.68** ±0.2325 157.4** ±23.4 92.3 ±9.6 0.705 34.0 ±5.4 144.6*** ±11.5 1.67*** ±0.3051 156.5** ±23.5 96.4* ±9.8 0.623 34.7 ±4.9 146.0*** ±12.0 1.69*** ±0.2793 161.1** ±23.3 91.5 ±9.5 0.761 35.1 ±5.0 150.2*** ±11.0 1.70*** ±0.28__________________________________________________________________________
TABLE 10__________________________________________________________________________ TC HDL--C AI TG PL LPOSample Diff. % of Diff. % of % of Diff. % of Diff. % of Diff. % of(Example No.) mg/dl diff. mg/dl diff. Diff. diff. mg/dl diff. mg/dl diff. nmol/ml diff.__________________________________________________________________________24 -27.9 -14.5 +7.5 +8.7 -0.474 -38.8 -1.6 4.3 -38.8 -22.5 -0.31 -13.750 -29.8 -15.5 +9.2 10.6 -0.525 -43.0 -1.6 -4.3 -33.8 -19.6 -0.37 -16.720 -23.4 -12.2 +3.9 +4.5 -0.355 -29.1 -1.1 -3.0 -29.3 -17.0 -0.22 -9.719 -36.1 -18.8 +5.4 +6.2 -0.523 -42.8 -4.7 -12.9 -19.0 -11.0 -0.61 -27.243 -34.8 -18.1 +5.4 +6.2 -0.509 -41.7 -3.0 -8.2 - 26.6 -15.4 -0.70 -31.3100 -33.1 -17.2 +3.6 +4.2 -0.456 -37.3 -2.0 -5.5 -17.6 -10.2 -0.56 -25.225 -34.8 -18.1 +5.8 +6.7 -0.517 -42.3 -2.3 -6.2 -28.0 -16.2 -0.57 -25.651 -35.7 -18.6 +9.9 +11.5 -0.599 -49.0 -1.6 -4.3 -26.6 -15.4 -0.55 -24.493 -31.1 -16.2 +5.0 +5.8 -0.461 -37.7 -1.2 -3.3 -22.4 -13.0 -0.54 -24.3__________________________________________________________________________
TABLE 11__________________________________________________________________________Sample TC HDL--C TG PL LPO(Example No.) mg/dl SD mg/dl SD AI mg/dl SD mg/dl SD nmol/ml SD__________________________________________________________________________C 167.1 ±16.4 58.7 ±6.7 1.847 24.8 ±4.7 148.4 ±13.6 2.34 ±0.2912 150.4* ±15.2 58.5 ±5.8 1.571 24.0 ±5.5 140.4 ±12.8 2.03* ±0.2216 150.2* ±15.3 59.4 ±5.7 1.529 22.0 ±5.3 140.1 ±12.7 2.04* ±0.2347 150.1 ±15.4 53.4 ±6.4 1.811 20.4 ±5.1 140.3 ±12.3 2.03* ±0.2223 147.6* ±15.0 58.9 ±6.2 1.506 20.2 ±5.1 133.1* ±12.6 2.06* ±0.2749 132.7*** ±17.0 58.0 ±5.2 1.288 18.3** ±4.9 128.4*** ±13.0 2.02* ±0.26__________________________________________________________________________
TABLE 12__________________________________________________________________________ TC HDL--C AI TG PL LPOSample Diff. % of Diff. % of % of Diff. % of Diff. % of Diff. % of(Example No.) mg/dl diff. mg/dl diff. Diff. diff. mg/dl diff. mg/dl diff. nmol/ml diff.__________________________________________________________________________12 -16.7 -10.0 -0.2 -0.3 -0.276 -14.9 -0.8 -3.2 -8.0 -5.4 -0.31 -13.216 -16.9 -10.1 +0.7 +1.2 -0.318 -17.2 -2.8 -11.3 -8.3 -5.6 -0.30 -12.847 -17.0 -10.2 -5.3 -9.0 -0.036 -1.9 -4.4 -17.7 -8.1 -5.5 -0.31 -13.223 -19.5 -11.7 +0.2 +0.3 -0.341 -18.5 -4.6 -18.5 -15.3 -10.3 -0.28 -12.049 -34.4 -20.6 -0.7 -1.2 -0.559 -30.3 -6.5 -26.2 -20.0 -13.5 -0.32 -13.7__________________________________________________________________________
TABLE 13__________________________________________________________________________Sample TC HDL--C TG PL LPO(Example No.) mg/dl SD mg/dl SD AI mg/dl SD mg/dl SD nmol/ml SD__________________________________________________________________________C 205.1 ±27.4 81.5 ±10.1 1.517 34.3 ±4.8 173.6 ±11.0 2.27 ±0.38100-1 174.3* ±30.4 79.1 ±9.4 1.204 28.3* ±6.0 150.0*** ±11.4 1.51*** ±0.30100-2 166.7** ±28.1 94.1** ±9.3 0.772 21.6*** ±5.6 143.0*** ±10.6 1.59*** ±0.33100-3 176.6* ±32.3 73.8 ±10.3 1.393 35.1 ±7.3 152.9*** ±10.6 1.89* ±0.26__________________________________________________________________________
TABLE 14__________________________________________________________________________ TC HDL--C AI TG PL LPOSample Diff. % of Diff. % of % of Diff. % of Diff. % of Diff. % of(Example No.) mg/dl diff. mg/dl diff. Diff. diff. mg/dl diff. mg/dl diff. nmol/ml diff.__________________________________________________________________________100-1 -30.8 -15.0 -2.4 -3.0 -0.313 -20.6 -6.0 -17.6 -23.1 -13.3 -0.76 -33.5100-2 -38.4 -18.7 +15.1 +18.5 -0.745 -49.1 -12.7 -37.0 -30.6 -17.6 -0.68 -29.8100-3 -28.5 -13.9 -7.7 -9.4 -0.124 -8.2 +0.8 +2.3 -20.7 -11.9 -0.38 -16.7__________________________________________________________________________
TABLE 15__________________________________________________________________________TC HDL--C TG PL LPOSample mg/dl SD mg/dl SD AI mg/dl SD mg/dl SD nmol/ml SD__________________________________________________________________________C 307.3 ±95.9 13.5 ±3.8 21.8 56.5 ±20.6 142.5 ±30.9 2.80 ±0.381 190.1** ±51.3 10.3** ±1.4 17.5 55.1 ±12.4 140.2 ±40.2 2.68 ±0.452 191.5** ±46.8 15.0 ±5.0 12.0 53.4 ±17.4 138.6 ±38.2 2.60 ±0.403 191.2** ±48.4 12.8 ±3.2 14.8 53.3 ±19.2 133.3 ±25.2 2.71 ±0.32__________________________________________________________________________ [Notes In Sample column, C: Serum of the control group of 16 rats given the hyperlipidemic diet in Tables 15 to 22. 1: Serum of the group of 8 rats given the hyperlipidemic diet containing 1% of cycloartenol as a control drug in Tables 15 to 18 and 21. 2: Serum of the group of 8 rats given the hyperlipidemic diet containing 1% of cyclobranol as a control drug in Tables 15 to 18 and 21. 3: Serum of the group of 8 rats given the hyperlipidemic diet containing 1% of 24:methylencycloartanol as a control drug in Tables 15 to 18 and 21
TABLE 16__________________________________________________________________________ TC HDL--C AI TG PL LPOSample Diff. % of Diff. % of % of Diff. % of Diff. % of Diff. % of(Example No.) mg/dl diff. mg/dl diff. Diff. diff. mg/dl diff. mg/dl diff. nmol/ml diff.__________________________________________________________________________1 -117.2 -38.1 -3.2 -23.7 -4.3 -19.7 -1.4 -2.5 -2.3 -1.6 -0.12 -4.32 -115.8 -37.7 +1.5 +11.1 -9.8 -45.0 -3.1 -5.5 -3.9 -2.7 -0.20 -7.13 -116.1 -37.8 -0.7 -5.2 -7.0 -32.1 -3.2 -5.7 -9.2 -6.5 -0.09 -3.2__________________________________________________________________________
TABLE 17__________________________________________________________________________TC HDL--C TG PL LPOmg/dl SD mg/dl SD AI mg/dl SD mg/dl SD nmol/ml SD__________________________________________________________________________SampleC 307.3 ±95.9 13.5 ±3.8 21.76 56.5 ±20.6 140.1 ±28.5 2.82 ±0.40N 43.4*** ±8.3 29.9*** ±6.7 0.452 54.0 ±12.1 67.3*** ±10.0 1.82*** ±0.251 202.4*** ±48.3 10.3** ±1.4 18.65 54.2 ±14.4 127.6 ±25.8 2.62 ±0.352 197.5** ±45.7 15.2 ±5.6 11.99 53.3 ±13.6 130.3 ±25.2 2.60 ±0.323 198.3** ±45.6 15.1 ±5.0 12.13 54.2 ±15.2 128.4 ±24.8 2.58 ±0.344 190.3** ±45.0 15.3 ±4.8 11.44 52.8 ±18.4 127.6 ±26.0 2.25** ±0.35Example114 138.2*** ±40.3 24.2*** ±5.6 4.711 39.0* ±14.6 96.7*** ±20.0 2.04*** ±0.22116 140.1*** ±38.3 61.4*** ±16.4 1.282 54.0 ± 19.0 97.4*** ±19.1 2.11*** ±0.20118 139.5*** ±39.3 47.4*** ±17.0 1.943 51.4 ±19.4 98.3*** ±16.9 2.08*** ±0.18120 203.2** ±47.4 24.6** ±8.7 7.260 53.0 ±18.0 105.3** ±20.1 2.06*** ±0.20140 197.4** ±45.2 54.8*** ±17.0 2.602 52.4 ±18.4 98.0*** ±17.3 2.02*** ±0.21130 201.3** ±44.2 21.0** ±6.8 8.586 53.4 ±18.0 107.2** ±19.0 2.07*** ±0.23146 198.4** ±47.5 23.4*** ±5.8 7.479 51.4 ±17.4 97.6*** ±18.2 2.02*** ±0.20__________________________________________________________________________ [Notes N: Serum of the group of 8 rats given the ordinary diet. The same applies in the following tables. 4: Serum of the group of 8 rats given the hyperlipidemic diet containing 1% of orizanol. Example No.: Serum of the group of 8 rats given the hyperlipidemic diet containing 1% of compounds of example numbers each in Tables 17 to 22. These notations are applied to the following tables.
TABLE 18__________________________________________________________________________TC HDL--C AI TG PL LPODiff. % of Diff. % of % of Diff. % of Diff. % of Diff. % ofmg/dl diff. mg/dl diff. Diff. diff. mg/dl diff. mg/dl diff. nmol/ml diff.__________________________________________________________________________SampleN -263.9 -85.9 +16.4 +121.5 -21.31 -97.9 -2.5 -4.4 -72.8 -52.0 -1.0 -35.51 -104.9 -34.1 -3.2 -23.7 -3.11 -14.3 -2.3 -4.1 -12.5 -8.9 -0.2 -7.12 -109.8 -35.7 +1.7 +12.6 -9.77 -44.9 -3.2 -5.7 -9.8 -7.0 -0.22 -7.83 -109.0 -35.5 +1.6 +11.9 -9.63 -44.3 -2.3 -4.1 -11.7 -8.4 -0.24 -8.54 -117.0 -38.1 +1.8 +13.3 - 10.32 -47.4 -3.7 -6.5 -12.5 -8.9 -0.57 -20.2Example114 -169.1 -55.0 +10.7 +79.3 -17.05 -78.4 -17.5 -31.0 -43.4 -31.0 -0.78 -27.7116 -167.2 -54.4 +47.9 +354.8 -20.48 -94.1 -6.1 -10.8 -42.7 -30.5 -0.71 -25.2118 -168.2 -54.6 +33.9 +251.1 -19.82 -91.9 -5.1 -9.0 -41.8 -29.8 -0.74 -26.2120 -104.1 -33.9 +11.1 +82.2 -14.5 -66.6 -3.5 -6.2 -34.8 -24.8 -0.76 -27.0140 -109.9 -35.8 +41.3 +305.9 -19.16 -88.0 -4.1 -7.3 -42.1 -30.0 -0.80 -28.4130 -106.0 -34.5 +7.5 +55.6 -13.17 -60.5 -3.1 -5.5 -32.9 -23.5 -0.75 -26.6146 -108.9 -38.1 +9.9 +73.3 -14.28 -65.6 -5.1 -9.0 -42.5 -30.3 -0.80 -28.4__________________________________________________________________________
TABLE 19__________________________________________________________________________TC HDL-C TG PL LPOSamplemg/dl SD mg/dl SD AI mg/dl SD mg/dl SD nmol/ml SD__________________________________________________________________________C 364.6 ±113.8 19.6 ±5.4 17.60 71.4 ±29.5 158.7 ±31.7 2.84 ±0.41N 73.13*** ±24.6 39.7*** ±9.3 0.842 71.5 ±19.4 90.3*** ±9.4 1.75*** ±0.20Example167 271.0** ±43.4 79.6*** ±16.5 2.405 67.1 ±18.6 126.4* ±16.4 2.28** ±0.29173 272.8** ±40.5 58.4*** ±9.0 3.671 65.2 ±27.5 127.2* ±16.3 2.23** ±0.28189 179.5*** ±45.5 35.4*** ±7.3 4.071 58.4 ±17.5 115.0** ±15.6 2.05*** ±0.22177 245.5** ±43.0 32.5*** ±6.0 6.554 63.1 ±26.4 125.8* ±16.5 2.29** ±0.30205 192.4*** ±41.3 37.4*** ±9.4 4.144 60.3 ±21.2 113.1** ±17.0 2.02*** ±0.20212 195.0*** ±41.9 37.2*** ±9.0 4.242 59.7 ±18.9 112.9** ±17.2 2.01*** ±0.21183 244.0** ±42.0 29.2** ±8.5 7.356 65.2 ±22.5 125.7* ±18.1 2.08*** ±0.22191 188.4*** ±32.6 28.4** ±8.0 5.634 60.4 ±23.4 117.3** ±16.9 2.08*** ±0.23197 221.6*** ±38.5 27.1** ±6.4 7.177 61.2 ±24.4 115.5** ±14.9 2.05*** ±0.21__________________________________________________________________________
TABLE 20__________________________________________________________________________TG HDL-C AI TG PL LPO Diff. % of Diff. % of % of Diff. % of Diff. % of Diff. % ofSample mg/dl diff. mg/dl diff. Diff. diff. mg/dl diff. mg/dl diff. n mol/ml diff.__________________________________________________________________________N -365.4 -8.7 +11.4 +71.3 -24.22 -96.3 -28.1 -34.6 -82.4 -46.6 -2.32 -66.9Sample171 -221.6 -53.0 +8.2 +51.3 -18.02 -71.6 -15.7 -19.3 -58.4 -33.0 -1.25 -36.0170 -157.0 -37.5 +19.7 +123.1 -18.83 -74.9 -17.8 -21.9 -51.1 -28.9 -0.49 -14.1178 -226.9 -54.2 +34.4 +215.0 -22.35 -88.9 -22.8 -28.0 -49.8 -28.2 -1.27 -36.6195 -223.1 -53.3 +33.7 +210.6 -22.22 -88.3 -23.5 -28.9 -60.4 -34.2 -1.29 -37.2213 -229.0 -54.7 +52.4 +327.5 -23.38 -93.0 -23.7 -29.2 -61.5 -34.8 -1.35 -38.9113 -164.7 -39.4 +8.9 +55.6 -15.96 -63.5 -20.9 -25.7 -52.5 -29.7 -0.42 -12.1117 -157.9 -37.7 +10.1 +63.1 -16.17 -64.3 -17.6 -21.6 -50.0 -28.3 -0.85 -24.5__________________________________________________________________________
TABLE 21__________________________________________________________________________ Body weight just before blood samplingBody weight during feed period (g ± SD) (g ± SD)Sample1st day 8th day 15th day 22nd day 28th day 29th day__________________________________________________________________________C 105 ± 4.0 143 ± 9.0 181 ± 20.8 231 ± 21.8 266 ± 22.2 252 ± 21.7N 106 ± 3.9 162*** ± 5.5 226*** ± 9.0 284*** ± 14.7 319*** ± 15.2 297*** ± 17.41 105 ± 3.6 144 ± 9.8 191 ± 18.0 241 ± 20.4 272 ± 20.7 258 ± 20.22 104 ± 3.7 147 ± 8.4 191 ± 12.8 240 ± 16.9 268 ± 20.4 258 ± 20.43 106 ± 4.2 147 ± 9.6 192 ± 16.2 240 ± 16.7 267 ± 13.2 258 ± 19.24 104 ± 3.1 147 ± 8.1 191 ± 12.8 241 ± 16.8 269 ± 13.4 258 ± 18.4Example114 105 ± 3.3 145 ± 9.5 194 ± 18.0 247 ± 16.6 277 ± 14.9 265 ± 14.5116 106 ± 5.9 146 ± 10.0 193 ± 17.5 244 ± 15.8 273 ± 20.4 260 ± 19.0118 106 ± 3.4 147 ± 9.2 192 ± 17.8 243 ± 15.4 274 ± 18.4 259 ± 20.4120 105 ± 3.2 144 ± 9.4 191 ± 18.2 242 ± 15.7 272 ± 20.1 258 ± 23.0140 105 ± 3.6 147 ± 9.5 194 ± 17.2 246 ± 15.8 273 ± 18.7 261 ± 15.6130 105 ± 3.3 144 ± 9.3 194 ± 18.1 245 ± 15.7 271 ± 18.0 258 ± 20.2146 106 ± 5.9 149 ± 11.0 193 ± 17.5 243 ± 15.8 271 ± 20.2 258 ± 19.1__________________________________________________________________________
TABLE 22__________________________________________________________________________ Body weight just before blood sampl-Body weight during feed period (g ± SD) ing (g ± SD)Sample1st day 8th day 15th day 22nd day 28th day 29th day__________________________________________________________________________C 105 ± 4.0 144 ± 9.5 182 ± 20.9 233 ± 22.4 268 ± 22.3 253 ± 22.0N 106 ± 4.0 163*** ± 5.8 227*** ± 8.9 286*** ± 14.0 320*** ± 14.8 298*** ± 16.8Example167 105 ± 3.4 143 ± 10.4 191 ± 18.4 241 ± 21.7 272 ± 20.8 259 ± 20.6173 105 ± 3.6 142 ± 10.5 190 ± 18.2 240 ± 23.5 271 ± 24.2 258 ± 23.6189 104 ± 3.8 142 ± 8.1 188 ± 12.6 239 ± 20.6 268 ± 22.7 256 ± 20.2177 104 ± 3.9 142 ± 9.6 187 ± 12.8 238 ± 21.2 267 ± 25.2 256 ± 27.1205 105 ± 3.7 142 ± 9.8 188 ± 13.2 238 ± 19.8 267 ± 20.4 256 ± 19.2212 104 ± 3.3 143 ± 9.2 190 ± 18.6 239 ± 15.8 268 ± 21.4 257 ± 19.0183 105 ± 3.9 142 ± 8.8 189 ± 11.9 239 ± 16.5 268 ± 20.9 257 ± 18.8191 104 ± 3.7 142 ± 9.6 188 ± 12.9 239 ± 14.9 268 ± 21.7 257 ± 20.6197 104 ± 3.4 142 ± 8.4 188 ± 13.6 239 ± 16.2 268 ± 20.8 257 ± 20.4__________________________________________________________________________
TABLE 23__________________________________________________________________________Sample TC HDL-C TG PL LPO(Example No.) mg/dl SD mg/dl SD AI mg/dl SD mg/dl SD nmol/ml SD__________________________________________________________________________C 326.2 ±101.4 36.9 ±8.0 7.840 34.0 ±6.4 165.6 ±13.9 2.80 ±0.42101 216.6** ±63.3 46.4* ±7.5 3.668 28.2* ±5.7 150.7* ±15.7 2.12*** ±0.25102 205.0** ±58.4 48.1** ±7.2 3.262 26.7* ±5.9 140.9*** ±11.2 2.02*** ±0.18104 204.8** ±57.8 48.7** ±7.3 3.205 27.4* ±6.2 143.7** ±12.0 2.01*** ±0.20108 215.6** ±59.5 46.6* ±9.0 3.627 29.0 ±6.6 151.4* ±15.4 2.20** ±0.18112 216.4** ±60.4 46.8* ±8.5 3.624 28.5 ±6.3 150.4* ±15.7 2.16*** ±0.20__________________________________________________________________________
TABLE 24__________________________________________________________________________ TC HDL-C AI TG PL LPOSample Diff. % of Diff. % of % of Diff. % of Diff. % of Diff. % of(Example No.) mg/dl diff. mg/dl diff. Diff. diff. mg/dl diff. mg/dl diff. nmol/ml diff.__________________________________________________________________________101 -109.6 -33.6 +9.5 +25.7 -4.172 -53.2 -5.8 -17.1 -14.9 -9.0 -0.68 -24.3102 -121.2 -37.2 +11.2 +30.4 -4.578 -58.4 -7.3 -21.5 -24.7 -14.9 -0.78 -27.9104 -121.4 -37.2 +11.8 +32.0 -4.635 -59.1 -6.6 -19.4 -21.9 -13.2 -0.79 -28.2108 -110.6 -33.9 +9.7 +26.3 -4.213 -53.7 -5.0 -14.7 -14.2 -8.6 -0.60 -21.4112 -109.8 -33.7 +9.9 +26.8 -4.216 -53.8 -5.5 -16.2 -15.2 - 9.2 -0.64 -22.9__________________________________________________________________________
In the anti-hyperlipidemic assay according to method A, the daily dosage of each compound according to the present invention was 1% of 10 g/day of the hyperlipidemic diet, i.e. 100 mg. For instance, cyclobranyl esters of m-, o-, and p-aminobenzoic acid (Examples 49, 47, and 43), cyclobranyl ester of linoleic acid (Example 51), and cyclobranyl ester of nicotinic acid (Example 50) (100 mg each) contain the bound m-, o-, and p-aminobenzoic acids (24.5 mg each), linoleic acid (39.9 mg), and nicotinic acid (22.6 mg), respectively.
These organic acids in free form were added each to the hyperlipidemic diet, and the resulting diets (10 g/day each) were administered to rats in the same manner as in the above anti-hyperlipidemic assay, but the anti-hyperlipidemic effect was not observed with the above doses (22.6-39.9 mg/day) of the free acids. Thus, it has been confirmed that the effect of the compounds of Examples 49, 47, 43, 51, and 50 is not attributable to the m-, o-, or p-aminobenzoic acid, linoleic acid, or nicotinic acid combining with cyclobranol.
In method B, the dosage of each compound according to the present invention is roughtly calculated as 210 mg/day for each rat at most from the amount of the fed diet containing the compound. For example, cycloartenyl ester of 4-hydroxy-3 -methoxy-α-methylcinnamic acid (Example 114), cyclobranyl ester of 3-ethoxy-4-hydroxy-α-methylcinnamic acid (Example 140), cylobranyl ester of 5-amino-2-methoxybenzoic acid (Example 173), cycloartenyl ester of p-amino-α-methylcinnamic acid (Example 205), and cyclobranonyl ester of m-amino-α-methylcinnamic acid (Example 212) (210 mg each) contain the bound 4-hydroxy-3-methoxy-α-methylcinnamic acid (70.8 mg), 3-ethoxy-4-hydroxy-α-methylcinnamic acid (72.5 mg), 5-amino-2-methoxybenzoic acid (59.4 mg), p-amino-α-methylcinnamic acid (63.4 mg), and m-amino-α-methylcinnamic acid (62.0 mg), respectively.
These organic acids in free form were added each to the hyperlipidemic diet, and the resulting diets were administered to rats in the same manner as in the above anti-hyperlipidemic assay, but the anti-hyperlipidemic effect was not observed with the above doses (59.4-72.5 mg/day) of the free acids. Thus, it has been proved that the effect of the compound according to the present invention is not attributable to the organic acid liberated by the hydrolysis of the triterpeny ester of organic acid.
Of the compounds according to the present invention, the most favorable as anti-hyperlipidemic agents are esters from combinations of the triterpenyl alcohols with substituted cinnamic, α-(C 1 -C 4 alkyl) cinnamic, and benzoic acid which have one or two substituents on the benzene ring, the one substituent being a hydroxyl or amino group and the two being C 1 -C 4 alkoxy and hydroxyl groups or C 1 -C 4 alkoxy and amino groups.
For clinical use, the compounds of the invention can be administered parenterally or preferably orally. Suitable forms of the compounds for oral dosage are of tablets (uncoated or coated with sugar or the like), granules, powders, coated tablets, sugar-coated tablets, capsules, emulsions, etc. which additionally contain pharmaceutically acceptable carriers. For example, the carriers include lactose, white sugar, mannitol, anhydrous dextrose, starch, sorbitol, glycine, potassium phosphate, and microcrystalline cellulose as excipients; starch, gelatin, gum arabic, anhydrous dextrose, white sugar, sorbitol, mannitol, traganth, hydroxypropylcellulose, hydroxypropoxymethylcellulose, carboxymethylcellulose, 2-methyl-5-vinylpyridinemethacrylic acid-methyl acrylate copolymer, polyvinylpyrrolidone, and sodium aliginate as binders; stearic acid, hardened oil, magnesium stearate, calcium stearate, polyoxyethylene monostearate, talc, silicon oxide, and polyethylene glycol as lubricants; potato starch and starch containing a surfactant or the like, as disintegrating agents; and sodium laurylsulfate as a wetting agent. For parenteral dosage, the present compounds can be used in the form of intramuscular-injectable or suppository composition. Base materials for the suppository include cacao butter, Witepsol, Subanal, polyethylene glycol, polypropylene glycol, glycerogelatin, gelatin capsules, etc. In addition, the suppository may contain a known safety preservative such as methyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, or butylhydroxyanisole, and pharmaceutically acceptable coloring matter.
While depending upon the mode of administration, the age, weight, and conditions of the patient, and the kind of disease, daily doses of the present compounds for man are generally from 0.01 to 5 g, preferably from 0.02 to 1.5 g.
Triterpenyl alcohols for the novel esters of the present invention include also lanosterol, lanostenol, agnosterol, cyclosadol (3β-hydroxy-24-methylene-9,19-cylo-9β-lanosta-23-ene), dihydroagnosterol, cyclolaudenol, cycloartanol, cycloeucalenol, euphol, butyrospermol, tirucallol, euphorbol, and dammerrdienol, besides cycloartenol, cyclobranol, and 24-methylenecycloartanol mentioned above. Further, anti-hyperlipidemic effect can also be expected for the esters of the organic acids, defined above, combined with sterols, e.g. dihydro-β -sitosterol, dihydro-γ-sitosterol, campesterol, β-sitosterol, γ-sitosterol, stigmasterol, 24-methylenecholesterol, episterol, and 22-dihydroergosterol, which are analogous in structure to triterpenyl alcohols.
EXAMPLE 1
Preparation of cycloartenyl-3,4-diacetoxycinnamate
Toluene (20 ml) was added to 3,4-diacetoxycinnamic acid (4.65 g, 0.018 mole) and cooled to 0° C. Thionyl chloride (10.0 ml, 10 equivalents) was added dropwise thereto and further pyridine (0.5 ml) was added. The reaction mixture was conducted at 60° C. for 3 hours. Then, the resulting mixture was evaporated to dryness under reduced pressure and cycloartenol (5.0 g, 0.012 mole) and pyrydine (50 ml) were added thereto and the mixture was stirred at 60° C. for 1 hour. Thereafter, the solvent was removed by distillation under diminished pressure. The residue was dissolved in chloroform, and the solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with chloroform (3×50 ml). The combined chloroform layer was dried, concentrated under reduced pressure, and purified by silica gel column chromatography (solvent:ethyl acetate-hexane (1:9, V/V)), giving cycloartenyl-3,4-diacetoxycinnamate (5.6 g) in a 71% yeild, m.p. 125.5°-126.5° C.
Specific rotation [α] D 24 +36.6° (C 1.00, CHCl 3 ).
Analysis, Calcd. for C 43 H 60 O 6 (M.W. 672.91): C, 76.75; H, 8.99. Found: C, 76.82; H, 9.04.
IRν, KBr (cm -1 ): 2930, 2860, 1773, 1710, 1637, 1502, 1370, 1257, 1205, 1176.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2 ABq, 4.2 Hz), 0.60 (1H, 1/2 ABq, 4.2 Hz), 0.70-2.40 (27H, m), 0.90 (6H, s), 0.96 (6H, s), 1.61 (3H, bs), 1.68 (3H, bs), 2.31 (6H, s), 4.40-5.40 (2H, m), 6.40 (1H, 1/2 ABq, 16 Hz), 7.00-7.60 (3H, m), 7.58 (1H, 1/2 ABq, 16 Hz).
EXAMPLE 2
Preparation of cycloartenyl-3,4-dihydroxycinnamate
Dioxane (540 ml) was added to cycloartenyl-3,4-diactoxycinnamate (27.0 g, 0.040 mole) prepared according to the procedure of Example 1. To the mixture cooled to 0° C. was added dropwise 25% aqueous ammonia (27 ml), and this reaction mixture was stirred at 20° C. for 1 hour. Then the resulting mixture was evaporated to dryness under reduced pressure to give crude crystals, which were then washed with water and recrystallized from acetone-water (1:1, V/V), thereby giving cycloartenyl-3,4-dihydroxycinnamate (21.1 g) in a 89% yield m.p. 230°-231° C.
Specific rotation [α] D 23 +44.7° (C 0.19, CHDCl 3 ).
Analysis, Calcd. for C 39 H 56 O 4 (M.W. 588.84): C, 79.54; H, 9.59. Found: C, 79.62; H, 9.52.
IRν, KBr (cm -1 ): 3470, 3300, 2910, 2850, 1680, 1602, 1525, 1440, 1275, 1180, 972.
PMR (CDCl 3 -DMSO-d 6 )δ: 0.20-0.70 (2H, m), 0.40-2.40 (27H, m), 0.90 (6H, s), 0.94 (6H, s), 1.58 (3H, bs), 1.65 (3H, bs), 4.30-4.80 (1H, m), 4.80-5.30 (1H, m), 6.17 (1H, 1/2 ABq, 15 Hz), 6.60-7.20 (2H, m), 6.99 (1H, bs), 7.40 (1H, 1/2 ABq, 15 Hz), 8.87 (1H, bs), 9.25 (1H, bs).
EXAMPLE 3
Preparation of Cycloartenyl-3,4-dipropionyloxycinnamate
Toluene (26 ml) and thionyl chloride (34ml, 4.6 equivalents) were added to 3,4-dipropionyloxycinnamic acid (29.0 g) at 0° C. This reaction mixture was stirred at 60° C. for 20 minutes. Then, the resulting mixture was evaporated to dryness under reduced pressure, and the residue was dissolved again in toluene (50 ml). To the mixture cooled to 0° C. was added a solution of cycloartenol (30.0 g, 0.070 mole) in pyridine (60 ml) and the whole was stirred at 20° C. for 1 hour. Then, the solvent was removed by distillation under diminished pressure. The resulting residue was dissolved in chloroform, and the solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with chloroform (3×500 ml). The combined chloroform layer was dried and evaporated to dryness under reduced pressure. The residue was purified by silica gel column chromatography (solvent: methylenechloride), giving cycloartenyl-3,4-dipropionyloxycinnamate (35.7 g) in a 72% yield.
EXAMPLE 4
Preparation of cycloartenyl-3,4-dihydroxycinnamate
Dioxane (20 ml) was added to cycloartenyl-3,4-dipropionyloxycinnamate (1.0 g, 1.43 mmoles) prepared according to the procedure of Example 3 and was stirred at 0° C. Thereto was added dropwise 25% aqueous ammonia (2.0 ml) and the whole was stirred at 20° C for 1 hour. The resulting mixture was evaporated to dryness under reduced pressure. The crude crystals were washed with water and recrystallized from acetone-water (1:1, V/V) giving cycloartenyl-3,4-dihydroxycinnamate (756 mg) in a 90% yield, m.p. 230°-231° C.
Specific rotation [α] D 23 +44.7° (C 0.19, CHCl 3 )
Analysis, Calcd. for C 39 H 56 O 4 (M.W. 588.84): C, 79.54; H, 9.59. Found: C, 79.59; H, 9.63.
IRν, KBr (cm -1 ): 3470, 3300, 2910, 2850, 1680, 1602, 1525, 1440, 1275, 1180, 972.
PMR (CDCl 3 -DMSO-d 6 )δ: 0.20-0.70 (2H, m), 0.40-2.40 (27H, m), 0.90 (6H, s), 0.94 (6H, s), 1.58 (3H, bs), 1.65 (3H, bs), 4.30-4.80 (1H, m), 4.80-5.30 (1H, m), 6.17 (1H, 1/2 ABq, 15 Hz), 6.60-7.20 (2H,m), 6.99 (1H, bs), 7.40 (1H, 1/2 ABq, 15 Hz), 8.87 (1H, bs), 9.25 (1H, bs).
EXAMPLE 5
Preparation of Cycloartenyl-p-Acetoxycinnam
Toluene (18 ml) was added to p-acetoxycinnamic acid (18.1 g, 0.088 mole) and the mixture was cooled to 0° C. Thionyl chloride (31 ml, 5 equivalents) and pyridine (1.0 ml) were added dropwise thereto, and the whole was heated at 60° C. for 15 minutes. After concentration of the resulting mixture, toluene (35 ml) and pyridine (50 ml) were added, and the whole was cooled to 0° C. Thereto was added dropwise a solution of cycloartenol (25.0 g, 0.059 mole) in pyridine (50 ml). The mixture was refluxed for 40 minutes and then evaporated to dryness under reduced pressure. The resulting residue was dissolved in chloroform, and the solution was washed with saturated aqueous solution of Sodium bicarbonate. The aqueous layer was extracted with chloroform (3×500 ml). The combined extracts was dried, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (solvent: methylene chloridehexane, (1:1, V/V)), giving cycloartenyl-p-acetoxycinnamate (32.0 g) in a 89% yield, m.p. 153°-156° C.
Specific rotation [α] D 21 .5 +42.6° (C 1.02, CHCl 3 )
Analysis, Calcd. for C 41 H 58 O 4 (M.W 614.87): C, 80.08; H, 9.51. Found: C, 80.13; H, 9.42.
IRν, KBr (cm -1 ) 2920, 2850, 1765, 1695, 1500, 1370, 1270, 1195, 1160.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2 ABq, 4.2 Hz), 0.60 (1H, 1/2 ABq, 4.2 Hz), 0.70-2.40 (27H, m), 0.90 (6H, s), 0.96 (6H, s), 1.60 (3H, bs), 1.67 (3H, bs), 2.30 (3H, s), 4.50-5.30 (2H, m), 6 40 (1H, 1/2 ABq, 15 Hz), 6.90-7.80 (4H, m), 7.60 (1H, 1/2 ABq, 15 Hz).
EXAMPLE 6
Preparation of Cycloartenyl-p-Hydroxycinnamate
Cycloartenyl-p-acetoxycinnamate (28.0 g, 0.046 mole) prepared according to the procedure of Example 5 was dissolved in dioxane (280 ml). Then 25% aqueous ammonia (28 ml) was added dropwise to the solution at 0° C. The reaction mixture was stirred at 50° C. for 2 hours, and then evaporated to dryness under reduced pressure. The residue was recrystallized from acetone-water (1:1, V/V), giving cycloartenyl-p-hydroxycinnamate (23.4 g) in a 90% yield, m.p. 248°-248.5° C.
Specific rotation [α] D 26 +45.9° (C 0.98, CHCl 3 )
IRν, KBr (cm -1 ): 3190, 2930, 2850, 1705, 1670, 6105, 1582, 1512, 1440, 1280, 1170, 830.
PMR (CDCl 3 -DMSO-d 6 )δ: 0.20-0.80 (2H, m), 0.50-2.40 (27H, m), 0.88 (6H, s), 0.95 (6H, s), 1.57 (3H, bs), 1.64 (3H, bs), 4.30-4.84 (1H, m), 4.84-5.30 (1H, m), 6.28 (1H, 1/2 ABq, 15 Hz), 6.60-7.00 (2H, m), 7.20-7.60 (2H, m), 7.44 (1H, 1/2 ABq, 15 Hz), 9.75 (1H, bs).
EXAMPLE 7
Preparation of Cycloartenyl-o-Acetoxybenzoate
Thionyl chloride (39.0 ml, 5 equivalents) and pyridine (2.0 ml) were added dropwise to acetylsalicylic acid (19.0 g, 0.106 mole) in benzene (95 ml) with stirring at 20° C. This reaction mixture was stirred at 50° C. for 1 hour, and then evaporated to dryness under reduced pressure. Benzene (100 ml) was added thereto and the whole was stirred at 0° C., and cycloartenol (30.0 g, 0.070 mole) dissolved in pyridine (100 ml) was added and the whole was stirred at 50° for 20 minutes. After the reaction mixture was concentrated under reduced pressure, the residue was dissolved in methylene chloride, and the solution was washed with saturated aqueous solution of Sodium binarbonate. The aqueous layer was extracted with methylene chloride (3×500 ml). The combined extracts were dried, evaporated under reduced pressure to remove methylene chloride, and the residue was purified by silica gel column chromatography (solvent: toluene-methylene chloride, (1:1, V/V)), giving cycloartenyl-o-acetoxybenzoate (30.9 g) in a 75% yield, m.p. 138°-139° C.
Specific rotation [α] D 25 +61.4(C 0.99, CHCl 3 )
Analysis, Calcd. for C 39 H 56 O 4 (M.W. 588.84): C, 79.54; H, 9.59. Found: C, 79.47; H, 9.63.
IRν, KBr (cm -1 ): 2993, 2850, 1768, 1715, 1605, 1447, 1288, 1260, 1190, 1120.
PMR (CDCl 3 )δ:0.38 (1H, 1/2 ABq, 4.2 Hz), 0.59 (1H, 1/2 ABq, 4.2 Hz), 0.70-2.30 (27H, m), 0.81 (6H, s), 0.97 (3H, s), 1.00 (3H, s), 1.60 (3H, bs), 1.67 (3H, bs), 2.35 (3H, s), 4.50-5.30 (2H, m), 6.90-8.20 (4H, m).
EXAMPLE 8
Preparation of cycloartenyl-o-hydroxybenzoate
Sixty milliliter of 25% aqueous ammonia was added dropwise to cycloartenyl-o-acetoxybenzoate (30.0 g, 0.051 mole) in dioxane (600 ml) with stirring at 0° C. The reaction mixture was stirred at 55° C. for 4 hours. Then the solvent was removed by distillation under reduced pressure, the residue was dissolved in methylene chloride, and the solution was washed with saturated aqueous solution of Sodium bicarbonate. The aqueous layer was extracted with methylene chloride (3×500 ml). The combined extracts were dried and evaporated to dryness under reduced pressure. The residue was recrystallized from methylene chloridemethanol (1:5, V/V), giving cycloartenyl-o-hydroxybenzoate (26.2 g) in a 95% yield, m.p. 132°-133° C.
Specific rotation [α] D 25 +72.9° (C 1.01, CHCl 3 )
Analysis, Calcd. for C 37 H 54 O 3 (M.W. 546.80): C, 81.27; H, 9.95. Found: C, 81.36; H, 9.90.
IRνKBr (cm -1 ): 3130, 2910, 2850, 1663, 1610, 1480, 1295, 1245, 1210, 1155, 1090, 965, 760.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2 ABq, 4.2 Hz), 0.61 (1H, 1/2 ABq, 4.2 Hz), 0.60-2.30 (27H, m), 0.91 (6H, s), 0.98 (3H, s), 1.04 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 4.60-5.30 (2H, m), 6.60-8.00 (5H, m).
EXAMPLE 9
Preparation of Cycloartenyl-p-Acetoxybenzoate
Thionyl chloride (52 ml, 5 equivalents) and Pyridine (1.0 ml) was added to p-acetoxybenzoic acid (25.4 g, 0.141 mole) in benzene (100 ml) with stirring at 0° C. The reaction mixture was stirred at 55° C. for 30 minutes, and evaporated under reduced pressure, then the residue was cooled to 5° C. After addition of benzene (200 ml) thereto, cycloartenol (40.0 g, 0.094 mole) dissolved in pyridine (200 ml) was added and the mixture was stirred at 60° C. for 30 minutes. Then the resulting mixture was concentrated under reduced pressure to remove the solvents. The residue was dissolved in chloroform, and the solution was washed with saturated aqueous solution of Sodium bicarbonate. The aqueous layer was extracted with chloroform (3×600 ml). The combined chloroform layer was dried and evaporated to dryness. The crude crystals were recrystallized from methylene chloride-methanol (1:5, V/V) giving cycloartenyl-p-acetoxybenzoate (52.5 g) in a 95% yield, m.p. 141°-142° C.
Specific rotation [α] D 25 +58.6° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 39 H 56 O 4 (M.W. 588.84): C, 79.54; H, 9.59. Found: C, 79.52; H, 9.68.
IRν, KBr (cm -1 ): 2930, 2850, 1760, 1720, 1600, 1360, 1272, 1189, 1159, 1120.
PMR (CDCl 3 )δ: 6: 0.40 (1H, 1/2 ABq, 4.2 Hz), 0.61 (1H, 1/2 ABq, 4.2 Hz), 0.60-2.30 (27H, m), 0.91 (6H, s), 0.98 (3H, s), 1.03 (3H, s), 1.60 (3H, bs), 1.69 (3H, bs), 2.32 (3H, s), 4.60-5.30 (2H, m), 6.96-7.40 (2H, m), 7.80-8.22 (2H, m).
EXAMPLE 10
Preparation of cycloartenyl-p-hydroxybenzoate
Dioxane (500 ml) was added to cycloartenyl-p-acetoxybenzoate (27.0 g, 0.046 mole) prepared according to the procedure of Example 1. Then 25% aqueous ammonia (50 ml) was added dropwise to the solution, and the reaction mixture was stirred at 20° C. for 2.5 hours. Then the mixture was evaporated under reduced pressure to remove the solvent. The resulting residue was purified by silica gel column chromatography (solvent: methylene chloride-ethanol, (98:2, V/V)), giving cycloartenyl-p-hydroxybenzoate containing a molecular ethanol in a 96% yield, m.p. 180°-182° C.
Specific rotation [α] D 25 +66.1° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 37 H 54 O 3 .C 2 H 5 OH (M.W. 592.87): C, 79.00; H, 10.20. Found: C, 79.11; H, 10.14.
IRν, KBr (cm -1 ) 3450, 3150, 2950, 2850, 1715, 1689, 1612, 1600, 1515, 1310, 1280, 1160.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2ABq, 4.2 Hz), 0.60 (1H, 1/2ABq, 4.2 Hz), 0.60-2.30 (27H, m), 0.91 (6H, s), 0.97 (3H, s), 1.03 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 4.50-5.30 (2H, m), 6.60-7.05 (2H, m), 6.88 (2H, 1/2ABq, 8.1 Hz), 7.11 (1H, bs), 7.60-8.20 (2H, m), 7.82 (2H, 1/2ABq, 8.1 Hz).
EXAMPLE 11
Preparation of cycloartenyl-m-acetoxybenzoate
Thionyl Chloride (52 ml, 5 equivalents) and Pyridine (0.5 ml) were added to m-acetoxybenzoic acid (25.0 g, 0.139 mole) in benzene (100 ml) with stirring at 0° C. The reaction mixture was stirred at 60° C. for 30 minutes and evaporated under reduced pressure. Benzene (200 ml) was added to the concentrate and the solution was stirred at 0° C. Cycloartenol (40.0 g, 0.094 mole) dissolved in pyridine (200 ml) was added dropwise thereto, and the reaction mixture was stirred at 60° C. for 1 hour. The resulting mixture was evaporated under reduced pressure, to give a crystalline residue. This residue was dissolved in chloroform, and the solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with chloroform (3×500 ml). The combined extracts were dried, concentrated under reduced pressure and the residue was purified by silica gel column chromatography (solvent: methylene chloride-hexane, (2:1, V/V)) giving cycloartenyl-m-acetoxybenzoate (49.0 g) in a 89% yield, m.p. 122°-123° C.
Specific rotation [α] D 25 .5 +60.8° (C,0.99, CHCl 3 )
Analysis, Calcd. for C 39 H 56 O 4 (M.W 588.84): C, 79.54; H, 9.59. Found: C, 79.60; H, 9.55.
IRν, KBr (cm -1 ) 2930, 2850, 1769, 1715, 1585, 1440, 1370, 1280, 1275, 1212.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2ABq, 4.2 Hz), 0.61 (1H, 1/2ABq, 4.2 Hz), 0.60-2.30 (27H, m), 0.91 (6H, s), 0.98 (3H, s), 1.03 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 2.32 (3H, s), 4.60-5.30 (2H, m), 7.10-8.05 (4H, m).
EXAMPLE 12
Preparation of cycloartenyl-m-hydroxybenzoate
Dioxane (400 ml) was added to cycloartenyl-m-acetoxybenzoate (27.0 g, 0.036 mole) prepared according to the procedure of Example 11. While stirring the mixture at 0° C., 25% aqueous ammonia (40 ml) was added dropwise. Then the reaction mixture was stirred at 40° C. for 1.5 hours. The resulting mixture was evaporated to dryness under reduced pressure. Then the residual crystals were dissolved in chloroform, and the solution was washed with saturated aqueous solution of Sodium bicarbonate. The aqueous layer was extracted with chloroform (3×300 ml). The combined extracts were dried and evaporated under reduced pressure, separating out crude crystals which were then recrystallized from methylene chloride-hexane (1:4, V/V), giving cycloartenyl-m-hydroxy benzoate (22.7 g) in a 91% yeild. m.p. 176°-177.5° C.
Specific rotation [α] D 25 .5 +65.4° (C 1.01, CHCl 3 )
Analysis Calcd. for C 37 H 54 O 3 (M.W. 546.80): C, 81.27; H, 9.95. Found: C, 81.21; H, 9.99.
IRν, KBr (cm -1 ) 3380, 2950, 2930, 2850, 1710, 1692, 1600, 1450, 1310, 1290, 1110, 970, 758.
PMR (CDCl 3 )δ: 0.38 (1H, 1/2ABq, 4.2 Hz), 0.60 (1H, 1/2ABq, 4.2 Hz), 0.60-2.30 (27H, m), 0.90 (6H, s), 0.97 (3H, s), 1.02 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 4.52-5.30 (2H, m), 6.90-7.70 (4H, m).
EXAMPLE 13
Preparation of cycloartenyl-o-methoxybenzoate
Cycloartenol (16.0 g, 0.038 ml) was dissolved in pyridine (160 ml). While the solution was stirred at 0° C., o-methoxybenzoyl chloride (7.0 ml, 1.2 equivalents) was added dropwise thereto and the mixture was allowed to react at 40° C. for 1 hour. Then the resulting mixture was evaporated under reduced pressure, and the crystalline residue was dissolved in chloroform, and the solution was washed with saturated aqueous solution of Sodium bicarbonate. The aqueous layer was extracted with chloroform (3×100 ml). The combined extracts were dried and evaporated to dryness under reduced pressure. The resulting crude crystals were recrystallized from methylene chloride-methanol (1:6, V/V), giving cycloartenyl-o-methoxybenzoate (18.0 g) in a 86% yield. m.p. 141°-142° C.
Specific rotation [α] D 25 +47.5° (C 1.02, CHCl 3 )
Analysis, Calcd. for C 38 H 56 O 3 (M.W. 560.83): C, 81.38; H, 10.07. Found: C, 81.33; H, 10.15.
IRν, KBr (cm -1 ) 2930, 2850, 1720, 1696, 1598, 1460, 1298, 1250, 1130.
PMR (CDCl 3 )δ: 0.38 (1H, 1/2ABq, 4.2 Hz), 0.60 (1H, 1/2ABq, 4.2 Hz), 0.60-2.30 (27H, m), 0.91 (3H, s), 0.96 (6H, s), 1.00 (3H, s), 1.60 (3H, bs), 1.67 (3H, bs), 3.88 (3H, s), 4.50-5.30 (2H, m), 6.70-8.00 (4H, m).
EXAMPLE 14
Preparation of cycloartenyl-p-methoxybenzoate
To a solution of cycloartenol (20.0 g, 0.047 mole) in pyridine (150 ml) cooled to 0° C., there was added dropwise p-methoxybenzoic chloride (9.5 ml, 1.2 equivalents), and the whole was stirred at 50° C. for 3 hours. The resulting mixture was evaporated to dryness under reduced pressure. The residual crystals were dissolved in chloroform, and the solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with chloroform (3×200 ml). The combined extracts were dried and evaporated to dryness under reduced pressure. The crude crystals were recrystallized from methylene chloride-methanol (1:7, V/V), giving cycloroartenyl-p-methoxybenzoate (25.0 g) in a 95% yield. m.p. 129.5°-130° C.
Specific rotation [α] D 25 +62.9° (C 0.99 CHCl 3 )
Analysis, Calcd. for C 38 H 56 O 3 (M.W. 560.83): C, 81.38; H, 10.07. Found: C, 81.31; H, 10.15.
IRν, KBr (cm -1 ): 2910, 2850, 1711, 1605, 1508, 1270, 1250, 1165, 1115, 1100.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2ABq, 4.2 Hz), 0.61 (1H, 1/2ABq, 4.2 Hz), 0.70-2.30 (27H, m), 0.91 (6H, s), 0.98 (3H, s), 1.03 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 3.84 (3H, s), 6.70-7.05 (2H, m), 7.80-8.12 (2H, m).
EXAMPLE 15
Preparation of cycloartenyl-m-methoxybenzoate
Thionyl Chloride (24 ml, 5 equivalents) and pyridine (0.5 ml) were added to m-methoxybenzoic acid (9.6 g, 0.063 mole) in benzene (50 ml) with stirring at 0° C. The reaction mixture was stirred at 40° C. for 30 minutes. The resulting mixture was evaporated under reduced pressure and benzene (100 ml) was added to the residue. Cycloartenol (18.0 g, 0.042 mole) dissolved in pyridine (100 ml) was added dropwise thereto at 0° C. and the whole was stirred at 40° C. for 1 hour and at 50° C. for 1 additional hour. Then the solvent was removed by distillation under reduced pressure. The residue was dissolved in chloroform, and the solution was washed with saturated aqueous solution of Sodium bicarbonate. The aqueous layer was extracted with chloroform (3×200 ml). The combined extracts were dried, and evaporated under reduced pressure. The crude crystals were recrystallized from methylene chloride-methanol (1:5, V/V), giving cycloartenyl-m-methoxybenzoate (23.0 g) in an almost quantitative yield. m.p. 127°-128° C.
Specific rotation [α] D 25 .5 +63.7° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 38 H 56 O 3 (M.W. 560.83): C, 81.38; H, 10.07. Found: C, 81.44; H, 10.01.
IRν, KBr (cm -1 ) 2930, 2850, 1715, 1700, 1584, 1450, 1285, 1275, 1100, 1045, 755.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2ABq, 4.2 Hz), 0.60 (1H, 1/2ABq, 4.2 Hz), 0.60-2.30 (27H, m), 0.91 (6H, s), 0.98 (3H, s), 1.04 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 3.84 (3H, s), 4.60-5.30 (2H, m), 6.90-7.80 (4H, m).
EXAMPLE 16
Preparation of cycloartenyl-o-nitrobenzoate
o-Nitrobenzoic acid (4.7 g, 0.028 mole) was dissolved in dioxane (50 ml). Thionyl chloride (10.0 ml, 5 equivalents) and dimethylformamide (0.2 ml) was added dropwise to the former solution with stirring at 0° C. The whole was stirred at 50° C. for 30 minutes. The resulting mixture was concentrated under reduced pressure to remove the excess thionyl chloride. Dioxane (50 ml) was added to the residue and the solution was stirred at 0° C. Cycloartenol (10.0 g, 0.023 mole) dissolved in pyridine (50 ml) was added dropwise thereto, and the mixture was stirred at 70° C. for 30 minutes. The resulting mixture was concentrated under reduced pressure, and dissolved in chloroform (100 ml). The solution was washed with saturated aqueous solution of Sodium bicarbonate. The aqueous layer was extracted with chloroform (3×100 ml). The combined extracts were dried and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (solvent:chloroform-hexane (1:2, V/V)), giving cycloartenyl-o-nitrobenzoate (13.0 g) in a 96% yield. m.p. 166°-167° C.
Specific rotation [α] D 22 +94.8° (C 1.01, CHCl 3 )
Analysis, Calcd. for C 37 H 53 O 4 N (M.W. 575.80): C, 77.17; H, 9.28; N, 2.43. Found: C, 77.28; H, 9.21; N, 2.42.
IRν, KBr (cm -1 ); 2930, 2850, 1710, 1535, 1375, 1300, 1130.
PMR (CDCl 3 )δ: 0.38 (1H, 1/2ABq, 4.2 Hz), 0.59 (1H, 1/2ABq, 4.2 Hz), 0.60-2.30 (27H, m), 0.89 (3H, s), 0.91 (3H, s), 0.94 (3H, s), 0.97 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 4.60-5.30 (2H, m), 7.50-8.00 (4H, m).
EXAMPLE 17
Preparation of cycloartenyl-o-aminobenzoate
Cycloartenyl-o-nitrobenzoate (20.0 g, 0.035 mole) prepared according to the procecure of Example 16 was suspended in acetic acid (800 ml). By adding zinc powder (20.0 g), the mixture was stirred at 50° C. for 3 hours. Then, zinc powder was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was dissolved in chloroform, and the solution was washed with saturated aqueous solution of Sodium bicarbonate. The aqueous layer was extracted with chloroform (3×500 ml). The combined extracts were dried, concentrated under reduced pressure and the residue was purified by silica gel chromatography (solvent: methylene chloride-hexane, (1:2, V/V)), giving cycloartenyl-o-aminobenzoate (15.0 g) in a 80% yield. m.p. 185°-186° C.
Specific rotation [α] D 25 .5 +77.5° (C 1.02, CHCl 3 )
Analysis, Calcd. for C 37 H 55 O 2 N (M.W. 545.82): C, 81.41; H, 10.16; N, 2.57. Found: C, 81.48; H, 10.18; N, 2.53.
IRν, KBr (cm -1 ) 3470, 3350, 2930, 2850, 1670, 1620, 1290, 1248, 1155, 760.
PMR (CDCl 3 )δ: 0.40 (1H, 1/2ABq, 4.2 Hz), 0.61 (1H, 1/2ABq, 4.2 Hz), 0.60-2.30 (27H, m), 0.91 (6H, s), 0.97 (3H, s), 1.03 (3H, s), 1.60 (3H, bs), 1.67 (3H, bs), 4.60-5.32 (2H, m), 5.50 (2H, bs), 6.40-8.00 (4H, m).
EXAMPLE 18
Preparation of cycloartenyl-p-nitrobenzoate
Dioxane (30 ml) was added to p-nitrobenzoic acid (2.95 g, 0.018 mole). Thionyl chloride (6.5 ml, 5 equivalents) and dimethylformamide (0.3 ml) were added dropwise to the former solution at 20° C. and the reaction mixture was continued to stir at 50° C. for 30 minutes. Then, the resulting mixture was distilled under reduced pressure to remove the excess thionyl chlorice completely. Dioxane (25 ml) was added to the resulting acid-chloride and cycloartenol (5.0 g, 0.012 mole) dissolved in pyridine (25 ml) was added thereto at 0° C. The mixture was stirred at 60° C. for 20 minutes, then the resulting mixture was concentrated under reduced pressure, the residue was dissolved in chloroform (50 ml), and the solution was washed with saturated aqueous solution of Sodium bicarbonate. The aqueous layer was extracted with chloroform (3×50 ml). The combined extracts were dried and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (solvent:chloroform-hexane (1:3, V/V)), giving cycloartenyl-p-nitrobenzoate (6.3 g) in a 93% yield. m.p. 221°-222° C.
Specific rotation [α] D 22 .5 +62.3° (C 1.01, CHCl 3 )
Analysis, Calcd. for C 37 H 53 O 4 N (M.W. 575.80): C, 77.17; H, 9.28; N, 2.43. Found: C, 77.25; H, 9.21; N, 2.50.
IRν, KBr (cm -1 ): 2930, 2850, 1715, 1520, 1350, 1290, 1120, 1100.
PMR (CDCl 3 )δ: 0.41 (1H, 1/2ABq, 4.2 Hz), 0.61 (1H, 1/2ABq, 4.2 Hz), 0.70-2.40 (27H, m), 0.91 (3H, s), 0.98 (3H, s), 1.05 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 4.60-5.30 (2H,m), 8.00-8.50 (4H, m).
EXAMPLE 19
Preparation of cycloartenyl-p-aminobenzoate
Cycloartenyl-p-nitrobenzoate (5.0 g, 8.70 mmoles) prepared according to the procedure of Example 18 was suspended in acetic acid (250 ml). By adding zinc powder (10.0 g), the mixture was stirred at 20°-25° C. for 2.5 hours. Then, zinc powder was removed by filtration and the filtrate was concentrated under reduced pressure. The residual solid was dissolved in chloroform, and the solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with chloroform. The combined extracts were dried, and distilled to remove the solvent. The resulting residue was purified by silica gel column chromatography (solvent: methylene chloride), giving cycloartenyl-p-aminobenzoate (4.0 g) in a 84% yield. m.p. 168°-169° C.
Specific rotation [α] D 25 +62.2° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 37 H 55 O 2 N (M.W. 545.82): C, 81.41; H, 10.16, N, 2.57. Found: C, 81.52; H, 10.12; N, 2.53.
IRν, KBr (cm -1 ): 3470, 3350, 2930, 2850, 1705, 1685, 1625, 1600, 1515, 1310, 1275, 1170, 1115.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2ABq, 4 Hz), 0.58 (1H, 1/2ABq, 4 Hz), 0.70-2.30 (27H, m), 0.95 (3H, s), 0.98 (6H, s), 1.00 (3H, s), 1.59 (3H, bs), 1.66 (3H, bs), 4.50 (2H, bs), 4.50-5.30 (2H, m), 6.40-6.80 (2H, m), 7.60-8.10 (2H, m).
EXAMPLE 20
Preparation of cycloartenyl-p-acetamidobenzoate
Dioxane (110 ml) was added to p-acetamidobenzoic acid (5.5 g, 0.031 mole). Thionyl chloride (21.0 ml, 0 equivalents) and pyridine (0.5 ml) were added dropwise to the former solution at 20° C. and the reaction mixture was stirred at 50° C. for 5 minutes. The resulting mixture was concentrated under reduced pressure to remove the unreacted thionyl chloride. Dioxane (50 ml) and a solution of cycloartenol (10.0 g, 0.023 mole) in benzene (50 ml) were added to the concentrate and then pyridine (20 ml) was added at 20° C. This reaction mixture was heated at 70° C. for 3 hours. Then the solvent was removed by distillation under reduced pressure the resulting residue was dissolved in chloroform (100 ml), and the solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with chloroform (5×100 ml). The combined extracts were dried, concentrated under reduced pressure and the residue was purified by silica gel column chromatography (solvent:chloroformethyl acetate, (7:1, V/V)) giving cycloartenyl-p-acetamidobenzoate (11.0 g) in a 80% yield. m.p. 202°-204° C.
Specific rotation [α] D 24 +59.6° (C 0.99, CHCl 3 )
Analysis, Calcd. for C 39 H 57 O 3 N (M.W. 587.85): C, 79.68; H, 9.77; N, 2.38. Found: C, 79.59; H, 9.82; N, 2.34.
IRν, KBr (cm -1 ): 3310, 2930, 2850, 1705, 1680, 1598, 1520, 1310, 1285, 1260, 1180, 1135.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2ABq, 4 Hz), 0.60 (1H, 1/2ABq, 4 Hz), 0.60-2.30 (27H, m), 0.91 (6H, s), 0.98 (3H, s), 1.03 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 2.20 (3H, s), 4.50-5.30 (2H, m), 7.51 (1H, bs), 7.59 (2H, 1/2ABq, 8.4 Hz), 7.97 (2H, 1/2ABq, 8.4 Hz).
EXAMPLE 21
Preparation of cycloartenyl-p-aminobenzoate
Tetrahydrofuran (200 ml) and 30% hydrochloric acid (100 ml) were added to cycloartenyl-p-acetamidobenzoate (10.0 g, 0.017 mole) prepared according to the procedure of Example 20. The mixture was refluxed for 2 hours. Then the solvent was removed by distillation under reduced pressure The residue was dissolved in chloroform (300 ml), and washed with 1N aqueous sodium hydroxide (200 ml) followed by saturated brine. The aqueous layer and brine were extracted with chloroform (3×200 ml). The combined extracts were dried and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (solvent: ethyl acetate-hexane, (1:4, V/V)) giving cycloartenyl-p-aminobenzoate (3.2 g) in a 34% yield. m.p. 168°-169° C.
Specific rotation [α] D 25 +62.2°
Analysis, Calcd. for C 37 H 55 O 2 N (M.W. 545.82): C, 81.41; H, 10.16; N, 2.57. Found: C, 81.48;
H, 10.23; N, 2.54.
EXAMPLE 22
Preparation of cycloartenyl-m-nitrobenzoate
Cycloartenol (15.0 g, 0.035 mole) was dissolved in pyridine (150 ml). m-Nitrobenzoyl chloride (8.5 g, 1.3 equivalents) was added dropwise to the solution at 0° C. and the mixture was stirred at 40° C. for 30 minutes. Then, the resulting mixture was concentrated under reduced pressure and the residue was dissolved in methylene chloride (100 ml). The solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with methylene chloride (3×100 ml). The combined extracts were dried and concentrated under reduced pressure. The concentrate was dissolved in methylene chloride (50 ml), and crystals separated out by adding methanol (100 ml), giving cycloartenyl-m-nitrobenzoate (19.5 g) in a 96% yield. m.p. 162.5°-163.5° C.
Specific rotation [α] D 22 +60.8° (C 0.99, CHCl 3 )
Analysis, Calcd. for C 37 H 53 O 4 N (M.W. 575.80): C 77.17; H, 9.28; N, 2.43. Found: C, 77.10; H, 9.33; N, 2.37.
IRν, KBr (cm -1 ) 2920, 2850, 1712, 1532, 1350, 1290, 1145, 980, 715.
PMR (CDCl 3 )δ: 0.42 (1H, 1/2ABq, 4.2 Hz), 0.64 (1H, 1/2ABq, 4.2 Hz), 0.60-2.40 (27H, m), 0.92 (6H, s), 0.98 (3H, s), 1.07 (3H, s), 1.60 (3H, bs), 1.67 (3H, bs), 4.60-5.30 (2H, m), 7.50-8.50 (4H, m).
EXAMPLE 23
Preparation of cycloartenyl-m-aminobenzoate
Cycloartenyl-m-nitrobenzoate (15.0 g, 0.026 mole) prepared according to procedure of Example 22 was suspended in acetic acid (750 ml). By adding zinc powder (30.0 g), the mixture was stirred at 40° C. for 2 hours. Then, stirred the zinc powder was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was dissolved in chloroform, and the solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with chloroform (5×300 ml). The combined extracts were dried and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (solvent:chloroform), giving cycloartenyl-m-aminobenzoate (12.6 g) in a 89% yield. m.p. 172.5°-173.5° C.
Specific rotation [α] D 25 .5 +62.6° (C 0.99, CHCl 3 )
Analysis. Calcd. for C 37 H 55 O 2 N (M.W. 545.82): C 81.41; H 10.16; N 2.57. Found: C 81.53; H 10.11; N 2.53.
IRν, KBr (cm -1 ) 3450, 3350, 2900, 2850, 1700, 1627, 1460, 1287, 1240, 1100, 975, 755.
PMR (CDCl 3 )δ: 0.40 (1H, 1/2ABq, 4.2 Hz), 0.61 (1H, 1/2ABq, 4.2 Hz), 0.60-2.30 (27H, m), 0.91 (6H, s), 0.98 (3H, s), 1.03 (3H, s), 1.61 (3H, bs), 1.68 (3H, bs), 3.70 (2H, bs), 4.60-5.30 (2H, m), 6.70-7.50 (4H, m).
EXAMPLE 24
Preparation of cycloartenyl nicotinate
Toluene (10 ml) was thionyl chloride (50 ml, 10 equivalents) were added to nicotinic acid (8.7 g, 0.071 mole) at 0° C., and the whole was stirred at 60° C. for 30 minutes. The reaction mixture was concentrated under reduced pressure, and cycloartenol (20.0 g, 0.047 mole), pyridine (100 ml) and toluene (50 ml) were added thereto at 0° C., and the reaction mixture was stirred at 100° C. for 30 minutes. Then, the solvent was removed by distillation under reduced pressure, the resulting residue was dissolved in methylene chloride and the solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with methylene (3×300 ml). The combined extracts was concentrated to dryness under reduced pressure, and the crude crystals were recrystallized from methylene chloride-methanol (1:4, V/V), giving cycloartenyl-nicotinate (24.4 g) in a 98% yield. m.p. 170.5°-171° C.
Specific rotation [α] D 25 +67.8° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 36 H 53 O 2 N (M.W. 531.79): C 81.30; H 10.05; N 2.63. Found: C 81.22, H 10.09, N 2.57.
IRν, KBr (cm -1 ): 2920, 2850, 1718, 1590, 1282, 1122, 965, 740.
PMR (CDCl 3 )δ: 0.40 (1H, 1/2 ABq, 4.2 Hz), 0.62 (1H, 1/2 ABq, 4.2 Hz), 0.60-2.40 (27H, m), 0.91 (6H, s), 0.98 (3H, s), 1.04 (3H, s), 1.60 (3H, bs), 1.67 (3H, bs), 4.50-5.30 (2H, m), 7.20-9.30 (4H, m).
EXAMPLE 25
Preparation of cycloartenyl linolate
Benzene (61 ml) was added to linoleic acid (23.0 g, 0.082 mole) and the solution was stirred at 0° C. Thionyl chloride (61 ml, 10 equivalents) was added dropwise thereto, and the reaction mixture was stirred at 40° C. for 30 minutes. Then the resulting mixture was concentrated under reduced pressure, and benzene (125 ml) was added with stirring at 0° C. Cycloartenol (25.0 g, 0.059 ml) dissolved in pyridine (125 ml) was added thereto and the whole was stirred at 40° C. for 10 minutes. Then the solvent was removed by distillation under reduced pressure. The resulting residue was dissolved in methylene chloride, and the solution was washed with saturated aqueous solution of sodium bicarbonate, and the aqueous layer was extracted with methylene chloride (3×500 ml). The combined extracts were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting oily material was purified by silica gel column chromatography (solvent: methylene chloride-hexane (1:1, V/V)), giving cycloartenyl linolate (36.1 g) in a 90% yield. m.p. (oily matter).
Specific rotation [α] D 21 .5 +39.3°
Analysis, Calcd. for C 48 H 80 O 2 (M.W. 689.12): C 83.65; H 11.70. Found: C 83.52; H 11.83.
IRν, neat (cm -1 ): 2910, 2850, 1730, 1460, 1373, 1170, 980.
PMR (CDCl 3 )δ: 0.33 (1H, 1/2 ABq, 4.2 Hz), 0.56 (1H, 1/2 ABq, 4.2 Hz), 0.60-2.50 (52H, m), 0.84 (3H, s), 0.87 (6H, s), 0.96 (3H, s), 1.60 (3H, bs), 1.67 (3H, bs), 2.76 (2H, bt, 5.0 Hz), 4.40-4.80 (1H, m), 4.90-5.64 (5H, m).
EXAMPLE 26
Preparation of cycloartenyl-3,4-diacetoxybenzoate
Toluene (50 ml) was added to 3,4-diacetoxybenzoic acid (20.9 g, 0.088 mole) and stirred at 0° C. Thionyl chloride (33 ml, 5 equivalents) was added dropwise to 3,4-diacetoxybenzoic acid (20.9 g, 0.088 mole) and the mixture was stirred at 70° for 10 minutes. The resulting mixture was concentrated under reduced pressure. Toluene (125 ml) was added to the concentrate at 0° C. Cycloartenol (25.0 g, 0.059 mole) dissolved in pyridine (60 ml) was added thereto and the mixture was stirred at 22° C. for 1 hour. Then the solvent was removed by distillation under reduced pressure. The resulting residue was dissolved in methylene chloride, and the solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with methylene chloride (3×400 ml). The combined extracts were dried and concentrated to dryness under reduced pressure. The residue was recrystallized from chloroform-methanol (1:5, V/V), giving cycloartenyl-3,4-diacetoxybenzoate (33.8 g) in a 89% yield. m.p. 148°-148.5° C.
Specific rotation [α] D 23 +53.3° (C 0.99, CHCl 3 )
Analysis, Calcd. for C 41 H 58 O 6 (M.W 646.87): C 76.12, H 9.04. Found: C76.01, H 9.17.
IRν, KBr (cm -1 ): 2910, 2850, 1775, 1710, 1610, 1498, 1420, 1370, 1280, 1195, 1160.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2 ABq, 4.2 Hz), 0.61 (1H, 1/2 ABq, 4.2 Hz), 0.70-2.40 (27H, m), 0.90 (6H, s), 0.97 (3H, s), 1.02 (3H, s), 1.60 (3H, s), 1.68 (3H, bs), 2.29 (6H, s), 4.60-5.30 (2H, m), 7.10-7.50 (2H, m), 7.78-8.20 (3H, m).
EXAMPLE 27
Preparation of cycloartenyl-3,4-dihydroxybenzoate
Dioxane (460 ml) was added to cycloartenyl-3,4-diacetoxybenzoate (23.0 g, 0.036 mole) prepared according to procedure of Example 26 and the solution was cooled to 0° C. After addition of 25% aqueous ammonia (46 ml) dropwise thereto, the mixture was stirred at 20° C. for 30 minutes and at 40° C. for 15 minutes to complete the reaction. Then the solvent was removed by distillation under reduced pressure. The resulting residue was recrystallized from chloroform-hexane (1:6, V/V), giving cycloartenyl-3,4-dihydroxybenzoate (18.6 g) in a 93% yield. m.p. 199°-199.5° C.
Specific rotation [α] D 26 +63.7° (C 0.97, CHCl 3 )
Analysis, Calcd. for C 37 H 54 O 4 (M.W. 562.80): C 78.96; H 9.67. Found: C 78.82; H 9.63.
IRν, KBr (cm -1 ): 3470, 3330, 2900, 2850, 1705, 1679, 1605, 1525, 1435, 1280, 1230, 1098, 975.
PMR (CDCl 3 )δ: 0.38 (1H, 1/2ABq, 4.2 Hz), 0.50 (1H, 1/2ABq, 4.2 Hz), 0.50-2.40 (27H, m), 0.88 (6H, s), 0.96 (3H, s), 1.00 (3H, s), 1.60 (3H, bs), 1.67 (3H, bs), 4.50-5.30 (2H, m), 5.80-6.80 (1H, bs), 6.70-7.90 (3H, m).
EXAMPLE 28
Preparation of cycloartenyl-4-acetoxy-3-methoxybenzoate
Toluene (26 ml) and thionyl chloride (23 ml) were added to 4-acetoxy-3-methoxybenzoic acid (13.0 g, 0.062 mole). The reaction mixture was stirred at 60° C. for 20 minutes. Then the resulting mixture was concentrated to dryness under reduced pressure. To the residue were added pyridine (25 ml) and toluene (25 ml), and the mixture was stirred at 0° C. Cycloartenol (20.0 g, 0.047 mole) dissolved in pyridine (25 ml) was added dropwise thereto, and the mixture was heated with stirring at 60° C. for 1.5 hours, at 80° C. for 1 hour, and at 100° C. for 2 hour to complete the reaction. The resulting mixture was concentrated under reduced pressure, and the residue was dissolved in chloroform (300 ml). The solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with chloroform (3×300 ml). The combined extracts was dried and concentrated under reduced pressure and the residue was purified by silica gel column chromatography (solvent: ethyl acetatehexane, (1:8, V/V)), giving cycloartenyl-4-acetoxy-3-methoxybenzoate (26.0 g) in a 90% yield. m.p. 157°-158° C.
Specific roatation [α] D 23 +58.9° (C 0.99, CHCl 3 )
Analysis, Calcd. for C 40 H 58 O 5 (M.W. 618.86): C 77.63; H 9.45. Found: C 77.75; H 9.40.
IRν, KBr (cm -1 ): 2920, 2850, 1770, 1710, 1600, 1500, 1410, 1280, 1210, 1195, 1170, 1100, 1030.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2 ABq, 4.2 Hz), 0.60 (1H, 1/2 ABq, 4.2 Hz), 0.60-2.40 (27H, m), 0.89 (6H, s), 0.96 (3H, s), 1.02 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 2.32 (3H, s), 3.86 (3H, s), 4.60-5.30 (2H, m), 6.80-7.90 (3H, m).
EXAMPLE 29
Preparation of cycloartenyl-4-hydroxy-3-methoxybenzoate
Dioxane (480 ml) was added to cycloartenyl-4-acetoxy-3-methoxybenzoate (24.0 g, 0.039 mole) prepared according to the procedure of Example 28. Thereto was added dropwise 25% aqueous ammonia (48 ml) at 0° C. and the whole was stirred at 35° C. for 1 hour. Then the resulting mixture was concentrated under reduced pressure and the residue was dissolved in chloroform (200 ml), and the solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with chloroform (3×200 ml). The combined extracts was dried and concentrated, and crystallized by adding ethanol, giving cycloartenyl-4-hydroxy-3-methoxybenzoate containing a molecular ethanol (21.0 g) in a 87% yield. m.p. 132°-133° C.
Specific rotation [α] D 26 +61.3° (C 1.00, CH 3 Cl)
Analysis, Calcd. for C 38 H 56 O 4 .C 2 H 5 OH (M.W. 622.90): C 77.12; H 10.03. Found: C 77.21; H 10.12.
IRν, KBr (cm -1 ): 3380, 2920, 2850, 1705, 1683, 1607, 1590, 1510, 1280, 1225.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2 ABq, 4.2 Hz), 0.60 (1H, 1/2 ABq, 4.2 Hz), 0.70-2.40 (27H, m), 0.91 (6H, s), 0.97 (3H, s), 1.03 (3H, s), 1.60 (3H, bs), 1.68 (3H, bs), 3.93 (3H, s), 4.60-5.30 (2H, m), 6.08 (1H, bs), 6.78-7.80 (3H, m).
EXAMPLE 30
Preparation of cyclobranyl-3,4-diacetoxycinnamate
Thionyl chloride (30 ml) was added to a suspension of 3,4-diacetylcaffeic acid (21.44 g, 0.081 mole) in toluene (100 ml). The mixture was stirred at 60° C. for 3 hours. The resulting mixture was distilled under reduced pressure to remove the solvent. The residue was suspended in a mixture of toluene (150 ml) and pyridine (30 ml). Cyclobranol (25 g, 0.0567 mole) was added to the suspension, and the mixture was stirred at 60° C. for 2 hours. Then the solvents were removed by distillation under reduced pressure. The residue was extracted with chloroform (300 ml). The extract was washed, dried, and evaporated to remove the chloroform. The residue was purified by silica gel column chromatography (solvent: toluene), giving cyclobranyl-3,4-diacetoxycinnamate (23.7 g) in a 61% yield. m.p. 174°-175° C.
Specific rotation [α] D 21 .5 +37.0° (C 1.00, CHCl 3 )
Analysis. Calcd. for C 44 H 62 O 6 (M.W. 686.94): C 76.93; H 9.10. Found: C 76.87; H 9.15.
IRν, KBr (cm -1 ): 3400, 2850, 1775, 1705, 1200, 1170.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.62 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.50 (27H, m), 0.88 (6H, s), 0.96 (6H, s), 1.62 (9H, s), 1.28 (3H, s), 4.50-4.88 (1H, m), 6.39 (1H, 1/2 ABq, 15.6 Hz), 7.08-7.43 (3H, m), 7.62 (1H, 1/2 ABq, 15.6 Hz).
EXAMPLE 31
Preparation of cyclobranyl-3,4-dipropionyloxycinnamate
Thionyl chloride (17.43 ml, 2 equivalents) was added to a suspension of 3,4-dipropionylcaffeic acid (35.07 g, 0.12 mole) in toluene (150 ml), and the reaction mixture was stirred at 60° C. for 2 hours. The resulting mixture was distilled under reduced pressure to remove the solvent. The residue was suspended in a mixture of toluene (240 ml) and pyridine (50 ml). Cyclobranol (40 g, 0.0908 mole) was added to the suspension, and the mixture was stirred at 60° C. for 2 hours. Then the solvents were removed by distillation under reduced pressure. The residue was extracted with chloroform (300 ml). The extract was dried and evaporated to remove the chloroform. The resulting residue was purified by silica gel column chromatography (solvent: toluene), giving cyclobranyl-3,4-dipropionyloxycinnamate (41.9 g) in a 64% yield. m.p. 163°-165° C.
Specific rotation [α] D 21 .5 +34.7° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 46 H 66 O 6 (M.W. 714.99): C 77.27; H 9.30. Found: C 77.34; H 9.23.
IRν, KBr (cm -1 ): 2920, 2850, 1770, 1710, 1250, 1170.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.62 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.20 (27H, m), 0.90 (6H, s), 0.96 (6H, s), 1.25 (6H, t, 7.2 Hz), 1.62 (9H, s), 2.57 (4H, q, 7.2 Hz), 4.50-4.88 (1H, m), 6.36 (1H, 1/2ABq, 15.6 Hz), 7.05 (3H, m), 7.60 (1H, 1/2 ABq, 15.6 Hz).
EXAMPLE 32
Preparation of cyclobranyl-3,4-dihydroxycinnamate
Cyclobranyl-3,4-dipropionyloxycinnamate (35 g, 0.049 mole) prepared according to the procedure of Example 31 was dissolved in dioxane (600 ml). To the solution was added 25% aqueous ammonia (70 ml) and the mixture was stirred at 50° C. for 2 hours. Then the solvent was removed by distillation under reduced pressure. The crude crystals were recrystallized from acetone-water (4:1, V/V), giving cyclobranyl-3,4-dihydroxycinnamate (22.3 g) in a 75% yield. m.p. 246°-247.5° C.
Specific rotation [α] D 25 +33.6° (C 1.10, CHCl 3 )
Analysis, Calcd. for C 40 H 58 O 4 (M.W. 602.86): C 79.69; H 9.70. Found: C 79.62, H 9.68.
IRν, KBr (cm -1 ): 3400, 2920, 2850, 1680, 1600, 1520, 1440, 1275, 1180, 970.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.59 (1H, 1/2 ABq, 4.8 Hz), 0.69-2.20 (27H, m), 0.85 (3H, s), 0.90 (3H, s), 0.96 (6H, s), 1.60 (9H, s), 4.36-4.80 (1H, m), 6.16 (1H, 1/2 ABq, 15.6 Hz), 6.60-7.16 (5H, m), 7.74 (1H, 1/2 ABq, 15.6 Hz).
EXAMPLE 33
Preparation of cyclobranyl-3,4-dihydroxycinnamate
The title compound was prepared according to following the procedure of Example 32 where cyclobranyl-3,4-diacetoxycinnamate (35 g, 0.051 mole) was used in place of cyclobranyl-3,4-dipropionyloxycinnamate. The yield was 22.1 g (64%). m.p. 246°-247° C.
Specific rotation [α] D 25 +33.6° (C 0.11, CHCl 3 )
Analysis, Calcd. for C 40 H 58 O 4 (M.W. 602.86): C79.69; H 9.70. Found: C 77.78; H 9.62.
EXAMPLE 34
Preparation of cyclobranyl-p-acetoxycinnamate
p-Acetyl coumaric acid (18.2 g, 0.0885 mole) suspended in toluene (100 ml) and thionyl chloride (12.82 ml, 2 equivalents) was heated at 60° C. for 2 hours with stirring. The resulting mixture was distilled under reduced pressure to remove the solvent. The residue was dissolved in a mixture of toluene (150 ml) and pyridine (30 ml), and to the mixture was added cyclobranol (30 g, 0.068 mole). The whole was heated at 60° C. for 2 hours with stirring. Then the solvents were removed by distillation under reduced pressure, and the residue was extracted with chloroform (250 ml). The extract was dried and evaporated to remove the chloroform. The residue was purified by silica gel column chromatography (solvent: toluene), giving cyclobranyl-p-acetoxycinnamate (32.1 g) in a 75% yield. m.p. 164°-165° C.
Specific rotation [α] D 21 .5 +40.8° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 42 H 60 O 4 (M.W. 628.90): C 80.21; H 9.62. Found: C 80.14; H 9.67.
IRν, KBr (cm -1 ): 2920, 2850, 1765, 1700, 1630, 1370, 1200, 1165.
PMR (CDCl 3 )δ: 0.35 (1H, 1/2 ABq, 4.8 Hz), 0.60 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.40 (27H, m), 0.90 (6H, s), 0.98 (6H, s), 1.62 (9H, s), 2.28 (3H, s), 4.50-4.88 (1H, m), 6.37 (1H, 1/2 ABq, 15.6 Hz), 6.90-7.20 (2H, m), 7.35-7.64 (2H, m), 7.62 (1H, 1/2 ABq, 15.6 Hz).
EXAMPLE 35
Preparation of cyclobranyl-p-hydroxycinnamate
Cyclobranyl-p-acetoxycinnamate (27 g, 0.043 mole) prepared according to the procedure of Example 34 was dissolved in tetrahydrofuran (400 ml), and heated with 25% aqueous ammonia (50 ml) at 40° C. for 2 hours with stirring. The resulting mixture was evaporated to dryness under reduced pressure to remove the solvent. The crystals separating out were recrystallized from acetone-water (5:1, V/V), giving cyclobranyl-p-hydroxycinnamate (22.2 g) in a 88% yield, m.p. 243°-244° C.
Specific rotation [α] D 25 +41.3° (C 1.09, CHCl 3 )
Analysis, Calcd. for C 40 H 58 O 3 (M.W. 586.86): C 81.86; H 9.96 Found: C 81.77; H 9.99.
IRν, KBr (cm -1 ): 3370, 2920, 2850, 1670, 1605, 1585, 1510, 1280, 1170, 830.
PMR (CDCl 3 )δ: 0.37 (1H, 1/2 ABq, 4.8 Hz), 0.62 (1H, 1/2 ABq, 4.8 Hz), 0.68-2.15 (27H, m), 0.88 (3H, s), 0.90 (3H, s), 0.97 (6H, s), 1.59 (9H, s), 4.39-4.78 (1H, m), 6.11 (1H, 1/2 ABq, 15.6 Hz), 6.55-6.83 (2H, m), 7.10-7.41 (3H, m), 7.42 (1H, 1/2 ABq, 15.6 Hz).
EXAMPLE 36
Preparation of cyclobranyl-4-acetoxy-3-methoxybenzoate
To 4-acetylvanillic acid (18.60 g, 0.0885 mole) dissolved in toluene (100 ml) was added thionyl chloride (12.86 ml, 2 equivalents) and the mixture was stirred at 60° C. for 2 hours. The resulting mixture was evaporated under reduced pressure and the residue was dissolved in toluene (150 ml) and pyridine (30 ml). To the solution was added cyclobranol (30 g 0.068 mole) and the mixture was stirred at 60° C. for 2 hours. Then the mixture was evaporated under the reduced pressure, and the residue was extracted with chloroform (300 ml). The extract was dried, concentrated in vacuo, and purified by silica gel column chromatography (solvent: ethylacetatehexane, (1:6, V/V)), giving cyclobranyl-4-acetoxy-3-methoxybenzoate ester (33.38g) in a 77% yield. m.p. 177°-178° C.
Specific rotation [α] D 21 .5 +54.1° (C 1.02, CHCl 3 )
Analysis, Calcd. for C 41 H 60 O 5 (M.W. 632.89): C 77.80; H 9.56. Found: C 77.71; H 9.64.
IRν, KBr (cm -1 ): 2920, 2850, 1770, 1710, 1285, 1190, 1170.
PMR (CDCl 3 )δ: 0.38 (1H, 1/2 ABq, 4.8 Hz), 0.63 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.40 (27H, m), 0.92 (6H, s), 0.98 (3H, s), 1.04 (3H, s), 1.62 (9H, s), 2.32 (3H, s), 3.88 (3H, s), 4.60-5.00 (1H, m), 6.92-7.20 (1H, m), 7.51-7.80 (2H, m).
EXAMPLE 37
Preparation of cyclobranyl-4-hydroxy-3-methoxybenzoate
Cyclobranyl-4-acetoxy-3-methoxybenzoate (30 g, 0.0474 mole) prepared according to the procedure of Example 36 was dissolved in tetrahydrofuran (300 ml), and to the solution was added 25% aqueous ammonia (60 ml). The mixture was stirred at 50° C. for 2 hours, then the resulting mixture was evaporated to dryness under reduced pressure. The residual crystals were recrystallized from acetone-water (5:1. V/V), giving cyclobranyl-4-hydroxy-3-methoxybenzoate (23.1 g), in a 82% yield. m.p. 191°-193° C.
Specific rotation [α] D 26 +55.8° (C 1.02, CHCl 3 )
Analysis, Calcd. for C 39 H 58 O 4 (M.W. 590.85): C 79.27; H 9.89. Found: C 79.35; H 9.80.
IRν, KBr (cm -1 ): 3400, 2920, 2850, 1700, 1590, 1510, 1275, 1220.
PMR (CDCl 3 )δ: 0.38 (1H, 1/2 ABq, 4.8 Hz), 0.64 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.2 (27H, m), 0.92 (6H, s), 1.0 (3H, s), 1.05 (3H, s), 1.64 (9H, s), 3.95 (3H, s), 4.6-5.0 (1H, m), 6.06 (1H, bs), 6.74-7.04 (1H, m), 7.44-7.77 (2H, s).
EXAMPLE 38
Preparation of cyclobranyl-3,4-diacetoxybenzoate
To diacetylprotocatechuic acid (21.08 g, 0.0885 mole) suspended in toluene (100 ml) was added thionyl chloride (12.86 ml, 2 equivalents), and the mixture was stirred at 60° C. for 2 hours. Then the resulting mixture was evaporated under reduced pressure. The residue was suspended in toluene (150 ml) and pyridine (30 ml), and to the suspension was added cyclobranol (30 g, 0.068 mole). The mixture was stirred at 60° C. for 2 hours. Then the solution was evaporated under reduced pressure. The residue was extracted with chloroform (300 ml). And the extract was dried, concentrated in vacuo, and purified by silica gel column chromatography (solvent: toluene), giving cyclobranyl-3,4-diacetoxybenzoate (24.2 g) in a 54% yield. m.p. 165°-166° C.
Specific rotation [α] D 21 .5 +51.3° (C 1.01, CHCl 3 )
Analysis, Calcd. for C 42 H 60 O 6 (M.W. 660.90): C 76.32; H 9.15. Found: C 76.45; H 9.10.
IRν, KBr (cm -1 ): 2920, 2850, 1770, 1715, 1280, 1195, 1160.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.62 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.40 (27H, m), 0.90 (6H, s), 0.96 (3H, s), 1.00 (3H, s), 1.60 (9H, s), 2.26 (6H, s), 4.60-4.98 (1H, m), 7.08-7.40 (1H, m), 7.73-8.06 (2H, m).
EXAMPLE 39
Preparation of cyclobranyl-3,4-dihydroxybenzoate
Cyclobranyl-3,4-diacetoxybenzoate (24.0 g, 0.0363 mole) prepared according to the procedure of Example 38 was dissolved in dioxane (480 ml) and to the solution was added 25% aqueous ammonia (48 ml). The mixture was stirred at 40° C. for 1 hour, then the resulting mixture was evaporated to dryness under reduced pressure. The residual crystals were recrystallized from ethanol, giving cyclobranyl-3,4-dihydroxybenzoate (17.5 g), in a 84% yield. m.p. 215°-216° C.
Specific rotation [α] D 26 +59.4° (C 0.98, CHCl 3 )
Analysis, Calcd. for C 38 H 56 O 4 (M.W. 576.83): C 79.12; H 9.79. Found: C 79.03; H 9.87.
IRν, KBr (cm -1 ) 3350, 2920, 2850, 1680, 1605, 1440, 1280, 1230, 1100, 975.
PMR (CDCl 3 )δ: 0.38 (1H, 1/2 ABq, 4.8 Hz), 0.61 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.20 (27H, m), 0.90 (6H, s), 0.98 (3H, s), 1.02 (3H, s), 1.62 (9H, s), 2.72-3.20 (2H, bs), 4.60-4.90 (1H, m), 6.70-6.96 (1H, m), 7.40-7.64 (2H, m).
EXAMPLE 40
Preparation of cyclobranyl-o-acetoxybenzoate
To acetylsalicylic acid (15.94 g, 0.088 mole) suspended in toluene (100 ml) was added thionyl chloride (40 ml, 6.3 equivalents) and the mixture was stirred at 80° C. for 3 hours. The resulting mixture was evaporated under reduced pressure, and the residue was dissolved in toluene (180 ml) and pyridine (40 ml), followed by addition of cyclobranol (30 g, 0.068 mole). The mixture was continued to stir at 60° C. for 2 hours, then the resulting mixture was evaporated under reduced pressure. The residue was extracted with chloroform (300 ml), and the extract was washed with 3% aqueous sodium bicarbonate, water, and saturated brine. The extract was dried, concentrated in vacuo, and the residue was purified by silica gel column chromatography (solvent: hexane-toluene, (1:1, V/V)), giving cyclobranyl-o-acetoxybenzoate (29.6 g), in a 72% yield. m.p. 165°-166° C.
Specific rotation [α] D 23 +58.4° (C 1.01, CHCl 3 )
Analysis, Calcd. for C 40 H 58 O 4 (M.W. 602.86): C 79.69; H 9.70. Found: C 79.64; H 9.78.
IRν, KBr (cm -1 ): 2920, 2850, 1770, 1720, 1260, 1190, 1080
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.60 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.40 (27H, m), 0.89 (6H, s), 0.96 (3H, s), 1.00 (3H, s), 1.62 (9H, s), 2.33 (3H, s), 4.60-4.95 (1H, m), 6.88-7.68 (3H, m), 7.82-8.10 (1H, m).
EXAMPLE 41
Preparation of cyclobranyl-o-hydroxybenzoate
Cyclobranyl-o-acetoxybenzoate (24 g, 0.0398 mole) prepared according to the procedure of Example 40 was dissolved in dioxane (400 ml) and to the solution was added 25% aqueous ammonia (60 ml) dropwise. The mixture was stirred at 50° C. for 2 hours and evaporated to dryness under reduced pressure. The residual crystals were recrystallized from acetone-water (1:1, V/V), giving cyclobranyl-o-hydroxybenzoate ester (20.2 g), in a 90% yield. m.p. 200°-201° C.
Specific rotation [α] D 23 +69.3° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 38 H 56 O 3 (M.W. 560.83): C 81.38; H 10.07. Found: C 81.29; H 10.02.
IRν, KBr (cm -1 ): 3120, 2920, 2850, 1670, 1615, 1300, 1250, 1220, 1165, 1095.
PMR (CDCl 3 )δ: 0.37 (1H, 1/2 ABq, 4.8 Hz), 0.62 (1H, 1/2 ABq, 4.8 Hz), 0.7-2.20 (27H, m), 1.05 (3H, s), 0.90 (6H, s), 0.97 (3H, s), 1.60 (9H, s), 4.60-5.00 (1H, m), 6.67-7.93 (4H, s), 10.92 (1H, s).
EXAMPLE 42
Preparation of cyclobranyl-p-nitrobenzoate
To p-nitrobenzoic acid (1 g, 0.006 mole) dissolved in dioxane (20 ml) was added thionyl chloride (3 ml, 7 equivalents) and the mixture was stirred at 60° C. for 2 hours. The resulting mixture was evaporated under reduced pressure, then dioxane (20 ml) and pyridine (3 ml) were added to the resulting residue. Cyclobranol (2 g, 0.0045 mole) was added to the solution and the mixture was stirred at 60° C. for 2 hours to complete the reaction. The mixture was evaporated under reduced pressure, and the residue was extracted with chloroform (30 ml). The extract was washed successively with 3% aqueous sodium carbonate, water, and saturated brine, dried, and evaporated to dryness under reduced pressure. The crude crystals were washed with ethanol (50 ml), and recrystallized from ethyl acetate, giving cyclobranol-p-nitrobenzoate (2.28 g) in a 90% yield. m.p. 244°-245° C.
Specific rotation [α] D 24 +60.1° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 38 H 55 O 4 N (M.W. 589.83): C 77.37; H 9.40; N 2.37. Found: C 77.45; H 9.33; N 2.42.
IRν, KBr (cm -1 ): 2920, 2850, 1715, 1525, 1350, 1290, 1120, 1100, 720.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2 ABq, 4.8 Hz), 0.64 (1H, 1/2 ABq, 4.8 Hz), 0.72-2.20 (27H, m), 0.92 (6H, s), 0.98 (3H, s), 1.06 (3H, s), 1.62 (9H, s), 4.59-5.02 (1H, m), 8.00-8.43 (4H, m).
EXAMPLE 43
Preparation of cyclobranyl-p-aminobenzoate
Cyclobranyl-p-nitrobenzoate (2 g, 0.0034 mole) prepared according to the procedure of Example 42 was suspended in acetic acid (80 ml), and was added zinc powder (2 g, 9 equivalents). The mixture was refluxed for 4 hours, then cooled and the zinc powder was separated by filtration. The filtrate was evaporated under reduced pressure, and extracted with chloroform (50 ml). The extract was dried, concentrated in vacuo, and the purified by silica gel column chromatography (solvent: chloroform). The thus obtained crystals were recrystallized from ethanol, giving cyclobranyl-p-aminobenzoic acid ester (1.37 g), in a 72% yield. m.p. 190°-191° C.
Specific rotation [α] D 26 +58.4° (C 1.01, CHCl 3 )
Analysis, Calcd. for C 38 H 57 O 2 N (M.W. 559.84): C 81.52; H 10.26; N 2.50. Found: C 81.49; H 10.21; N 2.57.
IRν, KBr (cm -1 ): 3450, 3350, 2920, 2850, 1685, 1620, 1600, 1510, 1275, 1170, 1110.
PMR (CDCl 3 )δ: 0.37 (1H, 1/2 ABq, 4.8 Hz), 0.61 (1H, 1/2 ABq, 4.8 Hz), 0.72-2.30 (27H, m), 0.89 (6H, s), 0.96 (3H, s), 1.00 (3H, s), 1.60 (9H, s), 3.60-4.40 (2H, b), 4.50-4.90 (1H, m), 6.44-6.76 (2H, m), 7.64-8.00 (2H,m).
EXAMPLE 44
Preparation of cyclobranyl-p-acetamidobenzoate
To p-acetamidobenzoic acid (15.85 g, 0.088 mole) dissolved in dioxane (150 ml) was added thionyl chloride (25.7 ml, 4 equivalents) and the mixture was stirred at 60° C. for 2 hours. The resulting mixture was evaporated under reduced pressure and dioxane (150 ml) and pyridine (50 ml) were added to the residue. Cyclobranol (30 g, 0.068 mole) was added to the solution, and the mixture was stirred at 60° C. for hours. The reactioh mixture was evaporated under reduced pressure, and to the residue was added ethyl acetate (300 ml). The crude crystals which separated out were filtered, and purified by silica gel column chromatography (solvent: chloroform). The resulting crystals were further recrystallized from ethanol, giving cyclobranyl-p-acetamidobenzoate (32 g), in a 78% yield. m.p. 197°-198° C.
Specific rotation [α] D 24 +54.7° (C 1.01, CHCl 3 )
Analysis, Calcd. for C 40 H 59 O 3 N (M.W. 601.88): C 79.82; H 9.88; N 2.33. Found: C 79.75; H 9.83; N 2.41.
IRν, KBr (cm -1 ) 3420, 2920, 2850, 1710, 1690, 1680, 1600, 1535, 1280, 1175.
PMR (CDOD-CDCl 3 )δ: 0.38 (1H, 1/2 ABq, 4.8 Hz), 0.62 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.28 (27H, m), 0.90 (6H, s), 0.98 (3H, s), 1.04 (3H, s), 1.62 (9H, s), 2.16 (3H, s), 4.50-4.96 (1H, m), 7.37 (1H, b), 7.44-8.12 (4H, m).
EXAMPLE 45
Preparation of cyclobranyl-p-aminobenzoate
Cyclobranyl-p-acetamidobenzoate (32 g, 0.053 mole) prepared according to the procedure of Example 44 was dissolved in tetrahydrofuran (300 ml) and conc. hydrochloric acid (60 ml) was added to it, and stirred at 70° C. for 2 hours. Then the mixture was evaporated under reduced pressure. The residue was extracted with chloroform (400 ml), then the extract was dried and concentrated. The residue was purified twice by silica gel column chromatography (solvent: toluene-hexane-ethyl acetate, (5:3:1, V/V)), giving cyclobranyl-p-aminobenzoate (17 g) in a 57% yield. m.p. 190°-191° C.
Specific rotation [α] D 26 +58.4° (C 1.01, CHCl 3 )
Analysis, Calcd. for C 38 H 57 O 2 N (M.W. 559.84): C 81.52; H 10.26; N 2.50. Found: C 81.57; H 10.34; N 2.44.
EXAMPLE 46
Preparation of cyclobranyl-o-nitrobenzoate
To o-nitrobenzoic acid (12.32 g, 0.074 mole) dissolved in dioxane (200 ml) was added thionyl chloride (30 ml, 5.6 equivalents) and the mixture was stirred at 60° C. for 2 hours. After the reaction was finished, the mixture was evaporated to dryness under reduced pressure. The resulting residue was dissolved in dioxane (150 ml) and pyridine (50 ml). To the solution was added cyclobranol (25 g, 0.0567 mole) and this mixture was stirred at 60° C. for 2 hours. Then the mixture was evaporated to dryness under reduced pressure, and the residue was extracted with chloroform (300 ml). The extract was washed successively with 3% aqueous sodium carbonate, water, and saturated brine, dried, and evaporated to dryness under reduced pressure. The crude crystals were washed with ethanol (100 ml), and recrystallized from acetone-water (1:1, V/V), giving cyclobranyl-o-nitrobenzoate (30.8 g), in a 92% yield. m.p. 217°-218° C.
Specific rotation [α] D 21 +90.8° (C 0.98, CHCl 3 )
Analysis, Calcd. for C 38 H 55 O 4 N (M.W. 589.83): C 77.37; H 9.40; N 2.37. Found: C 77.42, H 9.34; N 2.47.
IRν, KBr (cm -1 ): 2930, 2850, 1710, 1535, 1380, 1300.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.62 (1H, 1/2 ABq, 4.8 Hz), 0.75-2.20 (27H, m), 0.90 (3H, s), 0.92 (6H, s), 0.98 (3H, s), 1.64 (9H, s), 4.63-5.00 (1H, m), 7.46-7.98 (4H, m).
EXAMPLE 47
Preparation of cyclobranyl-o-aminobenzoate
Cyclobranyl-o-nitrobenzoic acid ester (30 g, 0.05 mole) prepared according to the procedure of Example 46 was suspended in acetic acid (1.2 l). And to the suspension was added zinc powder (30 g, 9 equivalents) which was washed with dilute hydrochloric acid before it. The mixture was refluxed for 5 hours, then cooled and the zinc powder was removed by filtration. The filtrate was evaporated under reduced pressure and the residue was extracted with chloroform (300 ml). The extract was dried, concentrated to dryness in vacuo, and purified by silica gel column chromatography (solvent: chloroform), giving cyclobranyl-o-aminobenzoate (20 g) in a 68% yield. m.p. 207°-208° C.
Specific rotation [α] D 24 +74.9° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 38 H 57 O 2 N (M.W. 559.84): C 81.52; H 10.26; N 2.50. Found: C 81.59; H 10.28; N 2.43.
Irν, KBr (cm -1 ) 3460, 3350, 2940, 2850, 1670, 1620, 1290, 1245, 1155, 755.
PMR (CDCl 3 )δ: 0.37 (1H, 1/2 ABq, 4.8 Hz), 0.62 (1H, 1/2 ABq, 4.8 Hz), 0.7-2.20 (27H, m), 0.92 (6H, s), 0.98 (3H, s), 1.04 (3H, s), 1.64 (9H, s), 4.50-4.95 (1H, m), 5.73 (2H, bs), 6.40-6.78 (2H, m), 7.00-7.40 (1H, m), 7.61-7.98 (1H, m).
EXAMPLE 48
Preparation of cyclobranyl-m-nitrobenzoate
Cyclobranol (18 g, 0.04 mole) dissolved in pyridine (200 ml) was stirred and cooled in a bath of ice water, and to it was added m-nitrobenzoyl chloride (9.85 g, 0.053 mole). Then the mixture was warmed to 20° C. and continued to stir for 12 hours. After the reaction is complete the mixture was evaporated under reduced pressure. Ice cold water (200 ml) was added to the residue and crystals begans to appear. The crude crystals were separated by filtration and recrystallized from acetone-water (1:1, V/V), giving cyclobranol-m-nitrobenzoate (20.1 g), in a 83% yield. m.p. 206°-207° C.
Specific rotation [α] D 21 +60.8° (C 0.99, CHCl 3 )
Analysis, Calcd. for C 38 H 55 O 4 N (M.W. 589.83): C 77.37; H 9.40; N 2.37. Found: C 77.44; H 9.33; N 2.45.
IRν, KBr (cm -1 ): 2930, 2850, 1715, 1530, 1350, 1290, 1140, 715.
PMR (CDCl 3 )δ: 0.40 (1H, 1/2 ABq, 4.8 Hz), 0.66 (1H, 1/2 ABq, 4.8 Hz), 0.80-2.20 (27H, m). 0.92 (6H, s), 0.98 (3H, s), 1.08 (3H, s), 1.64 (9H, s), 4.65-5.05 (1H, m), 7.44-7.80 (1H, m), 8.20-8.52 (2H, m), 8.72-8.89 (1H, m).
EXAMPLE 49
Preparation of cyclobranyl-m-aminobenzoate
Cyclobranyl-m-nitrobenzoate (24 g, 0.04 mole) prepared according to the procedure of Example 48 was suspended in acetic acid (1.3 l). Zinc powder (24 g, 9 equivalents) was added to the suspension, and the mixture was refluxed for 2 hours. After the reaction was finished mixture was cooled and the zinc powder was separated by filtration. The filtrate was evaporated under reduced pressure, and the residue was extracted with chloroform (300 ml). The extract was dried, evaporated to dryness under reduced pressure, and the residue was purified by silica gel column chromatography (solvent: chloroform), giving cyclobranyl-m-aminobenzoate (19 g) in a 83% yield. m.p. 187°-188° C.
Specific rotation [α] D 24 +61.7° (C 1.03, CHCl 3 )
Analysis, Calcd. for C 38 H 57 O 2 N (M.W. 559.84): C 81.52; H 10.26; N 2.50. Found: C 81.44; H 10.29; N 2.56.
IRν, KBr (cm -1 ): 3450, 3350, 2940, 2850, 1700, 1460, 1320, 1290, 1245, 755.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.61 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.28 (27H, m), 0.90 (6H, s), 0.98 (3H, s), 1.04 (3H, s), 1.64 (9H, s), 3.53 (2H, b), 4.59-4.90 (1H, m), 6.60-7.55 (4H, m).
EXAMPLE 50
Preparation of cyclobranylnicotinate
Thionyl chloride (30 ml, 4.6 equivalents) was added to nicotinic acid (10.9 g, 0.0885 mole) and the mixture was stirred at 80° C. for 2 hours to complete the reaction. Then the excess thionyl chloride was removed under reduced pressure. To the residue dissolved in a mixture of toluene (120 ml) and pyridine (50 ml) was added cyclobranol (30 g, 0.068 mole) and the mixture was stirred at 60° C. for 2 hours. Then the mixture was evaporated to dryness under reduced pressure, and the residue was extracted with chloroform (300 ml). The extract was dried, concentrated in vacuo, and the residue was purified by silica gel column chromatography (solvent: toluene), giving cyclobranylnicotinate (32.3 g), in a 87% yield. m.p. 176°-177° C.
Specific rotation [α] D 26 +63.4° (C 1.04, CHCl 3 )
Analysis, Calcd. for C 37 H 55 O 2 N (M.W. 545.82): C 81.41; H 10.16; N 2.57. Found: C 81.49; H 10.13; N 2.64.
IRν, KBr (cm -1 ): 2920, 2850, 1720, 1590, 1285, 1120, 965.
PMR (CDCl 3 )δ: 0.37 (1H, 1/2 ABq, 4.8 Hz), 0.62 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.27 (27H, m), 0.90 (6H, s), 0.93 (3H, s), 1.03 (3H, s), 1.62 (9H, s), 4.60-5.00 (1H, m), 7.13-7.50 (1H, m), 8.06-8.40 (1H, m), 8.60-8.82 (1H, m), 9.07-9.27 (1H, m).
EXAMPLE 51
Preparation of cyclobranyllinolate
Thionyl chloride (20 ml, 4.8 equivalents) was added to linoleic acid (16.5 g, 0.0588 mole) and the mixture was stirred at 40° C. for 1.5 hours. After the reaction was completed excess thionyl chloride was removed under reduced pressure, and the residue was dissolved in a mixture of toluene (100 ml) and pyridine (20 ml). Cyclobranol (20 g, 0.0454 mole) was added to the solution and the mixture was stirred at 40° C. for 2 hours, then evaporated under reduced pressure. The oily residue was extracted with chloroform (300 ml), and the extract was dried and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography (solvent: toluene-hexane, (2:1, V/V)), giving cyclobranyllinolate (22.2 g), in a 69% yield. m.p. oily matter.
Specific rotation [α] D 21 .5 +36.5° (C 0.95, CHCl 3 )
Analysis, Calcd. for C 49 H 82 O 2 (M.W. 703.15): C 83.69; H 11.76. Found: C 83.61; H 11.88.
Irν, KBr (cm -1 ): 2910, 2850, 1730, 1460, 1372, 1175.
PMR (CDCl 3 )δ: 0.34 (1H, 1/2 ABq, 4.8 Hz), 0.58 (1H, 1/2 ABq, 4.8 Hz), 0.68-2.43 (52H, m), 0.83 (3H, s), 0.89 (6H, s), 0.95 (3H, s), 1.60 (9H, s), 2.52-2.91 (2H, m), 4.40-4.80 (1H, m), 5.04-5.62 (4H, m).
EXAMPLE 52
Preparation of cyclobranyl-m-methoxybenzoate
m-Anisic acid (8.1 g, 0.053 mole) was added to thionyl chloride (20 ml), and the mixture was stirred at 60° C. for 2 hours. After the reaction is completed the excess thionyl chloride was removed under reduced pressure. The residue was dissolved in pyridine (80 ml) and cyclobranol (18 g, 0.041 mole) was added to the solution. The mixture was stirred at 60° C. for 2 hours, then evaporated to dryness under reduced pressure. The resulting residue was purified by silica gel column chromatography, and recrystallized from ethanol, giving cyclobranyl-m-methoxybenzoate (20.7 g), in a 88% yield. m.p. 163°-164° C.
Specific rotation [α] D 21 .5 +61.6° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 39 H 58 O 3 (M.W. 574.85): C 81.48; H10.17. Found: C 81.40; H 10.25.
IRν, KBr (cm -1 ): 2920, 2850, 1715, 1585, 1270, 1220, 1100, 750
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.60 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.20 (27H, m), 0.90 (6H, s), 0.98 (3H, s), 1.02 (3H, s), 1.61 (9H, s), 3.82 (3H, s), 4.60-4.95 (1H, m), 6.84-7.72 (4H, m).
EXAMPLE 53
Preparation of cyclobranyl-m-acetoxybenzoate
m-Acetoxybenzoic acid (19 g, 0.105 mole) and thionyl chloride (40 ml) was mixed and stirred at 60° C. for 2 hours. After the reaction is complete, the excess thionyl chloride was removed by distillation, and the residue was dissolved in a mixture of toluene (220 ml) and pyridine (60 ml). Cyclobranol (35 g, 0.0794 mole) was added to the solution and the mixture was stirred at 60° C. for 2 hours. After that the solution was evaporated under reduced pressure, and the residue was extracted with chloroform (300 ml). The extract was dried, concentrated in vacuo, and the residue was purified by silica gel column chromatography (solvent: chloroform), giving cyclobranyl-m-acetoxybenzoate (46.3 g), in a 97% yield. m.p. 42°-143° C.
Specific rotation [α] D 21 .5 +59.0° (C 0.97, CHCl 3 )
Analysis, Calcd. for C 40 H 58 O 4 (M.W. 602.86): C 79.69; H 9.70. Found: C 79.58; H 9.73.
IRνKBr (cm -1 ): 2920, 2850, 1770, 1720, 1290, 1270, 1200, 1100.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.61 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.38 (27H, m), 0.90 (6H, s), 0.96 (3H, s), 1.02 (3H, s), 1.62 (9H, s), 2.31 (3H, s), 4.60-4.96 (1H, m), 7.11-8.02 (4H, m).
EXAMPLE 54
Preparation of cyclobranyl-m-hydroxybenzoate
Cyclobranyl-m-acetoxybenzoate (24.5 g, 0.0406 mole) prepared according to the procedure of Example 53 was dissolved in tetrahydrofuran (300 ml). To the solution was added 25% aqueous ammonia (40 ml) and the mixture was stirred at 40° C. for 2 hours. The reaction mixture was evaporated to dryness under reduced pressure, and the resulting residue was recrystallized from ethanol, giving cyclobranyl-m-hydroxybenzoate (20.3 g), in a 86% yield. m.p. 203°-204.5° C.
Specific rotation [α] D 21 .5 +62.2° (C 0.95, CHCl 3 )
Analysis, Calcd. for C 38 H 56 O 4 (M.W. 576.83): C 79.12; H 9.79. Found: C 79.23; H 9.72.
IRν, KBr (cm -1 ): 3380, 2920, 2850, 1690, 1600, 1450, 1290, 1245, 1110, 760.
PMR (CDCl 3 )δ: 0.38 (1H, 1/2 ABq, 4.8 Hz), 0.61 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.20 (27H, m), 0.93 (6H, s), 0.98 (3H, s), 1.04 (3H, s), 1.64 (9H, s), 3.54 (1H, bs), 4.58-4.90 (1H, m), 6.84-7.66 (4H, m).
EXAMPLE 55
Preparation of cyclobranyl-p-methoxybenzoate
Cyclobranol (18 g, 0.041 mole) dissolved in pyridine (80 ml) was stirred and cooled in a bath of ice water, and to it was added p-methoxybenzoyl chloride (9.1 g, 0.0533 mole). The mixture was warmed to 20° C. and continued to stir for 15 hours. Then the mixture was evaporated under reduced pressure, and the residue was extracted with chloroform (300 ml). The extract was concentrated in vacuo, and the resulting residue was purified by silica gel column chromatography (solvent: chloroform), giving cyclobranyl-p-methoxybenzoate (21.7 g), in a 92% yield. m.p. 202°-203° C.
Specific rotation [α] D 21 .5 +60.2° (C 1.06, CHCl 3 )
Analysis, Calcd. for C 39 H 58 O 3 (M.W. 574.85): C 81.48; H 10.17. Found: C 81.32; H 10.25.
IRν, KBr (cm -1 ); 2920, 2850, 1705, 1605, 1510, 1270, 1255, 1170, 1110, 1100.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.61 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.38 (27H, m), 0.90 (6H, s), 0.98 (3H, s), 1.02 (3H, s), 1.62 (9H, s), 3.84 (3H, s), 4.60-4.95 (1H, m), 6.72-7.04 (2H, m), 7.80-8.12 (2H, m).
EXAMPLE 56
Preparation of cyclobranyl-o-methoxybenzoate
Cyclobranol (18 g, 0.041 mole) dissolved in pyridine (80 ml) was stirred and cooled in a bath of ice water, then to it was added o-methoxybenzoyl chloride (9 g, 0.0527 mole). The mixture was warmed to 20° C. and continued to stir for 15 hours. The mixture was evaporated under reduced pressure, and the residue was extracted with chloroform (300 ml). The extract was dried and the resulting residue was purified by silica gel column chromatography (solvent: chloroform), giving cyclobranyl-o-methoxybenzoate (21.9 g), in a 93% yield. m.p. 176°-177° C.
Specific rotation [α] D 21 .5 +46.3° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 39 H 58 O 3 (M W. 574.85): C 81.48; H 10.17. Found: C 81.40; H 10.25.
IRν, KBr (cm -1 ): 2920, 2850, 1695, 1600, 1460, 1300, 1250, 1130, 760.
PMR (CDCl 3 )δ: 0.35 (1H, 1/2 ABq, 4.8 Hz), 0.59 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.20 (27H, m), 0.90 (3H, s), 0.96 (6H, s), 0.99 (3H, s), 1.61 (9H, s), 3.86 (3H, s), 4.60-5.00 (1H, m), 6.72-7.94 (4H, m).
EXAMPLE 57
Preparation of cyclobranyl-p-acetoxybenzoate
p-Acetoxybenzoic acid (18.6 g, 0.103 mole) and thionyl chloride (40 ml) were mixed and stirred at 60° C. for 12 hours. Then, the excess thionyl chloride was removed by distillation under reduced pressure. And to the residue suspended in toluene (220 ml) and pyridine (60 ml) was added cyclobranol (35 g, 0.0794 mole) and the mixture was stirred at 60° C. for 2 hours. Then the solution was evaporated under reduced pressure, and the residue was extracted with chloroform (400 ml). The extract was dried and concentrated in vacuo, and the resulting product was purified by silica gel column chromatography (solvent: chloroform), giving cyclobranyl-p-acetoxybenzoate ester (44.1 g) in a 92% yield. m.p. 192°-193° C.
Specific rotation [α] D 22 +55.5° (C 0.93, CHCl 3 )
Analysis, Calcd. for C 40 H 58 O 4 (M.W. 602.86): C 79.69; H 9.70. Found: C 79.61; H 9.79.
IRν, KBr (cm -1 ): 2920, 2850, 1765, 1715, 1270, 1190, 1160, 1115.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.60 (1H, 1/2 ABq, 4.8 Hz), 0.68-2.40 (27H, m), 0.89 (6H, s), 0.96 (3H, s), 1.01 (3H, s), 1.60 (9H, s), 2.28 (3H, s), 4.60-5.00 (1H, m), 6.96-7.32 (2H, m), 7.90-8.25 (2H, m).
EXAMPLE 58
Preparation of cyclobranyl-p-hydroxybenzoate
Cyclobranyl-p-acetoxybenzoate (24 g, 0.0398 mole) prepared according to the procedure of Example 57 was dissolved in tetrahydrofuran (350 ml) and to that was added 25% aqueous ammonia (50 ml). The mixture was continued to stir at 40° C. for 1 hour, then, evaporated to dryness under reduced pressure. The residual crystals were recrystallized from ethanol, giving cyclobranyl-p-hydroxybenzoate (21.0 g), in a 94% yield. m.p. 174°-175° C.
Specific rotation [α] D 23 +57.7° (C 1.10, CHCl 3 )
Analysis, Calcd. for C 38 H 56 O 3 .C 2 H 5 OH (M.W. 606.9): C 79.16 ; H 10.30. Found: C 79.13; H 10.42.
IRν, KBr (cm -1 ): 3400, 2920, 2850, 1685, 1610, 1280, 1160.
PMR (CDCl 3 )δ: 0.38 (1H; 1/2 ABq, 4.8 Hz), 0.64 (1H, 1/2 ABq, 4.8 Hz), 0.70-2.42 (27H, m), 0.91 (6H, s), 0.98 (3H, s), 1.02 (3H, s), 1.28 (3H, t, 7.2 Hz), 1.62 (9H, s), 3.77 (2H, q. 7.2 Hz), 4.60-5.00 (1H, m), 6.72-7.18 (4H, m), 7.80-8.12 (2H, m).
EXAMPLE 59
Preparation of cycloartenyl-4-acetoxy-3-ethoxybenzoate
The title compound was prepared according to following the procedure of Example 28 where 4-acetoxy-3-ethoxybenzoic acid (13.9 g, 0.062 mole) was used in place of 4-acetoxy-3-methoxybenzoic acid (13.0 g); cycloartenyl-4-acetoxy-3-ethoxybenzoate was yielded 24.5 g (82%). m.p. 140°-141° C.
Specific rotation [α] D 24 58.2° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 41 H 60 O 5 (M.W. 632.89): C 77.80; H 9.56. Found: C 77.91; H 9.43.
EXAMPLE 60
Preparation of cycloartenyl-3-ethoxy-4-hydroxybenzoate
Cycloartenyl-4-acetoxy-3-ethoxybenzoate (30 g, 0.047 mole) prepared according to the procedure of Example 59 was dissolved in tetrahydrofuran (300 ml), and to it was added 25% aqueous ammonia (60 ml). After the mixture was stirred at 50° C. for 2 hours, the mixture was evaporated to dryness under reduced pressure. The residual crystals were recrystallized from acetone-water (2:1, V/V), giving cycloartenyl-3-ethoxy-4-hydroxybenzoate ester (20.5 g), in a 74% yield. m.p. 128°-130° C.
Specific rotation [α] D 24 +59.5° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 39 H 58 O 4 (M.W. 590.85): C 79.27; H 9.89. Found: C 79.21; H 9.82.
EXAMPLE 61
Preparation of cyclobranyl-4-acetoxy-3-ethoxybenzoate
The title compound was prepared according to following the procedure of Example 28 where 4-acetoxy-3-ethoxybenzoic acid (13.9 g, 0.062 mole) and cyclobranol (20.0 g, 0.045 mole) were used respectively, in place of 4-acetoxy-3-methoxybenzoic acid (13.0 g) and cycloartenol (20.0 g); cyclobranyl-4-acetoxy-3-methoxybenzoate was yielded 23.4 g (80%). m.p. 161°-162° C.
Specific rotation [α] D 24 +56.5° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 42 H 62 O 5 (M.W. 646.92): C 77.97; H 9.66. Found: C 78.05; H 9.61.
EXAMPLE 62
Preparation of cyclobranyl-3-ethoxy-4-hydroxybenzoate
Cyclobranyl-4-acetoxy-3-ethoxybenzoate (30 g, 0.046 mole) prepared according to procedure of Example 61 was dissolved in tetrahydrofuran (300 ml) and to it was added 25% aqueous ammonia (60 ml). After the mixture was stirred at 50° C. for 3 hours, the mixture was evaporated to dryness under reduced pressure, and the residual crystals were recrystallized from acetone-water (2:1, V/V), giving cycloartenyl-3-ethoxy-4-hydroxybenzoate (20.8 g), in a 74% yield. m.p. 175°-176° C.
Specific rotation [α] D 24 +57.5° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 40 H 60 O 4 (M.W. 604.88): C 79.42; H 10.00. Found: C 79.31; H 10.12.
EXAMPLE 63
Preparation of 24-methylenecycloartanyl-4-acetoxy-3-ethoxybenzoate
The title compound was prepared according to following the procedure of Example 28 where 4-acetoxy-3-ethoxybenzoic acid (13.9 g, 0.062 mole) and 24-methylenecycloartenol (20.0 g, 0.045 mole) were used in place of 4-acetoxy-3-methoxybenzoic acid (13.0 g) and cycloartenol (20.0 g), respectively; The yield was 23.1 g (79%). m.p. 152°-153° C.
Specific rotation [α] D 24 +57.8° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 42 H 62 O 5 (M.W. 646.92): C 77.97; H 9.66. Found: C 77.92; H 9.54.
EXAMPLE 64
Preparation of 24-methylenecycloartanyl-3-ethoxy-4-hydroxybenzoate
The title compound was prepared according to following the procedure of Example 55 where 24-methylenecycloartanol-4-acetoxy-3-ethoxybenzoate (30 g, 0.046 mole) obtained by the procedure of Example 63 was used; The yield was 20.1 g (72%). m.p. 141°-142° C.
Specific rotation [α] D 24 +58.4° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 40 H 60 O 4 (M.W. 604.88): C 79.42; H 10.00. Found: C 79.49 H 10.05.
EXAMPLE 65
Preparation of cyclobranyl-4-acetoxy-3-methoxycinnamate
To 4-acetoxy-3-methoxycinnamic acid (26.5 g, 0.112 mole) suspended in toluene (200 ml) was added thionyl chloride (16.3 ml, 3 equivalents) and the mixture was stirred at 60° C. for 2 hours. Then the mixture was evaporated under reduced pressure and the residue was suspended in toluene (150 ml) and pyridine (30 ml). Cyclobranol (33.1 g, 0.075 mole) was added to the suspension and the mixture was stirred at 60° C. for 2 hours. After the reaction was complete, the mixture was evaporated to dryness under reduced pressure, and the residue was extracted with chloroform (300 ml). The extract was washed, dried, and evaporated to dryness under reduced pressure. The residual crystals were recrystallized from ethanol, giving cyclobranyl-4-acetoxy-3-methoxycinnamate (44.9 g), in a 91% yield. m.p. 175°-176° C.
Specific rotation [α] D 25 +37.0° (C 1.00, CHCl 3 )
Analysis, Calcd. for C43H62O5 (M.W. 658.93): C 78.38; H 9.48. Found: 78.44; H 9.43.
EXAMPLE 66
Preparation of cycloartenyl-4-acetoxy-3-methoxycinnamate
The title compound was prepared according to following the procedure of Example 65 where cycloartenol (33 g, 0.077 mole) was used in place of cyclobranol (33 g); the yield was 42.4 g (86%). m.p. 187°-188° C.
Specific rotation [α] D 24 +40.7° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 42 H 60 O 5 (M.W. 644.90): C 78.22; H 9.38. Found: C78.34; H 9.30.
EXAMPLE 67
Preparation of 24-methylenecycloartanyl-4-acetoxy-3-methoxycinnamate
The title compound was prepared according to following the procedure of Example 65 where 24-methylenecycloartanol (33 g, 0.0749 mole) was used in place of cyclobranol; The yield was 43.7 g (88%). m.p. 216°-217° C.
Specific rotation [α] D 24 +40.1° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 43 H 62 O 5 (M W. 658.93): C 78.38; H 9.48. Found: C 78.46; H 9.40.
IRν, KBr (cm -1 ) 2920, 2850, 1765, 1710, 1635, 1510, 1275, 1258, 1200, 1170, 1155.
PMR (CDCl 3 )δ: 0.39 (1H, 1/2 ABq, 4.2 Hz), 0.61 (1H, 1/2 ABq, 4.2 Hz), 0.60-2.40 (28H, m), 0.82 (6H, s), 0.96 (6H, s), 1.02 (6H, d, 7.2 Hz), 2.32 (3H, s), 3.86 (3H, s), 4.70 (2H, bs), 4.50-4.90 (1H, m), 6.40 (1H, 1/2 ABq, 16 Hz),
6.90-7.30 (3H, m), 7.58 (1H, 1/2 ABq, 16 Hz).
EXAMPLE 68
Preparation of cycloartenyl-4-acetoxy-3-ethoxycinnamate
The title compound was prepared according to following the procedure of Example 65 where 4-acetoxy3-ethoxycinnamic acid (27.0 g, 0.108 mole) and cycloartenol (25.2 g, 0.059 mole) was used in place of 4-acetoxy-3-methoxycinnamic acid (26.5 g) and cyclobranol (33 g), respectively; the yield was 32.6 g (83%). m.p. 165°-166° C.
Specific rotation [α] D 24 +40.5° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 43 H 62 O 5 (M.W. 658.93): C 78.38; H 9.48. Found: C 78.27; H 9.53.
EXAMPLE 69
Preparation of cycloartenyl-3-ethoxy-4-hydroxycinnamate
Cycloartenyl-4-acetoxy-3-ethoxycinnamate (30.3 g, 0.046 mole) prepared according to procedure of Example 68 was dissolved in tetrahydrofuran (300 ml), followed by addition of 25% aqueous ammonia (60 ml). The mixture was stirred at 50° C. for 2 hours. After the reaction was complete, the mixture was evaporated to dryness under reduced pressure, and the residual crystals were recrystallized from acetone-water (2:1, V/V), giving cycloartenyl-3-ethoxy-4-hydroxycinnamate (19.7 g), in a 69% yield. m.p. 134°-135° C.
Specific rotation [α] D 24 +40.8° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 41 H 60 O 4 (M.w. 616.89): C 79.82; H 9.80. Found: C 79.89; H 9.73.
EXAMPLE 70
Preparation of cyclobranyl-4-acetoxy-3-ethoxycinnamate
The title compound was prepared according to following the procedure of Example 68 where cyclobranol (33.1 g, 0.075 mole) was used as starting material; the yield was 43.1 g (85%). m.p. 153°-154° C.
Specific rotation [α] D 24 +37.6° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 44 H 64 O 5 (M.W. 672.95): C 78.53; H 9.59. Found: C 78.48; H 9.64.
EXAMPLE 71
Preparation of cyclobranyl-3-ethoxy-4-hydroxycinnamate
The title compound was prepared according to following the procedure of Example 69 where cyclobranyl-4-acetoxy-3-ethoxycinnamate (30.9 g, 0.046 mole) obtained by the procedure of Example 70 was used; the yield was 22.8 g (78%). m.p. 181°-182° C.
Specific rotation [α] D 24 +38.0° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 42 H 62 O 4 (M.W. 630.92): C 79.95; H 9.91. Found: C 79.91; H 9.98.
EXAMPLE 72
Preparation of 24-methylenecycloartanyl-4-acetoxy-3-ethoxycinnamate
The title compound was prepared according to following the procedure of Example 68 where 24-methylenecycloartanol (33.1 g, 0.075 mole) was used as starting material; the yield was 42.7 g (84%). m.p. 184°-185° C.
Specific rotation [α] D 24 +39.9° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 44 H 64 O 5 (M.W. 672.95): C 78.53; H 9.59. Found: C 78.59; H 9.52.
EXAMPLE 73
Preparation of 24-methylenecycloartanyl-3-ethoxy-4-hydroxycinnamate
The title compound was prepared according to following the procedure of Example 69 where 24-methylenecycloartanyl-4-acetoxy-3-ethoxycinnamate (30.9 g, 0.046 mole) obtained according to the procedure of Example 72 was used; the yield was 23.4 g (80%). m.p. 146°-147° C.
Specific rotation [α] D 24 +40.1° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 42 H 62 O 4 (M.W. 630.92): C 79.95; H 9.91. Found: C 79.89; H 9.95.
EXAMPLE 74
Preparation of cycloartenyl-4-hydroxy-3-propoxycinnamate
The title compound was prepared according to following the procedure of Example 69 cycloartenyl-4-acetoxy-3-n-propoxycinnamate (31.0 g, 0.046 mole) obtained according to the procedure of Example 68; the yield was 20.5 g (70%). m.p. 144°-145° C.
Specific rotation [α] D 24 +40.2° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 42 H 62 O 4 (M.W. 630.92): C 79.95; H 9.91. Found: C 79.99; H 9.85.
EXAMPLE 75
Preparation of cyclobranyl-4-hydroxy-3-propoxycinnamate
The title compound was prepared according to following the procedure of Example 69 being used cyclobranyl-4-acetoxy-3-propoxycinnamate (31.6 g, 0.046 mole) obtained according to the procedure of Example 68; the yield was 22.8 g (76%). m.p. 187°-188° C.
Specific rotation [α] D 24 +37.4° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 43 H 64 O 4 (M.W. 644.94): C 80.07; H 10.00. Found: C 79.92; H 10.13.
EXAMPLE 76
Preparation of cycloartenyl-3,4-dimethoxycinnamate
Acetone (200 ml) and potassium carbonate (10.0 g) were added to cycloartenyl-4-hydroxy-3-methoxycinnamate (10.0 g, 0.017 mole) at 20° C. and the mixture was stirred. Thereto was added dimethyl sulfate (2.8 ml, 5 equivalents) and continued to stir at 50° C. for 3 hours. Then the potassium carbonate was separated by filtration, and the filtrate was evaporated under reduced pressure. The residue was dissolved in methylene chloride, and the methylene chloride layer washed with saturated aqueous solution of sodium bicarbonate. The aqueous layer was extracted with methylene chloride and the.combined extracts were dried, evaporated to dryness under reduced pressure, and the residue was recrystallized from methylene chloride-methanol (1:4, V/V), giving the title compound (9.6 g) in a 94% yield. m.p. 136°-137° C.
Specific rotation [α] D 23 +41.7° (C 1.03, CHCl 3 )
Analysis, Calcd. for C 41 H 60 O 4 (M.W. 616.89): C 79.82; H 9.80. Found: C 79.90; H 9.88.
EXAMPLE 77
Preparation of cycloartenyl-3-methoxy-4-propionyloxycinnamate
Pyridine (160 ml) was added to cycloartenyl-4-hydroxy-3-methoxycinnamate (40.0 g, 0.066 mole) and the mixture was stirred at 0° C. Thereto was added propionic anhydride (80 ml) dropwise and the solution was continued to stir at 20° C. for 1 hour, then allowed to stand at 5° C. for 48 hours. After the reaction was completed water (250 ml) was added to the solution to precipitate crystals of the title compound, which were then filtered and washed with water and methanol. The yield was 42.3 g (95%). m.p. 156-157° C.
Specific rotation [α] D 25 +40.2° (C 1.04, CHCl 3 )
Analysis, Calcd. for C 43 H 62 O 5 (M.W. 658.93): C 78.38; H 9.48. Found: C 78.45; H 9.42.
EXAMPLE 78
Preparation of cycloartenyl-3,4-dimethoxybenzoate
Toluene (10 ml), thionyl chloride (48 ml, 10 equivalents) and pyridine (1.0 ml) were added to 3,4-dimethoxybenzoic acid (11.8 g, 0.065 mole) at 0° C., and the mixture was stirred at 40° C. for 10 minutes. The reaction mixture was evaporated under reduced pressure, and to the residue were added cycloartenol (20.0 g, 0.043 mole) and pyridine (100 ml) at 0° C. The mixture was heated to 40° C. and stirred for 1 hour and furthermore continued to stir at 60° C. for 1 hour. The resulting mixture was evaporated under reduced pressure, and the residual crystals were dissolved in chloroform. The organic layer was washed with saturated aqueous solution of sodium bicarbonate, then aqueous layer was extracted with chloroform. The combined extracts were dried, and evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: toluene-methylene chloride, (2:1, V/V)), giving cycloartenyl-3,4-dimethoxybenzoate (25.9 g), in a 88% yield. m.p. 147°-147.5° C.
Specific rotation [α] D 26 +63.8° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 39 H 58 O 4 (M.W. 590.85): C 79.27; H 9.89. Found: C 79.34; H 9.82.
EXAMPLE 79
Preparation of cyclobranyl-3,4-dimethoxycinnamate
To 3,4-dimethoxycinnamic acid (16.53 g, 0.0794 mole) suspended in toluene (200 ml) was added thionyl chloride (11.5 ml, 2 equivalents) and the mixture was stirred at 100° C. for 2.5 hours. The resulting mixture was evaporated under reduced pressure, and the residue was suspended in a toluene (100 ml) and pyridine (50 ml). To the suspension was added cyclobranol (17.5 g, 0.0397 mole) and the mixture was stirred at 100° C. for 3 hours. The solution was evaporated under reduced pressure, and the residue was extracted with chloroform (300 ml). The extract was dried, concentrated in vacuo, and purified by silica gel column chromatography (solvent: toluene), giving cyclobranyl-3,4-dimethoxycinnamate (22.3 g), in a 93% yield. m.p. 168°-169° C.
Specific rotation [α] D 25 +38.5° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 42 H 62 O 4 (M.W. 630.92): C 79.95; H 9.91. Found: C 80.02; H 9.84.
EXAMPLE 80
Preparation of cyclobranyl-3,4-dimethoxybenzoate
To veratric acid (15.5 g, 0.085 mole) dissolved in toluene (150 ml) was added thionyl chloride (12.4 ml, 2 equivalents) and the mixture was stirred at 100° C. for 1.5 hours. The solution was evaporated under reduced pressure and the residue was dissolved in toluene (100 ml) and pyridine (50 ml). To the solution was added cyclobranol (25 g, 0.057 mole) and the mixture was stirred at 60° C. for 2 hours. The reaction mixture was evaporated to dryness under reduced pressure, and the residue was extracted with chloroform (300 ml). The extract was dried, concentrated in vacuo, and purified by silica gel column chromatography (solvent: toluene), giving cyclobranyl-3,4-dimethoxybenzoate (25.6 g), in a 76% yield. m.p. 158°-159° C.
Specific rotation [α] D 26 +59.2° (C 0.89, CHCl 3 )
Analysis, Calcd. for C 40 H 60 O 4 (M.W. 604.88): C 79.42; H 10.00. Found: C 79.34; H 10.12.
EXAMPLES 81-100
The esters of 24-methylenecycloartanol in Examples 81-100 were prepared according to following the corresponding procedures of the cyclobranol's mentioned above. In these procedures the same amounts (by mole) of 24-methylenecycloartanol, in place of cyclobranol, was used. Yields (%), melting points (°C.), and specific rotations (C1.00, CHCl 3 ) of these compounds are summarized in Table 25.
TABLE 25______________________________________ SpecificExample Original organic acid Yield M.P. rotationNo. of ester (%) (°C.) [α].sub.D.sup.24______________________________________81 3,4-Diacetoxycinnamic 62 143-145 +36.2° acid82 3,4-Dihydroxycinnamic 73 236-237 +42.5° acid83 p-Acetoxycinnamic acid 76 158-159 +42.0°84 p-Hydroxycinnamic acid 87 240-241 +43.5°85 4-Acetoxy-3-methoxy- 76 162-163 +58.2° benzoic acid86 4-Hydroxy-3-methoxy- 80 155-156 +60.2° benzoic acid87 3,4-Diacetoxybenzoic 62 153-154 +52.3° acid88 3,4-Dihydroxybenzoic 85 205-206 +61.4° acid89 p-Nitrobenzoic acid 89 229-230 +61.8°90 p-Aminobenzoic acid 72 174-175 +60.2°91 Nicotinic acid 86 173-174 +66.5°92 o-Hydroxybenzoic acid 69 161-16293 Linoleic acid 69 oily +38.1° matter94 p-Hydroxybenzoic acid 92 177-178 +64.4°95 m-Acetoxybenzoic acid 90 133-134 +60.1°96 m-Hydroxybenzoic acid 85 185-186 +64.2°97 o-Nitrobenzoic acid 89 190-191 +92.5°98 o-Aminobenzoic acid 67 196-197 +76.1°99 m-Nitrobenzoic acid 85 170-171 +60.8°100 m-Aminobenzoic acid 82 178-179 +62.0°______________________________________
EXAMPLE 100-1
Preparation of cycloartenyl-4-hydroxy-3-methoxycinnamate
Methanol (350 ml) was added to a solution or γ-oryzanol (1.0 kg, cycloartenol ester content 44%) in acetone (5.0 1) at an elevated temperature. Then the mixture was cooled and allowed to stand overnight at 20° C. The thus separated crystals were filtered, giving γ-oryzanol (680 g) in which the content of cycloartenyl ester was 60%. Similar recrystallization of this γ-oryzanol by using acetone (3.4 1) and methanol (68 ml) gave γ-oryzanol (450 g) of cycloartenyl ester content 75%. Further repeated recrystallizations the first time from acetone (2.25 1), the second ethyl acetate (1.25 1), the third acetone (1.29 1), and the fourth acetone (960 ml), respectively, ylelded 250 g (88% purity on cycloartenyl ester), 184 g (92% purity), 120 g (97% purity) and 91 g (98% purity) of γ-oryzanol, and the final recrystallization from ethyl acetate (640 ml) gave cycloartenyl-4-hydroxy-3-methoxycinnamate (53 g), in a 5.3% yield. m.p. 153°-153.5° C.
Specific rotation [α] D 21 .5 +41.2° (C 0.99, CHCl 3 )
Analysis, Calcd. for C 40 H 58 O 4 (M.W. 602.86): C 79.69; H 9.70. Found: C 79.73; H 9.62.
IRν, KBr (cm -1 ): 3400, 2910, 1700, 1672, 1599, 1510, 1270, 1155.
PMR (CDCl 3 )δ: 0.38 (1H, 1/2 ABq, 4.2 Hz), 0.58 (1H, 1/2 ABq, 4.2 Hz), 0.70-2.40 (27H, m), 0.89 (6H, s), 0.96 (6H, s), 1.61 (3H, bs), 1.68 (3H, bs), 3.91 (3H, s), 4.50-4.90 (1H, m), 4.80-5.30 (1H, m), 5.87 (1H, s), 6.28 (1H, 1/2 ABq, 15 Hz), 6.76-7.10 (2H, m), 7.00 (1H, s), 7.55 (1H, 1/2 ABq, 15 Hz).
EXAMPLE 100-2
Preparation of cyclobranyl-4-hydroxy-3-methoxycinnamate
Cyclobranyl-4-actoxy-3-methoxycinnamate (44.9 g, 0.068 mole) prepared according to the procedure of Example 65 was dissolved in dioxane (900 ml), and to the solution was added 25% aqueous ammonia (90 ml) dropwise. After the mixture was stirred at 50° C. for 2 hours, the solution was evaporated to dryness under reduced pressure. The residual crystals were washed with ethanol, giving cyclobranyl-4-hydroxy-3-methoxycinnamate (40.0 g), in a 95.2% yield. m.p. 191°-192° C.
Specific rotation [α] D 23 .5 +38.5° (C 0.99, CHCl 3 )
Analysis, Calcd. for C 41 H 60 O 4 (M.W. 616.89): C 79.82; H 9.80. Found: C 79.77; H 9.88.
IRν, KBr (cm -1 ): 3500, 2920, 2850, 1690, 1600, 1510, 1265, 1155.
PMR (CDCl 3 )δ: 0.36 (1H, 1/2 ABq, 4.8 Hz), 0.60 (1H, 1/2 ABq, 4.8 Hz), 0.68-2.20 (27H, m), 0.89 (6H, s), 0.96 (6H, s), 1.62 (9H, s), 3.90 (3H, s), 4.50-4.90 (1H, m), 5.97 (1H, b), 6.27 (1H, 1/2 ABq, 15.6 Hz), 6.75-7.20 (3H, m), 7.9 (1H, 1/2 ABq, 15.6 Hz).
EXAMPLE 100-3
Preparation of 24-methylenecycloartanyl-4-hydroxy-3-methoxycinnamate
Commercial available γ-oryzanol (100 g, 24-methylenecycloartanol content 45%) was acetylated with acetic anhydride in pyridine. This acetylated γ-oryzanol was recrystallized repeatedly from chloroform-ethyl acetate-ethanol (4:3:2, V/V), giving acetyl ferulate (18 g) of 24-methylenecycloartanol content 95%. This acetyl ferulate was completely saponified in the solution of 2N NaOH-ethanol, then the obtained alcohol was converted into the benzoate. This benzoate was recrystallized repeatedly, and completely saponified to give 24-methylenecycloartanol (5 g). A portion (2 g, 0.0045 mole) thereof wa converted into 24-methylenecycloartanol-4-acetoxy-3-methoxycinnamate according to following the procedure of Example 65. This ester was then deacetylated according to following the procedure of Example 100-2, giving 24-methylenecycloartanol-4-hydroxy-3-methoxycinnamate (2.58 g), in a 90% yield. m.p. 166°-167° C.
Specific rotation [α] D 24 +40.6° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 41 H 60 O 4 .1/3C 2 H 5 OH (M.W. 632.25): C 79.15; H 9.88. Found: C 79.11; H 9.94.
IRν, KBr (cm -1 ): 3400 2920, 2850, 1688, 1630, 1600, 1510, 1463, 1425, 1265, 1158
PMR (CDCl 3 )δ: 0.39 (1H, 1/2 ABq, 4.2 Hz), 0.59 (1H, 1/2 ABq, 4.2 Hz), 0.60-2.50 (28H, m), 0.82 (6H, s), 0.95 (6H, s), 1.02 (6H, d, 7.2 Hz), 3.91 (3H, s), 4.70 (2H, bs), 4.50-4.90 (1H, m), 5.95 (1H, s), 6.70-7.30 (3H, m), 6.32 (1H, 1/2 ABq, 16 Hz), 7.56 (1H, 1/2 ABq, 16 Hz).
EXAMPLE 101
Preparation of cycloartenyl ester of p-nitro cinnamic acid
Thionyl chloride (112 ml, 4 equivalents) and dimethylformamide (1 ml) were added to p-nitrocinnamic acid (73.0 g, 0.378 mole) and the mixture was stirred at 60° C. for 2 hours. Then the resulting mixture was concentrated under reduced pressure. Dioxane (250 ml), pyridine (250 ml), and then cycloartenyl (125 g, 0.293 mole) were added to the residue. After 2 hours' stirring at 60° C., the solvents were removed by distillation under reduced pressure, and the residue was extracted with chloroform. The extracts were washed successively with water and saturated aqueous NaHCO 3 , then dried, and concentrated under reduced pressure. The residual crystals were recrystallized from methylene chloride-methanol (1:5,v/v),giving cycloartenyl ester of p-nitrocinnamic acid (158.0 g), in a 89.6% yield. m.p. 199°-200° C.
Specific rotation [α] D 26 +43.8° (C1.00, CHCl 3 ).
Analysis, Calcd. for C 39 H 55 NO 4 (M.W.601.83): C,77.83; H,9.2l; N,2.33. Found: C,77.89; H,9.16; N,2.28.
IRν, KBr(cm -1 ): 2930, 1708, 1640, 1600, 1520, 1345, 1205, 1175.
PMR(CDCl 3 )δ: 0.38(1H, 1/2 ABq, 4.2 Hz), 0.6l(1H, 1/2ABq, 4.2 Hz), 0.52-2.36(27H, m), 0.91(6H, s), 0.98(6H, s), 1.61(3H, s), 1.63(3H, s), 4.83-4.90(1H, m), 4.90-5.31(1H, m), 6.55(1H, 1/2 ABq, 16.2 Hz), 7.65(2H, ABq, 8.7 Hz), 7.67 (1H, 1/2ABq, 16.2 Hz), 8.24(2H, ABq, 8.7 Hz).
EXAMPLE 102
Preparation of cycloartenyl ester of p-amino-cinnamic acid
Cycloartenyl ester of p-nitro cinnamic acid (160.0 g, 0.266 mole) prepared according to the procedure of Example 101 was suspended in a mixture of acetic acid (1.5 l) and dioxane (1.5 l). To the suspension were added 6N-HCl-dioxane (95 ml) and zinc powder (80 g) and the mixture was stirred at 40° C. for 3 hours. After the reaction, zinc powder was removed by filtration. The filtrate was concentrated under reduced pressure, and the residue was extracted with chloroform. The extracts were washed successively with water and saturated aqueous NaHCO3, then dried, and concentrated under reduced pressure. The residual crystals were recrystallized from chloroform-ethanol (1:5, v/v), giving cycloartenyl ester of p-aminocinnamic acid (140.0 g), in a 92.0% yield. m.p. 185°-187° C.
Specific rotation [α] D 26 +42.3(C 1.00, CHCl 3 )
Analysis, Calcd. for C 39 H 57 NO 2 (M.W.571.85): C,81.91; H,10.05; N,2.45. Found: C,81.87; H, 10.03; N,2.53.
IRν, KBr(cm -1 ): 3450, 3350, 2920, 1695, 1620, 1600, 1515, 1440, 1205, 1165.
PMR(CDCl 3 )δ: 0.38(1H, 1/2ABq, 4.2 Hz), 0.61(1H, 1/2ABq, 4.2 Hz), 0.72-2.80(27H, m), 0.91(6H, s), 0.96(6H s), 160(3H, s), 168(3H, s), 3.92(2H, bs), 4.48-4.88(1H, m), 4.88-5.32(1H, m), 6.22(1H, 1/2ABq, 15.8 Hz), 6.63(2H, ABq, 8.4 Hz), 7.35(2H, ABq, 8.4 Hz), 7.56(1H, 1/2ABq, 15.8 Hz).
EXAMPLE 103
Preparation of cyclobranyl ester of p-nitrocinnamic acid
Thionyl chloride (60 ml, 2 equivalents),dioxane (300 ml), and dimethylformamide (1 ml) were added to p-nitrocinnamic acid (75 g, 0.388 mole), and the mixture was stirred at 60° C. for 2 hours. Then the resulting mixture was concentrated under reduced pressure. To the residue were added dioxane (300 ml), pyridine (200 ml) and then cylobranol (130 g, 0.295 mole). After 2 hours' stirring at 60° C., the solvents were removed by distillation under reduced pressure, and the residue was extracted with chloroform. The extracts were washed successively with water and saturated aqueous NaHCO 3 , then dried, and concentrated in vacuo. The residue was recrystallized from chloroform-ethanol (1:3, v/v), giving cyclobranyl ester of p-nitrocinnamic acid (168.4 g), in a 92.7% yield. m.p. 231°-232° C.
Specific rotation [α] D 26 +40.6°(C 1.00, CHCl 3 )
Analysis Calcd. for C 40 H 57 NO 4 (M.W.615.86): C,78.01; H,9.33; N,2.27. Found: C,78.10; H,9.24; N,2.36.
IRν, KBr(cm -1 ): 2930, 1710, 1635, 1600, 1520, 1345, 1300, 1175.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.8 Hz), 0.61(1H, 1/2ABq, 4.8 Hz), 0.68-2.20(27H, m), 0.91(6H, s), 0.97(6H, s), 1.62(9H, s), 4.48-4.92(1H, m), 6.55(1H, 1/2ABq, 15.6 Hz), 7.67(2H, ABq, 8.4 Hz), 7.69(1H, 1/2ABq, 15.6 Hz), 8.22(2H, ABq, 8.4 Hz).
EXAMPLE 104
Preparation of cyclobranyl ester of p-aminocinnamic acid
Cyclobranyl ester of p-nitrocinnamic acid (165.0 g, 0.268 mole) prepared according to the procedure of Example 103 was suspended in a mixture of acetic acid (1.5 l) and tetrahydrofuran (2 l). To the suspension were added 6N-HCl-dioxane (125 ml) and zinc powder (165 g) and the mixture was stirred at 20° C. for 2 hours. Then the reaction mixture was filtered to remove zinc powder. The filtrate was concentrated under reduced pressure, and the residue was extracted with chloroform. The extracts were washed successively with water and saturated aqueous NaHCO3, then dried, and concentrated in vacuo. The residual crystals were recrystallized from chloroform-ethanol (1:3, v/v), giving cyclobranyl ester of p-aminocinnamic acid (119.2 g), in a 75.9% yield. m.p. 206°-207° C.
Specific rotation [α] D 26 +40.1°(C 1.00, CHCl 3 )
Analysis Calcd. for C 40 H 59 NO 2 (M.W.585.87): C,82.00; H,10.15; N,2.39. Found: C,81.92; H,10.14; N,2.43.
IRν, KBr(cm -1 ): 3450, 3350, 2930, 1690, 1620, 1595, 1515, 1440, 1300, 1270, 1170.
PMR(CDCl 3 )δ: 0.35(1H, 1/2ABq, 4.8 Hz), 0.59(1H, 1/2ABq, 4.8 Hz), 0.68-2.36(27H, m), 0.90(6H, s), 0.96(6H, s), 1.62(9H, s), 3.76-4.08(2H, m), 4.44-4.87(1H, m), 6.22(1H, 1/2ABq, 15.6 Hz), 6.62(2H, ABq, 8.4 Hz), 7.34(2H, ABq, 8.4 Hz), 7.57(1H, 1/2ABq, 15.6 Hz).
EXAMPLE 105
Preparation of 24-methylenecycloartanyl ester of p-nitrocinnamic acid
The title compound was prepared according to following the procedure of Example 103 where 24-methylenecycloartanol (130 g, 0.295 mole) was used as a starting material in place of cyclobranol. The yield was 164.8 g (90.7%). m.p. 223°-224° C.
Specific rotation [α] D 26 +43.1°(C 1.00, CHCl 3 )
Analysis Calcd. for C 40 H 57 NO 4 (M.W.615.86): C,78.01; H,9.33; N,2.27. Found: C,78.08; H,9.25; N,2.34.
EXAMPLE 106
Preparation of 24-methylenecycloartanyl ester of p-aminocinnamic acid
The title compound was prepared according to following the procedure of Example 104 where 24-methylenecycloartanyl ester of p-nitrocinnamic acid (163.5 g, 0.265 mole) as a starting material. The yield was 118.3 g (76.2%). m.p. 201°-202° C.
Specific rotation [α] D 26 +42.0°(C 1.00, CHCl 3 )
Analysis, Calcd. for C 40 H 59 NO 2 (M.W 585.87): C,82.00; H,10.15; N2.39. Found: C,81.95; H, 10.19; N2.42.
EXAMPLE 107
Preparation of cycloartenyl ester of m-nitrocinnamic acid
The title compound was prepared according to following the procedure of Example 101 but m-nitrocinnamic acid (73.0 g, 0.378 mole) was used as a starting material in place of p-nitrocinnamic acid. The yield was 156.8 g (88.9%). m.p. 181°-182° C.
Specific rotation [α] D 26 +42.4°(C 1.00, CHCl 3 )
Analysis, Calcd. for C 39 H 55 NO 4 (M.W.601.83): C,77.83 H,9.21; N,2.33. Found: C,77.76; H,9.26; N,2.39.
EXAMPLE 108
Preparation of cycloartenyl ester of m-aminocinnamic acid
The title compound was prepared according to following the procedure of Example 102 but cycloartenyl ester of m-nitrocinnamic acid (160.0 g, 0.266 mole) obtained according to the procedure of Example 107 was used in place of cycloartenyl ester. The yield was 135.8 g (89.2%). m.p. 189°-190° C.
Specific rotation [α] D 26 +43.1°(C 1.00, CHCl 3 )
Analysis Calcd. for C 39 H 57 NO 2 (M.W.571.85): C,81.91; H,10.05; N,2.45. Found: C,81.87; H,10.08; N,2.53.
EXAMPLE 109
Preparation of cyclobranyl ester of
m-nitrocinnamic acid
The title compound was prepared according to following the procedure of Example 103 but m-nitrocinnamic acid (75 g, 0.388 mole) was used as a starting material. The yield was 167.6 g (92.2%). m.p.204°-205° C.
Specific rotation [α] D 26 +40.5°(C 1.00, CHCl 3 )
Analysis Calcd. for C 40 H 57 NO 4 (M.W.615.86): C,78.01; H,9.33; N,2.27. Found: C,77.95; H,9.38; N,2.32.
EXAMPLE 110
Preparation of Cyclobranyl ester of m-aminocinnamic acid
The title compound was prepared according to following the procedure of Example 104 but cyclobranyl ester of m-nitrocinnamic acid (163.2 g, 0.265 mole) obtained according to the procedure of Example 109, was used as a starting material. The yield was 117.4 g (75.6%). m.p.211°-212° C.
Specific rotation [α] D 26 +41.2°(C 1.00, CHCl 3 )
Analysis Calcd. for C 40 H 59 NO 2 (M.W.585.87): C,82.00; H,10.15; N,2.39. Found: C,82.07; H,10.08; N,2.43.
EXAMPLE 111
Preparation of 24-methylene cycloartanyl ester of m-nitrocinnamic acid
The title compound was prepared according to following the procedure of Example 103 but m-nitrocinnamic acid (75 g, 0.388 mole) and 24-methylenecycloartanol (130 g, 0.295 mole) was used in place of p-nitrocinnamic acid and cyclobranol, respectively. The yield was 167.2 g (92.0%). m.p.193°-194° C.
Specific rotation [α] D 26 +42.3°(C 1.00, CHCl 3 )
Analysis Calcd. for C 40 H 57 NO 4 (M.W.615.86): C,78.01; H,9.33; N,2.27. Found: C,78.05; H,9.27; N,2.34.
EXAMPLE 112
Preparation of 24-methylenecycloartanyl ester of m-aminocinnamic acid
The title compound was prepared according to following the procedure of Example 104 but 24-methylenecycloartanyl ester of m-nitrocinnamic acid (160.4 g, 0.260 mole) obtained according to the procedure of Example 111 was used as a starting material. The yield was 114.8 g (75.3%). m.p. 197°-198° C.
Specific rotation [α] D 26 +42.7°(C 1.00, CHCl 3 )
Analysis Calcd. for C 40 H 59 NO 2 (M W.585.87): C,82.00; H,l10.15; N,2.39. Found: C,81.93; H,10.22;
N,2.44.
EXAMPLE 113
Preparation of cycloartenyl ester of 3-methoxy-4-propionyloxy-α-methyl cinnamic acid
To 3-Methoxy-4-propionyloxy-α-methylcinnamic acid (72.0 g, 0.272 mole) were added thionyl chloride (40.0 ml, 2 equivalents), toluene (400 ml) and dimethylformamide (0.5 ml) and the mixture was stirred at 60° C. for 1.5 hours. After concentration of the mixture under reduced pressure, thereto dioxane (100 ml) was added and the whole was stirred at 0° C. To the mixture was added cycloartenol (80.0 g, 0.187 mole) dissolved in pyridine (300 ml) and the whole was stirred at 60° C. for 3 hours. The reaction mixture was evaporated under reduced pressure and the residue was dissolved in chloroform (800 ml). The solution was washed with saturated aqueous NaHCO 3 , and the aqueous layer was extracted with chloroform (500 ml×2). The combined chloroform layer was dried and evaporated under reduced pressure, and the residue was purified by silica gel column chromatography [solvent hexane-methylene chloride, (5:1, v/v)] giving cycloartanyl ester of 3-methoxy-4-propionyloxy-α-methylcinnamic acid (110 g), in a 87.1% yield. m.p. 130°-131° C.
Specific rotation [α] D 19 +41.4°(C 1.00, CHCl 3 )
Analysis Calcd. for C 44 H 64 O 5 (M.W.672.95): C,78.53; H,9.59. Found: C,78.59; H,9.52.
IRν, KBr(cm -1 ): 2920, 2850, 1765, 1710, 1630, 1600, 1510, 1240, 1140, 1110.
PMR(CDCl 3 )δ: 0.39(1H, 1/2ABq, 4.2 Hz), 0.60(1H, 1/2ABq, 4.2 Hz), 0.60-2.20(27H, m), 0.90(6H, s), 0.98(6H, s), 1.27(3H, t, 7.2 Hz), 1.58(3H, bs), 1.68(3H, bs), 2.12(3H, d, 1.2 Hz), 2.62(2H, q, 7.2 Hz), 3.80(3H, s), 4.50-5.30(2H, m), 6.80-7.70(4H, m).
EXAMPLE 114
Preparation of cycloartenyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid (another name: cycloartenyl ester of α-methylferulic acid)
To cycloartenyl ester of 3-methoxy-4-propionyloxy-α-methyl-cinnamic acid (84.0 g, 0.125 mole) prepared according to the procedure of Example 113 dissolved in dioxane (1000 ml) was added 25% aqueous ammonia (200 ml) and the solution was stirred at 50° C. for 2 hours. Then, the reaction mixture was concentrated under reduced pressure to remove the solvent, and the residue was dissolved in chloroform. The chloroform solution was washed with saturated brine (500 ml), and the aqueous layer were extracted with chloroform (300 ml×2). The combined chloroform layer was dried, concentrated under reduced pressure, and the residue was recrystallized from methylene chloride-methanol (1:4, v/v), giving cycloartenyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid (73.0 g), in a yield 94.8%. m.p.143°-144° C.
Specific rotation [α] D 19 +44.1°(C 1.00, CHCl 3 )
Analysis Calcd. for C 41 H 60 O 4 (M.W.616.93): C,79.82; H,9.80. Found: C,79.88; H,9.81.
IRν, KBr(cm -1 ): 3400, 2900, 2850, 1695, 1690, 1625, 1600, 1510, 1250, 1110.
PMR(CDCl 3 )δ: 0.38(1H, 1/2ABq, 4.2 Hz), 0.59(1H, 1/2ABq, 4.2 Hz), 0.60-2.30(27H, m), 0.88(6H, s), 0.97 (6H, s), 1.60(3H, bs), 1.66(3H, bs), 2.12(3H, d, 1.2 Hz), 3.88(3H, s), 4.50-5.30(2H, m), 5.80(1H, bs), 6.70-7.70(4H, m).
EXAMPLE 115
Preparation of cyclobranyl ester of 3-methoxy-4-propionyloxy-α-methylcinnamic acid
To 3-Methoxy-4-propionyloxy-α-methylcinnamic acid (15.59 g, 0.059 mole) suspended in toluene (50 ml) was added thionyl chloride (20 ml, 4.6 equivalents) and dimethyl formamide (5 drops) and the mixture was stirred at 60° C. for 2 hours. Then the solvent was removed by distillation under reduced pressure. The residue was suspended in toluene (150 ml) and anhydrous pyridine (30 ml), and to the suspension was added cyclobranol (20 g, 0.045 mole). The mixture was stirred at 60° C. for 2 hours, then concentrated under reduced pressure. The residue was extracted with chloroform (300 ml), and the chloroform solution was washed, dried, and evaporated to dryness under reduced pressure. The crystalline residue was washed with ethanol (50 ml), and recrystallized from acetone-water (19:1, v/v), giving cyclobranyl ester of 3-methoxy-4-propionyloxy-α-methylcinnamic acid (24.69 g), in a 79.2% yield. m.p.146°-147° C.
Specific rotation [α] D 19 +39.2°(C 1.00, CHCl 3 )
Analysis Calcd. for C 45 H 66 O 5 (M.W.686.98): C,78.67; H,9.68. Found: C,78.75; H9.62.
IRν, KBr(cm -1 ): 3400, 2590, 2850, 1760, 1710, 1630, 1600, 1240, 1150, 1120.
PMR(CDCl 3 )δ: 0.37(1H, 1/2ABq, 4.8 Hz), 0.62(1H, 1/2ABq, 4.8 Hz), 0.70-2.22(27H, m), 0.92(6H, s), 0.99(6H, s), 1.29(3H, t, 7.2 Hz), 1.64(9H, s), 2.14(3H, d, 1.2 Hz), 2.63(2H, q, 7.2 Hz), 3.84(3H, s), 4.48-4.88(1H, m), 6.80-7.08(3H, m), 7.59(1H, q, 1.2 Hz).
EXAMPLE 116
Preparation of cyclobranyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid
Cyclobranyl ester of 3-methoxy-4-propionyloxy-α-methyl cinnamic acid (24.69 g, 0.036 mole) obtained according to the procedure of Example 115 was dissolved in dioxane (400 ml) and to the solution was added 25% aqueous ammonia dropwise. The mixture was stirred at 50° C. for 2 hours, then the solvent was removed by distillation under reduced pressure. The crystalline residue was washed with ethanol, and recrystallized from acetone-water (19:1, v/v), giving cyclobranyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid (21.72 g)in a 95.8% yield. m.p. 185°-186° C.
Specific rotation [α] D 20 +43.7°(C 1.00, CHCL 3 )
Analysis Calcd. for C 42 H 62 O 4 (M.W.630.92): C,79.95; H,9.91. Found: C,79.90; H,9.98.
IVν, KBr(cm -1 ): 3380, 2920, 2850, 1693, 1600, 1510, 1285, 1250, 1120.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.8 Hz), 0.61(1H, 1/2ABq, 4.8 Hz), 0.76-2.30(27H, m), 0.91(6H, s), 0.99(6H, s), 1.63(9H, s), 2.14(3H, d, 1.2 Hz), 3.90(3H, s), 4.48-4.84(1H, m), 5.84(1H, bs), 6.80-6.98(3H, m), 7.55(1H, q, 1.2 Hz).
EXAMPLE 117
Preparation of 24-methylenecycloartanyl ester of 3-methoxy-4-propionyloxy-α-methylcinnamic acid
To 3-methoxy-4-propionyloxy-α-methylcinnamic acid (0.8 g, 0.003 mole) suspended in toluene (2 ml) was added thionyl chloride (0.5 ml, 2.2 equivalent) and dimethylformamide (2 drops), and the mixture was stirred at 60° C. for 2 hours. Then the solvent was removed by distillation under reduced pressure. The residue was suspended in toluene (2 ml) and anhydrous pyridine (1 ml), and to the suspension was added 24-methylene cycloartanyl (lg, 0.0023 mole). The mixture was stirred at 60° C. for 2 hours, then the solvents wer removed by distillation under reduced pressure. The residue was extracted with chloroform (20 ml) and the chloroform extract was washed with sodium bicarbonate, dried, and evaporated under reduced pressure. The crystalline residue was washed with ethanol (5 ml), and recrystallized from acetonemethanol (1:1, v/v), giving 24-methylenecycloartanyl ester of 3-methoxy-4-propionyloxy-α-methylcinnamic acid (1.35 g), in a 86.6% yield. m.p. 134°-135° C.
Specific rotation [α] D 19 +41.2°(C 1.00, CHCl 3 )
Analysis Calcd. for C 45 H 66 O 5 (M.W.686.98): C,78.67; H,9.68. Found: C,78.75; H,9.62.
IRν, KBr(cm -1 ): 3400, 2920, 2850, 1760, 1700, 1240, 1115.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.2 Hz), 0.61(1H, 1/2ABq, 4.2 Hz), 0.70-2.22(34H, m), 0.88(6H, s), 0.96(6H, s), 1.26(3H, t, 7.2 Hz), 2.11(3H, d, 1.2 Hz), 2.60(2H, q, 7.2 Hz), 3.80(3H, s), 4.44-4.86(1H, m), 4.86-5.26(2H, m), 6.76-7.08 (3H, m), 7.55(1H, q, 1.2 Hz).
EXAMPLE 118
Preparation of 24-methylenecycloartanyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid
24-Methylenecycloartanyl ester of 3-methoxy-4-propionyloxy-α-methylcinnamic acid (1.35 g, 0.002 mole) obtained according to the procedure of Example 117 was dissolved in dioxane (20 ml), and to the solution was added 25% aqueous ammonia (2 ml) dropwise. The mixture was stirred at 50° C. for 2 hours, then the solvents were removed by distillation under reduced pressure. The crystalline residue was washed with ethanol, and recrystallized from ethanol, giving 24-methylenecycloartanyl-ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid (1.02 g), in a 82.2% yield. m.p. 144°-145° C.
Specific rotation [α] D 20 +44.8°(1.00, CHCl 3 )
Analysis Calcd. for C 43 H 62 O 4 (M.W.630.92): C,79.95; H,9.91. Found: C,79.99; H,9.84.
IRν, KBr(cm -1 ): 3400, 2900, 2850, 1690, 1600, 1510, 1250, 1110.
PMR(CDCl 3 )δ: 0.37(1H, 1/2ABq, 4.2 Hz), 0.61(1H, 1/2ABq, 4.2 Hz), 0.70-2.21(34H, m), 0.89(6H, s), 0.98 (6H, s), 2.14(3H, d, 1.2 Hz), 3.88(3H, s), 4.50-4.88(1H, m), 4.88-5.28(2H, m), 5.80(1H, bs), 6.82-7.10(3H, m), 7.59(1H, q, 1.2 Hz)
EXAMPLE 119
Preparation of cycloartenyl ester of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid
Thionyl chloride (15.0 ml, 3.3 equivalents) was added dropwise to a solution of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid (18.0 g, 0.062 mole) in benzene (40 ml) at 0° C., and the mixture was heated to 60° C. and allowed to stirr for 2 hours. Then the excess thionyl chloride and the solvent were removed by distillation under reduced pressure. Pyridine (10 ml) and dioxane (40 ml) were added to the residue. While cooling the mixture at 0° C., a solution of cycloartenol (17.5 g, 0.041 mole) in pyridine (30 ml) was added dropwise. This reaction mixture was allowed to stir overnight at 20° C. Then the solvents were removed by distillation under reduced pressure. The residue was extracted with chloroform (200 ml) and the extract was concentrated in vacuo. The residue was recrystallized from acetone-methanol (1:1, v/v), giving cycloartenyl ester of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid (22.4 g) in a 77.9% yield. m.p. 118.5°-119.5° C.
Specific rotation [α] D 20 +35.7°(C 1.00, CHCl 3 )
Analysis Calcd. for C 46 H 68 O 5 (M.W.701.00): C,78.81; H 9.78. Found: C,78.72; H 9.86.
IRν, KBr(cm -1 ): 3400, 2920, 2800, 1700, 1600, 1510, 1230, 1120.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.2 Hz), 0.52-2.26(29H, m), 0.61(1H, 1/2ABq, 4.2 Hz), 0.90(6H, s), 0.96 (6H, s), 1.04(3H, t, 7.2 Hz), 1.18(3H, t, 7.2 Hz), 1.60(3H, s), 1.66(3H, s), 2.26-2.82(4H, m), 3.79(3H, s), 4.50-4.88(1H, m), 4.88-5.28(1H, m), 6.70-7.12(3H, m), 7.48-7.68(1H, m).
EXAMPLE 120
Preparation of cycloartenyl ester of 4-hydroxy-3-methoxy-α-ethylcinnamic acid
Cycloartenyl ester of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid (22.0 g, 0.0314 mole) obtained according to the procedure of Example 119 was dissolved in dioxane (200 ml), and to the solution was added 25% aqueous ammonia (20 ml) dropwise. The mixture was heated at 50° C. for 5 hours. Then the solvent was removed by distillation under reduced pressure. The residue was extracted with chloroform (200 ml), and the extract was concentrated under in vacuo. The residue was recrystallized from acetone-methanol (1:1, v/v), giving cycloartenyl ester of 4-hydroxy-3-α-ethylcinnamic acid (17.2 g), in a 86.8% yield. m.p. 136°-137° C.
Specific rotation [α] D 20 +41.5°(C 1.00, CHCl 3 )
Analysis Calcd. for C 42 H 62 O 4 (M.W.630.92): C,79.95; H,9.96. Found: C,79.90; H,9.83.
IRν, KBr(cm -1 ): 3400, 2830, 1700, 1595, 1510, 1240, 1120.
PMR(CDCl 3 )δ: 0.35(1H, 1/2ABq, 4.2 Hz), 0.50-2.18(27H, m), 0.60(1H, 1/2ABq, 4.2 Hz), 0.89(6H, s), 0.95(6H, s), 1.19(3H, t, 7.2 Hz), 1.57(3H, s), 1.65(3H, s), 2.56(2H, bq, 7.2 Hz), 3.87(3H, s), 4.47-4.85(1H, m), 4.85-5.24(1H, m), 5.76(1H, bs), 6.96-7.09(3H, m), 7.24-7.64(1H, m).
EXAMPLE 121
Preparation of cyclobranyl ester of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid
Thionyl chloride (15.0 ml, 3.3 equivalents) was added dropwise to a solution of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid (18.0 g, 0.062 mole) in benzene (40 ml) at 0° C., and the mixture was heated at 60° C. for 2 hours. Then the excess thionyl chloride and the solvent were removed by distillation under reduced pressure. Pyridine (40 ml) and dioxane (40 ml) were added to the residue. While cooling the mixture at 0° C., cyclobranol (18.1 g, 0.041 mole) was added, then the mixture was warmed to 20° C. and allowed to stir overnight. The solvents were removed by distillation under reduced pressure and the residue was extracted with chloroform (200 ml). The extract was concentrated in vacuo, and the residue was recrystallized from acetone-ethanol (1:1, v/v), giving cyclobranyl ester of 4-butyryloxy-3-methoxy-α-ethyl-cinnamic acid (22.3 g), in a 76.0% yield. m.p. 138°-139° C.
Specific rotation [α] D 20 +33.7°(C 1.00, CHCl 3 )
Analysis Calcd. for C 47 H 70 O 5 (M.W.715.03): C,78.94; H,9.87. Found: C,78.89; H,9.88.
IRν, KBr(cm -1 ): 3400, 2920, 2850, 1760, 1710, 1625, 1510, 1230, 1120.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.8 Hz), 0.52-2.22(29H, m), 0.61(1H, 1/2ABq, 4.8 Hz), 0.92(6H, s), 0.97(6H, s), 1.03(3H, t, 7.2 Hz), 1.18(3H, t, 7.2 Hz), 1.60(9H, s), 2.22-2.82 (4H, m), 3.81(3H, s), 4.48-4.90(1H, m), 6.70-7.18(3H, m), 7.40-7.64(1H, m).
EXAMPLE 122
Preparation of cyclobranyl ester of 4-hydroxy-3-methoxy-α-ethylcinnamic acid
Cyclobranyl ester of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid (21.3 g, 0.0298 mole) obtained according to the procedure of Example 121 was dissolved in dioxane (200 ml), and to the solution was added 25% aqueous ammonia (20 ml) by dropwise. The mixture was heated to 50° C. and stirred for 5 hours. Then the solvent was removed by distillation under reduced pressure and the residue was extracted with chloroform (200 ml). The extract was concentrated in vacuo, and the residue was recrystallized from ethanol to give cyclobranyl ester of 4-hydroxy-3-methoxy-α-ethylcinnamic acid (17.1 g), in a 88.9% yield. m.p. 156°-157° C.
Specific rotation [α] D 20 +37.7°(C 1.00, CHCl 3 )
Analysis Calcd. for C 43 H 64 O 4 (M.W.644.94): C,80.07; H 10.00. Found: C,80.13; H 10.12.
IRν, KBr(cm -1 ): 3400, 2930, 1696, 1235, 1130.
PMR(CDCl 3 )δ: 0.38(1H, 1/2ABq, 4.8 Hz), 0.52-2.22(27H, m), 0.62(1H, 1/2ABq, 4.8 Hz), 0.91(6H, s), 0.97(6H, s), 1.21(3H, t, 7.2 Hz), 1.62(9H, s), 2.57(2H, bq, 7.2 Hz), 3.98(3H, s), 4.48-4.86(1H, m), 5.78(1H, bs), 6.70-7.00(3H, m), 7.53(1H, m).
EXAMPLE 123
Preparation of cycloartenyl ester of 4-propionyloxy-α-methylcinnamic acid
Thionyl chloride (18.1 ml, 3.3 equivalents) and dimethylformamide (0.5 ml) were added dropwise to a solution of 4-propionyloxy-α-methylcinnamic acid (17.6 g, 0.075 mole) in benzene (40 ml) at 0° C. The mixture was heated to 60° C. and allowed to stir for 2 hours. Then the excess thionyl chloride and the solvent were removed by distillation under reduced pressure. Dioxane (40 ml) and pyridine (10 ml) were added to the residue. While cooling the mixture at 0° C., a solution of cycloartenol (21.3 g, 0.050 mole) in pyridine (40 ml) was added dropwise. This reaction mixture was warmed to 20° C. and allowed to stir overnight. Then the solvents were removed by vacuum distillation, and the residue was extracted with chloroform (200 ml). The extract was concentrated under reduced pressure, and the residue was recrystallized from acetone-ethanol (1:2, v/v), giving cycloartenyl ester of 4-propionyloxy-α-methylcinnamic acid (27.0 g) in a 83.9 % yield. m.p. 87°-88° C.
Specific rotation [α] D 19 +45.9°(C 1.00, CHCl 3 )
Analysis Calcd. for C 43 H 62 O 4 (M.W.642.93): C,80.33; H 9.72. Found: C,80.31; H 9.79.
IRν, KBr(cm -1 ): 3400, 2920, 2850, 1760, 1700, 1260, 1215, 1115.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.2 Hz), 0.52-2.20(27H, m), 0.61(1H, 1/2ABq, 4.2 Hz), 0.89(6H, s), 0.97(6H, s), 1.25(3H, t, 7.2 Hz), 1.57(3H, s), 1.65(3H, s), 2.10(3H, d, 1.2 Hz), 2.58(2H, q, 7.2 Hz), 4.28-4.84 (1H, m), 4.92-5.24(1H, m), 6.92-7.09(2H, m), 7.11-7.50(2H, m), 7.50-7.70(1H, m).
EXAMPLE 124
Preparation of cycloartenyl ester of 4-hydroxy-α-methylcinnamic acid
Cycloartenyl ester of 4-propionyloxy-α-methylcinnamic acid (27.0 g, 0.042 mole) obtained by the procedure of Example 123 was dissolved in dioxane (200 ml), and to the solution was added 25% aqueous ammonia dropwise. The mixture was heated to 50° C. and allowed to stir for 2 hours. Then the solvent was removed by distillation under reduced pressure, and the residue was extracted with chloroform (200 ml). The extract was concentrated in vacuo, and the residue was recrystallized from ethanol, giving cycloartenyl ester of 4-hydroxy-α-methylcinnamic acid (20.5 g), in a 83.1% yield. m.p. 190°-191° C.
Specific rotation [α] D 19 +45.8°(C 1.00, CHCl 3 )
Analysis Calcd. for C 40 H 58 O 3 (M.W. 586.86): C,81.86; H 9.96. Found: C,81.77, H 9.99.
IRν, kBr(cm -1 ): 3400, 2992, 2985, 1700, 1675, 1600, 1510, 1260, 1200, 1170.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.2 Hz), 0.52-2.24(27H, m), 0.61(1H, 1/2ABq, 4.2 Hz), 0.90(6H, s), 0.98(6H, s), 1.61(3H, s), 1.64(3H, s), 2.13(3H, d, 1.2 Hz), 4.50-4.88(1H, m), 4.88-5.24(1H, m), 5.88-6.60 (1H, m), 6.68-7.12(2H, m), 7.12-7.50(1H, m), 7.50-7.68(1H, m).
EXAMPLE 125
Preparation of cyclobranyl ester of 4-propionyloxy-α-methylcinnamic acid
Thionyl chloride (18.1 ml, 3.3 equivalents) and dimethylformamide (0.5 ml) were added dropwise to a solution of 4-propionyloxy-α-methylcinnamic acid (17.6 g, 0.075 mole) in benzene (40 ml) at 0° C. The mixture was heated to 60° C. and continued to stir for 2 hours. Then the excess thionyl chloride and the solvent were removed by distillation under reduced pressure. Dioxane (20 ml) and pyridine (40 ml) were added to the residue. While cooling the mixture at 0° C., cyclobranol (22.0 g, 0.050 mole) was added, then the mixture was warmed to 20° C. and continued to stir overnight. Then, the solvents were removed by distillation in vacuo, and the residue was extracted with chloroform (200 ml). The extract was concentrated under reduced pressure, and the residue was recrystallized from acetone-methanol (1:1, v/v), giving cyclobranyl ester of 4-propionyloxy-α-methylcinnamic acid (26.3 g), in a 80.0% yield. m.p. 107°-108° C.
Specific rotation [α] D 19 +34.7°(C 1.00, CHCl 3 )
Analysis Calcd. for C 44 H 64 O 4 (M.W.656.95): C,80.44; H 9.82. Found: C,80.39; H 9.77.
IRν, KBr(cm -1 ): 3400, 2920, 2850, 1860, 1710, 1630, 1260, 1200, 1165, 1120
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.8 Hz), 0.61(1H, 1.2ABq, 4.8 Hz), 0.74-2.32(27H, m), 0.89(6H, s), 0.96 (6H, s), 1.26(3H, t, 7.2 Hz), 1.61(9H, s), 2.10 (3H, d, 1.2 Hz), 2.58(2H, q, 7.2 Hz), 4.46-4.86 (1H, m), 6.90-7.52(4H, m), 7.52-7.70(1H, m).
Example 126
Preparation of cyclobranyl ester of 4-hydroxy-α-methylcinnamic acid
Cyclobranyl ester of 4-propionyloxy-α-methylcinnamic acid (26.3 g, 0.040 mole) obtained according to the procedure of Example 125 was dissolved in dioxane (200 ml), and to the solution was added 25% aqueous ammonia dropwise. The mixture was heated to 50° C. and continued to stir for 2 hours. Then the solvent was removed by distillation under reduced pressure, and the residue was extracted with chloroform (200 ml). The extract was concentrated in vacuo, and the residue was recrystallized from acetone-methanol (1:1, v/v), giving cyclobranyl ester of 4-hydroxy-α-methylcinnamic acid (20.7 g), in a 83.1% yield. m.p. 203°-204° C.
Specific rotation [α] D 19 +46.0°(C1.00, CHCl 3 )
Analysis Calcd. for C 41 H 60 O 3 (M.W.600.89): C,81.95; H,10,07. Found: C 81.99, H 10.07.
IRν, KBr(cm -1 ): 3400, 2920, 2850, 1780, 1605, 1510, 1265, 1200, 1170, 1125.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.8 Hz), 0.61(1H, 1/2ABq, 4.8 Hz), 0.80-2.33(27H, m), 0.90(6H, s), 0.98 (6H, s), 1.60(9H, s), 2.12(3H, d, 1.2 Hz), 4.08-4.88(1H, m), 5.56-5.80(1H, m), 6.70-6.92 (2H, m), 7.12-7.44(2H, m), 7.58(1H, q, 1.2 Hz).
EXAMPLE 127
Preparation of 24-methylenecycloartanyl ester of 4-propionyloxy-α-methylcinnamic acid
The title compound was prepared according to following the procedure of Example 125 but 24-methylenecycloartanol was used in place of cyclobranol. The yield was 25.8 g (78.5%). m.p. 94°-95° C.
Specific rotation [α] D 19 +44.2°(C 1.00, CHCl 3 )
Analysis Calcd. for C 44 H 64 O 4 (M.W.656.95): C,80.44; H,9.82. Found: C,80.48; H 9.78.
EXAMPLE 128
Preparation of 24-metnylenecycloartanyl ester of 4-hydroxy-α-methylcinnamic acid 24-Methylenecycloartanyl ester of 4-propionyloxy-α-methylcinnamic acid (24.0 g, 0.036 mole) obtained according to the procedure of Example 127 was dissolved in dioxane (200 ml) and to the solution was added 25% aqueous ammonia dropwise. The mixture was heated to 50° C. and continued to stir for 2 hours. Then the solvent was removed by distillation under reduced pressure, and the residue was extracted with chloroform (200 ml). The extract was concentrated in vacuo and the residue was recrystallized from acetone-methanol (1:1,v/v), giving 24-methylenecycloartanyl ester of 4-hydroxy-α-methylcinnamic acid (19.4 g) in a 89.6% yield. m.p. 195°-196° C.
Specific rotation [α] D 19 +43.8°(C 1.00, CHCl 3 )
Analysis Calcd. for C 41 H 60 O 3 (M.W.600.89): C,81.95; H 10.07. Found: C,81.90; H 10.14.
Example 129 Preparation of cycloartenyl ester of 4-butyryloxy-α-ethylcinnamic acid
Thionyl chloride (4.8 ml, 5 equivalents) was added dropwise to a solution of 4-butyryloxy-α-ethylcinnamic acid (3.50 g, 0.0133 mole) in benzene (7 ml) at 0° C. The mixture was heated to 60° C. and continued to stir for 2 hours. Then the excess thionyl chloride and the solvent were removed by distillation under reduced pressure. After addition of pyridine (10 ml) to the residue, a solution of cycloartenol (2.85 g, 0.0067 mole) in pyridine (10 ml) was added to the mixture dropwise at 0° C. This mixture was warmed to 20° C. and continued to stir overnight. Then the solvent was removed by distillation under reduced pressure and the residue was extracted with chloroform (40 ml). The extract was concentrated in vacuo, and the residue was recrystallized from acetone-ethanol (1:1, v/v), giving cycloartenyl ester of 4-butyryloxy-α-ethylcinnamic acid (3.63 g) in a 80.7% in a yield. m.p. 88°-89° C.
Specific rotation [α] D 20 +41.2° (C 1.00, CHCl 3 )
Analysis Calcd. for C 45 H 66 O 4 (M W.670.98): C,80.55; H 9.92. Found: C,80.64; H,9.84.
IRν, KBr(cm -1 ): 3400, 2940, 2860, 1760, 1710, 1240, 1200, 1170, 1125.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.2 Hz), 0.52-2.22(29H, m), 0.61(1H, 1/2ABq, 4.2 Hz), 0.90(6H, s), 0.96 (6H, s), 1.03(3H, t, 7.2 Hz), 1.18(3H, t, 7.2 Hz), 1.58(3H, s), 1.66(3H, s), 2.22-2.80(4H, m), 4.42-4.88(1H, m), 4.88-5.24(1H, m), 6.89-7.18 (2H, m), 7.18-7.46(2H, m), 7.46-7.64(1H, m).
EXAMPLE 130
Preparation of cycloartenyl ester of 4-hydroxy-α-ethylcinnamic acid
Cycloartenyl ester of 4-butyryloxy-α-ethylcinnamic acid (2.00 g, 0.003 mole) obtained according to the procedure of Example 129 was dissolved in dioxane (20 ml), and to the solution was added 25% aqueous ammonia (2 ml) dropwise. Then the mixture was warmed to 50° C. and continued to stir for 5 hours. The solvent was removed by distillation under reduced pressure, and the residue was extracted with chloroform (20 ml). The extract was concentrated in vacuo, and the residue was recrystallized from acetone, giving cycloartenyl ester of 4-hydroxy-α-ethylcinnamic acid (1.68 g), in a 93.2 % yield. m.p. 162.5°-163° C.
Specific rotation [α] D 20 +46.1° (C 1.00, CHCl 3 )
Analysis Calcd. for C 41 H 60 O 3 (M.W.600.89): C,81.95; H,10.07. Found: C,81.88; H 10.12.
IRν, KBr(cm -1 ): 3300, 2920, 2800, 1760, 1710, 1625, 1500, 1280, 1240, 1200, 1165, 1120.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.2 Hz), 0.52-2.22(27H, m), 0.61(1H, 1/2ABq, 4.2 Hz), 0.90(6H, s), 0.96(6H, s), 1.19(3H, t, 7.2 Hz), 1.60(3H, s), 1.67(3H, s), 2.57(2H, bq, 7.2 Hz), 4.47-4.88(1H, m), 4.92-5.32(1H, m), 6.43-6.67(1H, m), 6.68-7.04(2H, m), 7.12-7.48(2H, m), 7.52-7.69(1H, m).
EXAMPLE 131
Preparation of cyclobranyl ester of 4-butyryloxy-α-ethylcinnamic acid
Thionyl chloride (7.3 ml, 5 equivalents) was added dropwise to a solution of 4-butyryloxy-α-ethylcinnamic acid (5.25 g, 0.02 mole) in benzene (10 ml) at 0° C. The mixture was heated to 60° C. and allowed to stir for 2 hours. Then the excess thionyl chloride and the solvent were removed by distillation under reduced pressure. After addition of pyridine (40 ml) to the residue, cyclobranol (4.41 g, 0.001 mole) was added while cooling the mixture at 0° C. The mixture was warmed to 20° C. and continued to stir overnight. Then the solvent was removed by distillation under reduced pressure, and the residue was extracted with chloroform (60 ml). The extract was concentrated in vacuo, and the residue was recrystallized from acetone-ethanol (1:1, v/v), giving cyclobranyl ester of 4-butyryloxy-α-ethylcinnamic acid (4.80 g), in a 70.1 % yield. m.p. 117.5°-118° C.
Specific rotation [α] D 20 +38.6° (C 1.00, CHCl 3 )
Analysis Calcd. for C 46 H 68 O 4 (M.W.685.00): C,80.65; H,10.01. Found: C,80.59; H 10.06.
IRν, KBr(cm -1 ): 3400, 2900, 2850, 1770, 1710, 1625, 1510, 1230, 1120.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.8 Hz), 0.52-2.24(29H, m), 0.61(1H, 1/2ABq, 4.8 Hz), 0.90(6H, s), 0.96(6H, s), 1.03(3H, t, 7.2 Hz), 1.18(3H, t, 7.2 Hz), 1.59 (9H, s), 2.24-2.82(4H, m), 4.48-4.84(1H, m), 6.90-7.18(2H, m), 7.18-7.48(2H, m), 7.48-7.68(1H, m).
EXAMPLES 132
Preparation of cyclobranyl ester of 4-hydroxy-α-ethylcinnamic acid
Cyclobranyl ester of 4-butyryloxy-α-ethylcinnamic acid (4.11 g, 0.0060 mole) obtained according to the procedure of Example 131 was dissolved in dioxane (30 ml), and to the solution was added 25% aqueous ammonia (3 ml) dropwise. The mixture was heated to 50° C. and allowed to stir for 5 hours. Then, the solvent was removed by distillation under reduced pressure, and the residue was extracted with chloroform (40 ml). The 5 extract was concentrated in vacuo, and the residue was recrystallized from acetone, giving cyclobranyl ester of 4-hydroxy-α-ethylcinnamic acid (3.39 g), in a 91.9% yield. m.p. 202°-203° C.
Specific rotation [α] D 20 +44.0° (C 1.00, CHCl 3 )
Analysis Calcd. for C 42 H 62 O 3 (M.W.614.92): C,82.03; H,10.16. Found: C,81.97; H,10.18.
IRν, KBr(cm -1 ): 3350, 2920, 2860, 1680, 1600, 1510, 1275, 1245, 1200, 1170, 1130.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.8 Hz), 0.52-2.24 (27H, m), 0.61 (1H, 1/2ABq, 4.8 Hz), 0.90(6H, s), 0.97(6H, s), 1.19(3H, t, 7.2 Hz), 1.61(9H, s) 2.57(2H, bq, 7.2 Hz), 4.52-4.84(1H, m), 6.43-6.64(1H, m), 6.64-7.02(2H, m), 7.12-7.48(2H, m), 7.48-7.67(1H, m).
EXAMPLE 133
Preparation of cycloartenyl ester of 3-methoxy-4-valeryloxy-α-propylcinnamic acid
The title compound was prepared according to following the procedure of Example 119 but 3-methoxy-4-valeryoxy-α-propylcinnamic acid (17.9 g, 0.056 mole) was used as a starting material, in place of 4-butyryloxy 3-methoxy-α-ethylcinnamic acid. The yield was 23.2 g (77.6%). m.p. 113°-114° C.
Specific rotation [α] D 20 +34.2° (C 1.00, CHCl 3 )
Analysis Calcd. for C 48 H 72 O 5 (M.W. 729.06): C,79.07; H 9.95. Found: C,79.13; H 9.88.
EXAMPLE 134
Preparation of cycloartenyl ester of 4-hydroxy-3-methoxy-α-propylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but cycloartenyl ester of 3-methoxy-4-valeryloxy-α-propyl-cinnamic acid (23.3 g, 0.032 mole) obtained according to the procedure of Example 133 was used as a starting material. The yield was 18.1 g (87.6 %). m.p. 122°-123° C.
Specific rotation [α] D 20 +41.2° (C 1.00, CHCl 3 )
Analysis Calcd. for C 43 H 64 O 4 (M.W.644.94): C,80.07; H,10.00. Found: C,80.14; H,9.97.
EXAMPLE 135
Preparation of cycloartenyl ester of 4-capryloxy-3-methoxy-α-butylcinnamic acid
The title compound was prepared according to following the procedure of Example 119 but 4-capryloxy-3-methoxy-α-butylcinnamic acid (19.2 g, 0.0551 mole) was used in place of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid. The yield was 22.7 g(54.4 %). m.p. 100°-101° C.
Specific rotation [α] D 20 +33.5° (C 1.00, CHCl 3 )
Analysis Calcd. for C 50 H 76 O 5 (M.W.757.11): C,79.31; H,10.12. Found: C,79.38; H,10.05.
EXAMPLE 136
Preparation of cycloartenyl ester of 4-hydroxy-3-methoxy-α-butylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but cycroartenyl ester of 4-capryloxy-3-methoxy-α-butylcinnamic acid (24.4 g, 0.032 mole) was used as a starting material. The yield was 17.8 g (84.4 %). m.p. 110°-111° C.
Specific rotation [α] D 20 +40.6° (C 1.00, CHCl 3 )
Analysis Calcd. for C 44 H 66 O 4 (M.W.672.99): C,80.19; H,10.10. Found: C,80.24; H,10.05.
EXAMPLE 137
Preparation of cyclobranyl ester of 4-hydroxy-3-methoxy-α-butylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but cyclobranyl ester of 4-capryloxy-3-methoxy-α-butylcinnamic acid (26.2 g, 0.034 mole) was used as a starting material. The yield was 18.4 g ((80.4 %). m.p. 132°-133° C.
Specific rotation [α] D 20 +37.0° (C 1.00, CHCl 3 )
Analysis Calcd. for C 45 H 68 O 4 (M.W.672.99): C,80.31; H,10.18. Found: C,80 39; H,10.04
EXAMPLE 138
Preparation of 24-methylenecycloartanyl ester of 4-hydroxy-3-methoxy-α-butylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but 24-methylenecycloartanyl ester of 4-capryloxy-3-methoxy-α-butylcinnamic acid (26.2 g, 0.034 mole) was used as a starting material. The yield was 18.1 g (79.1%). m.p. 124°-125° C.
Specific rotation [α] D 20 +39.8(C 1.00, CHCl 3 )
Analysis Calcd. for C 45 H 68 O 4 (M.W.672.99): C,80.31; H,10.18. Found: C,80.25; H,10.22.
EXAMPLE 139
Preparation of cycloartenyl ester of 3-ethoxy-4-propionyloxy-α-methylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but cycloartenyl ester of 3-ethoxy-4-propionyloxy-α-methylcinnamic acid (22.0 g, 0.032 mole) was used as a starting material. The yield was 15.8 g (78.2 %). m.p. 132°-133° C.
Specific rotation [α] D 20 +43.9° (C 1.00, CHCl 3 )
Analysis Calcd. for C 42 H 62 O 4 (M.W.630.92): C,79.95; H,9.91. Found: C,79.90; H 9.99.
EXAMPLE 140
Preparation of cyclobranyl ester of 3-ethoxy-4-hydroxy-α-methylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but cyclobranyl ester of 3-ethoxy-4-propionyloxy-α-methylcinnamic acid (21.7 g, 0.031 mole) was used as a starting material. The yield was 16.1 g (80.5%). m.p. 174°-175° C.
Specific rotation [α] D 20 +42.4° (C 1.00, CHCl 3 )
Analysis Calcd. for C 43 H 64 O 4 (M.W.644.94): C,80.07; H,10.00. Found: C,80.18; H,10.05.
EXAMPLE 141
Preparation of 24-methylenecycloartanyl ester of 3-ethoxy-4-hydroxy-α-methylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but 24-methylenecycloartanyl ester of 3-ethoxy-4-propionyloxy-α-methylcinnamic acid (22.2 g, 0.0317 mole) was used as a starting material. The yield was 16.7 g (81.6 %). m.p. 134°-135° C.
Specific rotation [α] D 20 +40.2° (C 1.00, CHCl 3 )
Analysis Calcd. for C 43 H 64 O 4 (M.W.644.94): C,80.07; H,10.00. Found: C,80.13; H,9.92.
EXAMPLE 142
Preparation of cycloartenyl ester of 3-ethoxy-4-hydroxy-α-ethylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but cycloartenyl ester of 4-butyryloxy-3-ethoxy-α-methylcinnamic acid (21.5 g, 0.030 mole) was used as a starting material. The yield was 15.4 g (79.6 %). m.p. 124°-125° C.
Specific rotation [α] D 20 +41.2° (C 1.00, CHCl 3 )
Analysis Calcd. for C 43 H 64 O 4 (M.W.644.94): C,80.07; H,10.00. Found: C,80.04; H,10.08.
EXAMPLE 143
Preparation of cycloartenyl ester of 3-ethoxy-4-hydroxy-α-propylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but cycloartenyl ester of 3-ethoxy-4-valeryloxy-α-propylcinnamic acid (26.0 g, 0.035 mole) was used as a starting material. The yield was 16.8 g (72.8%). m.p. 111°-112° C.
Specific rotation [α] D 20 +40.7° (C 1.00, CHCl 3 )
Analysis Calcd. for C 44 H 66 O 4 (M.W.658.97): C,80.19; H,10.10. Found: C,80.26; H,10.02.
EXAMPLE 144
Preparation of cyclobranyl ester of 3-ethoxy-4-hydroxy-α-propylcinnamic acid
The title compound was prepared according to follwoing the procedure of Example 120 but cyclobranyl ester of 3-ethoxy-4-valeryloxy-α-propylcinnamic acid (24.2 g, 0.032 mole) was used as a starting material. The yield was 16.7 g(72.8%). m.p. 134°-135° C.
Specific rotation [α] D 20 +37.1° (C 1.00, CHCl 3 )
Analysis Calcd. for C 45 H 68 O 4 (M.W.672.99): C,80.31; H,10.18. Found: C,80.25; H,10.24.
EXAMPLE 145
Preparation of cycloartenyl ester of 3-ethoxy-4-hydroxy-α-butylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but cycloartenyl ester of 4-capryloxy-3-ethoxy-α-butylcinnamic acid (23.1 g, 0.030 mole) was used as a starting material. The yield was 16.2 g (80.2 %). m.p. 99°-100° C.
Specific rotation [α] D 20 +40.0° (C 1.00, CHCl 3 )
Analysis Calcd. for C 45 H 68 O 4 (M.W.672.99): C,80.31; H,10.18. Found: C,80.21; H,10.22.
EXAMPLE 146
Preparation of cycloartenyl ester of 4-hydroxy-3-propoxy-α-methylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but cycloartenyl ester of 4-propionyloxy-3-propoxy-α-methylcinnamic acid (23.1 g, 0.033 mole) was used as a starting material. The yield was 17.2 g (80.8 %). m.p. 138°-139° C.
Specific rotation [α] D 20 +43.7° (C 1.00, CHCl 3 )
Analysis Calcd. for C 43 H 64 O 4 (M.W.644.94): C,80.07; H,10.00. Found: C,80.19; H,10.04.
EXAMPLE 147
Preparation of cycloartenyl ester of 4-hydroxy-3-butoxy-α-methylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 but cycloartenyl ester of 4-propionyloxy-3-butoxy-α-methylcinnamic acid (22.9 g, 0.032 mole) was used as a starting material. The yield was 16.5 g (78.2 %). m.p. 126°-127° C.
Specific rotation [[] D 20 +39.7° (C 1.00, CHCl 3 )
Analysis Calcd. for C 44 H 66 O 4 (M.W.658.97): C,80.19; H,10.10. Found: C,80.24; H,10.03.
EXAMPLE 148
Preparation of 24-methylenecycloartanyl ester of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid
The title compound was prepared according to follwoing the procedure of Example 121 but 24-methylenecycloartanol (18.1 g, 0.041 mole) was used as a starting material. The yield was 22.8 g (77.8 %). m.p. 127°-128° C.
Specific rotation [α] D 20 +35.1° (C 1.00, CHCl 3 )
Analysis Calcd. for C 47 H 70 O 5 (M.W.715.03): C,78.94; H,9.87. Found: C,78.90; H,9.79.
EXAMPLE 149
Preparation of 24-methylenecycloartanyl ester of 4-hydroxy-3-methoxy-α-ethylcinnamic acid
The title compound was prepared according to following the procedure of Example 122 but 24-methylenecycloartanyl ester of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid (21.5 g, 0.0301 mole) was used as a starting material. The yield was 17.3 g (89.1%). m p. 137°-138° C.
Specific rotation [α] D 20 +40.7° (C 1.00, CHCl 3 )
Analysis, for C 43 H 64 O 4 (M.W.644.94): Calcd. (%): C 80.07, H 10.00. Found (%): C 80.11, H 9.93.
EXAMPLE 150
Preparation of cyclobranyl ester of 4-hydroxy-3-propoxy-α-ethylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 where cyclobranyl ester of 4-butyryloxy-3-propoxy-α-ethylcinnamic acid (22.1 g, 0.0297 mole) was used in place of cycloartenyl ester of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid. The yield was 17.8 g (89.1%). m.p. 140°-141° C.
Specific rotation [α] D 20 +36.8° (C 1.00, CHCl 3 )
Analysis. for C 45 H 68 O 4 (M.W.672.99): Calcd. (%): C 80.31, H 10.18. Found (%): C 80.36, H 10.12.
EXAMPLE 151
Preparation of 24-methylenecycloartanyl ester of 4-hydroxy-3-propoxy-α-propylcinnamic acid
The title compound was prepared according to following the procedure of Example 120 where 24-methylenecycloartanyl ester of 3-propoxy-4-valeryloxy-αpropylcinnamic acid (23.5 g, 0.0305 mole) was used in place of cycloartenyl ester of 4-butyryloxy-3-methoxy-α-ethylcinnamic acid. The yield was 17.2 g (82.1%). 121° C.
Specific rotation [α] D 20 +39.1° (C 1.00, CHCl 3 )
Analysis, for C 46 H 70 O 4 (M.W.687.02): Calcd. (%): C 80.41, H 10.27. Found (%): C 80.32, H 10.34.
EXAMPLES 152-154
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of 3-propionyloxy-α-methylcinnamic acid
The title compounds were prepared according to following the procedure of Example 123 where cycloartenol (21.3 g, 0.050 mole), cyclobranol (22.0 g, 0.050 mole), and 24-methylenecycloartanol (22.0 g, 0.050 mole), respectively, and 3-propionyloxy-α-methyl-cinnamic acid (17.6 g, 0.075 mole) were used for each preparation. The yield (%), m.p. (°C.), and specific rotation {[α] D 20 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 3-propionyloxy-α- Yield point rotationNo. methylcinnamic acid (%) (°C.) [α].sub.D.sup.20______________________________________152 Cycloartenyl ester 83.1 80-81 +44.5°153 Cyclobranyl ester 82.4 100-101 +34.3°154 24-Methylene 82.0 85-86 +44.0° cycloartanyl ester______________________________________
EXAMPLES 155-157
Preparation of cycloartenyl, cyclobranyl, and 24-methylene cycloartanyl ester of 3-hydroxy-α-methylcinnamic acid
The title compounds were prepared according to following the procedure of Example 124 where the compounds (each 0.042 mole) of Examples 152-154 were used respectively. The yield (%), m.p. (°C.), and specific rotation {[α] D 20 (C 1.00, CHCl 3 )} of each produce were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 3-hydroxy-α-methyl- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.20______________________________________155 Cycloartenyl ester 86.2 178-179 +44.3°156 Cyclobranyl ester 87.2 191-192 +45.2°157 24-Methylene- 85.8 188-189 +42.7° cycloartanyl ester______________________________________
EXAMPLES 158-160
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl ester of 3-butyryloxy-α-ethylcinnamic acid
The title compounds were prepared according to following the procedure of Example 129 where 3-butyryloxy-α-ethylcinnamic acid (3.50 g, 0.0135 mole) and cycloartenol (2.85 g, 0.0067 mole), cyclobranol (2.95 g, 0.0067 mole), and 24-methylenecycloartanol (2.95 g, 0.0067 mole), respectively were used for each preparation. The yield (%), m.p. (°C.), and specific rotation {[α] D 20 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 3-butyryloxy-α- Yield point rotationNo. ethylcinnamic acid (%) (°C.) [α].sub.D.sup.20______________________________________158 Cycloartenyl ester 81.4 82-83 +41.4°159 Cyclobranyl ester 82.3 112-113 +37.4°160 24-Methylene 79.4 89-90 +40.8° cycloartanyl ester______________________________________
EXAMPLES 161-163
Preparationof cycloartenol, cyclobranol, and 24-methylenecycloartanol ester of 3-hydroxy-α-ethylcinnamic acid
The title compounds were prepared according to following the porcedure of Example 129 where the compounds (each 0.003 mole) of Examples 158-160 were used, respectively. The yield (%), m.p. (° C., and specific rotation {[α] D 20 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 3-hydroxy-α-ethyl- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.20______________________________________161 Cycloartenyl ester 92.4 161-162 +44.8°162 Cyclobranyl ester 93.4 188-189 +46.0°163 24-Methylene- 91.8 173-174 +44.2° cycloartanyl ester______________________________________
EXAMPLES 164-165
Preparation of cycloartenyl and cyclobranyl esters of 2-hydroxy-α-methylcinnamic acid
Cycloartenyl and cyclobranyl esters of 2-propionyloxy-α-methylcinnamic acid (27.5 g, yield 85.5%; 27.5 g, yield 82.8%, respectively) were prepared according to following the procedure of Example 123 where cycloartenol (21.3 g, 0.050 mole) and cyclobranol (22.0 g, 0.050 mole), respectively, and 2-propionyloxy-α-methylcinnamic acid (17.6 g, 0.075 mole were used) for preparation. Using these esters (each 24.5 g), the title compounds were prepared according to following the procedure of Example 124. The yield (%), m.p. (°C.), and specific rotation {[α] D 20 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 2-hydroxy-α- Yield point rotationNo. methylcinnamic acid (%) (°C.) [α].sub.D.sup.20______________________________________164 Cycloartenyl ester 85.4 185-186 +46.4°165 Cyclobranyl ester 86.2 197-198 +48.7°______________________________________
EXAMPLE 166
Preparation of cycloartenyl ester of 3-methoxy-4-nitrobenzoic acid
To 3-methoxy-4-nitrobenzoic acid (15.0 g, 0.076 mole) were added thionyl chloride (34 ml, 6 equivalents) and dimethylformamide (0.5 ml), and the mixture was stirred at 60° C. for 2 hours. Then the reaction mixture was concentrated under reduced pressure and the residue was mixed with dioxane (75 ml) at 0° C. Thereto was added a solution of cycloartenol (25.0 g, 0.059 mole) in pyridine (110 ml). This reaction mixture was stirred at 70° C. for 20 minutes. After thus completing the reaction, the solvents were removed by distillation under reduced pressure. The resulting residue was dissolved in chloroform, and the chloroform layer was washed with saturated aqueous NaHCO 3 solution, and dried. The chloroform solution was concentrated under reduced pressure. The residual crystals were recrystallized from methylene chloride-methanol (1:2, v/v), giving cycloartenyl ester of 3-methoxy-4-nitrobenzoic acid (30.5 g) in a 85.3% yield. m.p. 182°-183° C.
Specific rotation [α] D 22 .5 +57.7° (C 1.00, CHCl 3 )
Analysis, for C 38 H 55 NO 5 (M.W.605.82): Cald. (%): C 75.33, H 9.15, N 2.31. Found (%): C 75.42, H 9.07, N 2.36.
IRν, KBr(cm -1 ): 2940, 1720, 1610, 1530, 1410, 1350, 1310, 1290, 1245.
PMR(CDCl 3 )δ: 0.38(1H, 1/2ABq, 4.2 Hz), 0.62(1H, 1/2ABq, 4.2 Hz), 0.50-2.36(27H, m), 0.95(1H, s), 0.97 (3H, s), 1.04(3H, s), 1.60(3H, s), 1.69(3H, s), 4.00(3H, s), 4.50-5.32(2H, m), 7.42-8.01 (3H, m).
EXAMPLE 167
Preparation of cycloartenyl ester of 4-amino-3-methoxy benzoic acid
Acetic acid (400 ml) and dioxane (400 ml) were added to cycloartenyl ester of 3-methoxy-4-nitrobenzoic acid (40.0 g, 0.066 mole) prepared according to the procedure of Example 166. Thereto 6N-HCl-dioxane (22 ml, 2 equivalents) and zinc powder (40 g) were added at 0° C. and the mixture was stirred at 25° C. for 2 hours. After the reaction, zinc powder was removed by filtration. The filtrate was concentrated under reduced pressure, and the residue was extracted with chloroform. The chloroform extracts were washed successively with water and saturated aqueous NaHCO 3 solution, then dried, and concentrated. The residual crystals were recrystallized from methylene chloride-methanol (1:2, v/v), giving cycloartenyl ester 4-amino-3-methoxybenzoic acid (32 g) in a 84.1% yield. m.p. 186°-188° C.
Specific rotation [α] D 26 .5 +64.3°(C 1.00, CHCl 3 )
Analysis, for C 38 H 57 NO 3 (M.W.575.83): Calcd. (%): C 79.26, H 9.98, N 2.43. Found (%): C 79.32, H 9.99, N 2.39.
IRν, KBr(cm -1 ): 3450, 3350, 2930, 1700, 1620, 1520, 1460, 1305, 1285, 1260, 1220, 1180, 1105.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.2 Hz), 0.61(1H, 1/2ABq, 4.2 Hz), 0.48-2.39(27H, m), 1.61 (3H, s), 1.67 (3H, s), 3.88(3H, s), 4.20(2H, bs), 4.51-5.31 (2H, m), 6.46-6.77(1H, m), 7.30-7.71(2H, m).
EXAMPLE 168
Preparation of cyclobranyl ester of 3-methoxy-4-nitrobenzoic acid
3-Methoxy-4-nitrobenzoic acid (50.0 g, 0.254 mole) was allowed to react with thionyl chloride (60 ml, 3.2 equivalents) by adding dimethylformamide (0.5 ml) and the mixture was stirred at 60° C. for 2 hours. Then the reaction mixture was concentrated under reduced pressure. Dioxane (100 ml) was added thereto, and further a solution of cyclobranol (93 g, 0.211 mole) in pyridine (150 ml) was added at 0° C. The mixture was stirred at 70° C. for 30 minutes. After the reaction, the solvents were removed by distillation under reduced pressure. The resulting residue was dissolved in chloroform, and the chloroform layer was washed with saturated aqueous NaHCO 3 solution, and dried. This chloroform solution was concentrated under reduced pressure, and the residual crystals were recrystallized from chloroform-ethanol (1:3, v/v), giving cyclobranyl ester of 3-methoxy-4-nitrobenzoic acid (94.4 g) in a 72.1% yield. m.p. 213°-214° C.
Specific rotation [α] D 25 .5 +53.9°(C 1.00, CHCl 3 )
Analysis, for C 39 H 57 NO 5 (M.W.619.85): Calcd. (%): C 75.57, H 9.27, N 2.26. Found (%): C 75.63, H 9.22, N 2.33.
IRν, KBr(cm -1 ): 2930, 1715, 1610, 1530, 1410, 1360, 1310, 1285, 1240.
PMR(CDCl 3 )δ: 0.39(1H, 1/2ABq, 4.8 Hz), 0.62(1H, 1/2ABq, 4 8 Hz), 0.50-2.28(27H, m), 0.92(6H, s), 0.99 (3H, s), 1.05(3H, s), 1.63(9H, s), 4.01(3H, s), 4.62-5.03(1H, m), 7.48-7.96(3H, m).
EXAMPLE 169
Preparation of cyclobranyl ester of 4-amino-3-methoxybenzoic acid
Cyclobranyl ester of 3-methoxy-4-nitrobenzoic acid (94.3 g, 0.152 mole) prepared according to the procedure of Example 168 was suspended in a mixture of acetic acid (1.2 l) and tetrahydrofuran (1.2 l), and thereto 6N-HCl-dioxane (100 ml) and zinc powder (94 g) were added, and the reaction mixture was stirred at 25° C. for 2 hours. After the reaction, zinc powder was removed by filtration. The filtrate was concentrated under reduced pressure and the residue was extracted with chloroform. The chloroform extracts were washed successively with water and saturated aqueous NaHCO 3 solution, then dried, and concentrated. The residual crystals were recrystallized from chloroform-ethanol (1:4, v/v), giving cyclobranyl ester of 4-amino-3-methoxybenzoic acid ester (64.2 g) in a 71.5% yield. m.p. 235°-236° C.
Specific rotation [α] D 25 +60.8°(C 1.00, CHCl 3 )
Analysis, for C 39 H 59 NO 3 (M.W.589.86): Calcd. (%): C 79.41, H 10.08, N 2.37. Found (%): C 79.49, H 10.12, N 2.42.
IRν, KBr(cm -1 ): 3450, 3350, 2900, 1680, 1620, 1310, 1280, 1260, 1110.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.8 Hz), 0.61(1H, 1/2ABq, 4.8 Hz), 0.50-2.20(27H, m), 0.89(6H, s), 0.96 (3H, s), 1.01(3H, s), 3.85(3H, s), 3.9204.36 (2H, bs), 4.51-4.91(1H, m), 6.42-6.72(1H, m), 7.26-7.72(2H, m).
EXAMPLE 170
Preparation of cycloartenyl ester of 2-methoxy-5-nitrobenzoic zcid
2-methoxy-5-nitrobenzoic acid (17,3 g, 0.088 mole) was allowed to react thionyl chloride (65 ml, 10 equivalents) by adding dimethylformamide (0.3 ml) and the mixture wa stirred at 50° C. for 1.5 hours. Then, the reaction mixture was concentrated under reduced pressure, dioxane (125 ml) was added thereto and further a solution of cycloartenol (25.0 g, 0.059 mole) in pyridine (125 ml) was added dropwise at 0° C. This reaction mixture was stirred at 60° C. for 1.5 hours. After the reaction, the solvents were removed by distillation under reduced pressure, the residue was extracted with chloroform, and the chloroform extracts were washed successively with water and saturated aqueous NaHCO 3 solution, then dried, and concentrated. The residue was recrystallized from methylene chloride-hexane (1:3, v/v), giving cycloartenyl ester of 2-methoxy-5-nitrobenzoic acid (31.5 g) in an 88.7% yield. m.p. 186°-187° C.
Specific rotation [α] D 25 +43.9°(C 1.00, CHCl 3 )
Analysis, for C 38 H 55 NO 5 (M.W.605.82): Calcd. (%): C 75.33, H 9.15, N 2.31. Found (%) : C 75.30, H 9.22, N 2.29.
IRν, KBr(cm -1 ): 2930, 1695, 1610, 1520, 1340, 1280, 1135.
PMR(CDCl 3 )δ: 0.39(1H, 1/2ABq, 4.2 Hz), 0.62(1H, 1/2ABq, 4.2 Hz), 0.50-2.40(27H, m), 0.90(3H, s), 0.96 (6H, s), 1.01(3H, s), 2.60(3H, bs), 2.68(3H, bs), 4.00(3H, s), 4.65-5.30(3H, m), 7.08(1H, d, 9.4 Hz) 8.34(1H, dd, 3.0 Hz, 9.4 Hz), 8.64(1H, d, 3.0 Hz).
EXAMPLE 171
Preparation of cycloartenyl ester of 5-amino-2-methoxybenzoic acid
Cycloartenyl ester of 2-methoxy-5-nitrobenzoic acid (34.0 g, 0.056 mole) prepared according to the procedure of Example 170 was suspended in acetic acid (1.2 l) at 20° C., and thereto 6N-HCl-dioxane (19 ml, 2 equivalent) and zinc powder (68 g) were added. The mixture was stirred at 30° C. for 1 hour. Then, zinc powder was removed by filtration, and the filtrate was concentrated under reduced pressure and the residue was extracted with chloroform. The chloroform extracts were washed successively with water and saturated aqueous NaHCO 3 solution, then dried, concentrated, and the residual crystals were recrystallized from methylene chloride-hexane (1:4, v/v), giving cycloartenyl ester of 5-amino-2-methoxybenzoic acid (27.2 g) in a 84.4% yield. m.p. 180°-182° C.
Specific rotation [α] D 26 .5 +47.8°(C 1.00, CHCl 3 )
Analysis, for C 38 H 57 NO 3 (M.W.575.83): Calcd. (%): C 79.26, H 9.98, N 2.43. Found (%): C 79.32, H 9.94, N 2.41.
IRν, KBr(cm -1 ): 3450, 3350, 2900, 2860, 1690, 1630, 1500, 1440, 1300, 1270, 1245.
PMR(CDCl 3 )δ: 0.38(1H, 1/2ABq, 4.2 Hz), 0.59(1H, 1/2ABq, 4.2 Hz), 0.50-2.30(27H, m), 0.90(6H, s), 0.93 (6H, s), 1.59(3H, bs), 1.67(3H, bs), 3.55(2H, bs), 3.88(3H, s), 4.50-5.30(2H, m), 6.68-7.24(3H, m).
EXAMPLE 172
Preparation of cyclobranyl ester of 2-methoxy-5-nitrobenzoic acid
2-Methoxy-5-nitrobenzoic acid (11.6 g, 0.059 mole) was allowed to react with thionyl chloride (20 ml) and dimethylformamide (0.2 ml) and the mixture was stirred at 50° C. for 2 hours. Then the reaction mixture was concentrated under reduced pressure. Toluene (150 ml), pyridine (30 ml), and further cyclobranol (20 g, 0.045 mole) were added to the residue and the mixture was stirred at 60° C. for 2 hours. After the reaction, the solvents were removed by distillation under reduced pressure and the residue was extracted with chloroform. The chloroform extracts were washed successively with water and saturated aqueous NaHCO 3 solution, then dried, concentrated, and the residue was recrystallized from chloroform-ethanol (1:3, v/v),giving cyclobranyl ester of 2-methoxy-5-nitrobenzoic acid (25.9 g) in a 92.0% yield. m.p. 207°-208° C.
Specific rotaion [α] D 25 +32.5°(C 1.00, CHCl 3 )
Analysis, for C 39 H 57 NO 5 (M.W. 619.85): Calcd. (%): C 75.57, H 9.27, N 2.26. Found (%): C 75.52, H 9.34, N 2.30.
IRν, KBr(cm -1 ): 2390, 1700, 1610, 1520, 1345, 1280 1130.
PMR(CDCl 3 )δ: 0.39(1H, 1/2ABq, 4.8 Hz), 0.62(1H, 1/2ABq, 4.8 Hz), 0.76-2.24(27H, m), 0.91(3H, s), 0.96 (6H, s), 1.01(3H, s), 1.63(9H, s), 4.01(3H, s), 4.64-5.02(1H, m), 7.06(1H, d, 9.6 Hz), 8.34(1H, dd, 9.6 Hz, 3.6 Hz), 8.67(1H, d, 3.6 Hz).
EXAMPLE 173
Preparation of cyclobranyl ester of 5-amino-2-methoxybenzoic acid
Cyclobranyl ester of 2-methoxy-5-nitrobenzoic acid (25.0 g, 0.040 mole) prepared according to the procedure of Example 172 was suspended in acetic acid (1 l), and thereto 6N-HCl-dioxane (21 ml) and zinc powder (25.0 g) were added. The mixture was stirred at 30° C. for 2 hours. After the reaction, zinc powder was removed by filtration. The filtrate was concentrated under reduced pressure, and the residue was extracted with chloroform. The extracts were washed successively with water and saturated aqueous NaHCO 3 solution, then dried, concentrated, and the residue was recrystallized from chloroform-ethanol (1:2, v/v), giving cyclobranyl ester of 5-amino-2-methoxybenzoic acid (13.7 g) in a 57.5% yield. m.p. 193°-195° C.
Specific rotation [α] D 26 .5 +41.5°(C 1.00, CHCl 3 )
Analysis, for C 39 H 59 NO 3 (M.W.589.86): Calcd (%): C 79.41, H 10.08, N 2.37. Found (%): C 79.35, H 10.15, N 2.35.
IRν, KBr(cm -1 ): 3430, 3350, 2930, 1690, 1500, 1460, 1430, 1310, 1270, 1245.
PMR(CDCl 3 )δ: 0.36(1H, 1/2ABq, 4.8 Hz), 0.61(1H, 1/2ABq, 4.8 Hz), 0.50-2.28(27H, m), 0.92(3H, s), 0.96 (6H, s), 1.00(3H, s), 1.64(9H, s), 2.88-3.26 (2H, m), 3.81(3H, s), 4.52-5.02(1H, m), 6.74-6.90(1H, m), 7.08-7.22(2H, m).
EXAMPLES 174-176
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of 3-methoxy-4-nitrocinnamic acid
The title compounds were prepared according to following the procedure of Example 166 where 3-methoxy-4-nitrocinnamic acid (17.0 g, 0.076 mole) for each preparation and cycloartenol (25.0 g), cyclobranol (26.0 g), and 24-methylenecycloartanol (26.0 g), respectively were used. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 3-methoxy-4-nitro- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.20______________________________________174 Cycloartenyl ester 86.2 190-194 +43.6°175 Cyclobranyl ester 85.3 220-221 +42.3°176 24-Methylene- 85.8 210-211 +43.0° cycloartanyl ester______________________________________
EXAMPLES 177-179
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl ester of 4-amino-3-methoxycinnamic acid
The title compounds were prepared according to following the procedure of Example 167 but where using cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of 3-methoxy-4-nitrocinnamic acid (41.7 g, 42.6 g and 42.6 g, respectively, each 0.066 mole) obtained in Examples 174-176 were used, respectively. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 4-amino-3-methoxy- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________177 Cycloartenyl ester 85.2 194-195 +42.3°178 Cyclobranyl ester 85.8 240-241 +41.0°179 24-Methylene- 86.4 227-228 +41.8° cycloartanyl ester______________________________________
EXAMPLES 180-182
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of 2-ethoxy-5-nitrocinnamic acid
The title compounds were prepared according to following the procedure of Example 170 where 2-ethoxy-5-nitrocinnamic acid (19.5 g, 0.082 mole) for each preparation and cycloartenol (25.0 g, 0.059 mole), cyclobranol (26.0 g, 0.059 mole), and 24-methylenecycloartanol (26.0 g, 0.059 mole), respectively were used. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 2-ethoxy-5-nitro- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________180 Cycloartenyl ester 87.8 182-183 +42.7°181 Cyclobranyl ester 88.4 203-204 +40.4°182 24-Methylene- 87.2 198-199 +42.1° cycloartanyl ester______________________________________
EXAMPLES 183-185
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of 5-amino-2-ethoxycinnamic acid
The title compounds were prepared according to following the procedure of Example 171 where cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of 2-ethoxy-5-nitrocinnamic acid (36.2 g, 37.0 g, and 37.0 g, respectively, each 0.056 mole) obtained in Examples 180-182, respectively were used. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 5-amino-2-ethoxy- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________183 Cycloartenyl ester 85.3 176-177 +43.2°184 Cyclobranyl ester 84.8 190-191 +41.0°185 24-Methylene- 85.8 181-182 +42 2° cycloartanyl ester______________________________________
EXAMPLE 186-188
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl ester of 3-methoxy-4-nitro-α-methylcinnamic acid
The title compounds were prepared according to following the procedure of Example 166 where 3-methoxy-4-nitro-α-methylcinnamic acid (17.3 g, 0.073 mole) for each preparation and cycloartenol (25.0 g, 0.059 mole), cyclobranol (26.0 g, 0.059 mole), and 24-methylenecycloartanol (26.0 g, 0.059 mole), respectively were used. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 3-methoxy-4-nitro-α- Yield point rotationNo. methylcinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________186 Cycloartenyl ester 83.4 178-180 +44.3°187 Cyclobranyl ester 84.2 208-209 +43.7°188 24-Methylene- 82.5 199-200 +44.1° cycloartanyl ester______________________________________
EXAMPLES 189-191
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of 4-amino-3-methoxy-α-methylcinnamic acid
The title compounds were prepared according to following the procedure of Example 167 where cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of 3-methoxy-4-nitro-α-methylcinnamic acid (43.6 g, 44.5 g, and 44.5 g, respectively, each 0.066 mole) obtained in Examples 186-188, respectively were used. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 4-amino-3-methoxy-α- Yield point rotationNo. methylcinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________189 Cycloartenyl ester 85.6 183-184 +43.0°190 Cyclobranyl ester 84.5 225-226 +42.0°191 24-Methylene- 85.0 213-214 +42.7° cycloartanyl ester______________________________________
EXAMPLES 192-194
Preparation of cycloartenyl cyclobranyl, and 24-methylenecycloartanyl esters of 5-nitro-2-propoxy-α-methylcinnamic acid
The title compounds were prepared according to following the procedure of Example 170 where 5-nitro-2-propoxy-α-methylcinnamic acid (21.2 g, 0.080 mole) for each preparation and cycloartenol (25.0 g, 0.059 mole), cyclobranol (26.0 g, 0.059 mole), and 24-methylenecycloartanol (26.0 g, 0.059 mole), respectively were used. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 5-nitro-2-propoxy-α- Yield point rotationNo. methylcinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________192 Cycloartenyl ester 86.4 184-185 +43.2°193 Cyclobranyl ester 88.4 204-205 +41.3°194 24-Methylene 87.2 196-197 +42.7° cycloartanyl ester______________________________________
EXAMPLES 195-197
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of 5-amino-2-propoxy-α-methylcinnamic acid
The title compounds were prepared according to following the procedure of Example 171 where cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of 5-nitro-2-propoxy-α-methylcinnamic acid (37.7 g, 38.5 g, and 38.5 g respectively, each 0.056 mole) obtained in Examples 192-194, respectively, were used. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 5-amino-2-propoxy-α- Yield point rotationNo. methylcinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________195 Cycloartenyl ester 84.4 175-176 +44.2°196 Cyclobranyl ester 83.5 194-195 +41.7°197 24-Methylene- 84.2 187-188 +43.6° cycloartanyl ester______________________________________
EXAMPLES 198 AND 199
Preparation of cycloartenyl and cyclobranyl esters of 3-methoxy-4-nitro-α-isopropyl cinnamic acid
The title compounds were prepared according to following the procedure of Example 166 where 3-methoxy 4-nitro-α-isopropylcinnamic acid (19.1 g, 0.072 mole) for each preparation and cycloartenol (25.0 g, 0.059 mole) and cyclobranol (26.0 g, 0.059 mole), respectively were used. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of 3-methoxy-4-nitro-α- Melting SpecificExample isopropylcinnamic Yield point rotationNo. acid (%) (°C.) [α].sub.D.sup.25______________________________________198 Cycloartenyl ester 84.2 155-156 +41.2°199 Cuclobranyl ester 84.6 190-191 +40.5°______________________________________
EXAMPLES 200 AND 201
Preparation of cycloartenyl and cyclobranyl esters of 4-amino-3-methoxy-α-isopropylcinnamic acid
The title compounds were prepared according to following the procedure of Example 167 where cycloartenyl and cyclobranyl esters of 3-methoxy-4-nitro-α-isopropylcinnamic acid (44.5 g and 45.4 g, respectively, each 0.066 mole) obtained in Examples 198 and 199, respectively were used. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample 4-amino-3-methoxy-α- Yield point rotationNo. isopropylcinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________200 Cycloartenyl ester 85.8 163-164 +40.8°201 Cyclobranyl ester 84.2 201-202 +39.7°______________________________________
EXAMPLES 202-204
Preparation of cycloartenyl, cyclobranyl and 24-methylenecycloartanyl esters of p-nitro-α-methylcinnamic acid
Thionyl chloride (112 ml, 4 equivalents) and dimethylformamide (1 ml) were added to p-nitro-α-methylcinnamic acid (78.3 g, 0.378 mole) and the mixture was stirred at 60° C. for 2 hours. Then the resulting mixture was evaporated to dryness under reduced pressure, and the residue was mixed with dioxane (250 ml) and with pyridine (250 ml), and the mixture was allowed to react with cycloartenol (125.0 g, 0.293 mole), cyclobranol (129.1 g, 0.293 mole), or 24-methylenecycloartanol (129.1 g, 0.293 mole) at 60° C. for 2 hours. Then, the solvents were distilled off under reduced pressure, and the residue was extracted with chloroform. The extracts were washed successively with water and saturated aqueous solution of sodium bicarbonate, then dried, and evaporated to dryness under reduced pressure. The residual crystals were recrystallized from chloroformethanol (1:3, v/v), giving each of the title compounds. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample p-nitro- -methyl- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________204 Cycloartenyl ester 88.7 188-189 +44.2°205 Cyclobranyl ester 89.5 222-223 +41.7°206 24-Methylene- 88.8 211-212 +43.5° cycloartanyl ester______________________________________
EXAMPLES 205-207
Preparation of cycloartenyl cyclobranyl, and 24-methylenecycloartanyl esters of p-amino-α-methylcinnamic acid
Each of cycloartenyl, cyclobranyl, and 24-methylene-cycloartanyl esters of p-nitro-α-methylcinnamic acid (16.6 g, 17.0 g, and 17.0 g, respectively, 0.027 mole each) obtained in Examples 204-206, respectively, was suspended in a mixture of acetic acid (150 ml) and dioxane (150 ml), 6N-hydrochloric acid-dioxane (9.5 ml) and zinc powder (8 g) were added to the suspension and the mixture was stirred at 40° C. for 3 hours. After the reaction, zinc powder was removed by filtration. The filtrate was evaporated to dryness under reduced pressure. The residue was extracted with chloroform. The extracts were washed successively with water and saturated aqueous sodium bicarbonate solution, then dried, and evaporated to dryness. The residual crystals were recrystallized from chloroform-ethanol (1:3, v/v), giving each of the title compounds. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample p-amino-α-methyl- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________205 Cycloartenyl ester 91.2 168-169 +42.6°206 Cyclobranyl ester 91.8 202-203 +41.2°207 24-Methylene- 92.0 193-194 +42.3° cycloartanyl ester______________________________________
EXAMPLES 208-210
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of m-nitro-α-methylcinnamic acid
Thionyl chloride (60 ml, 2.1 equivalent) and dimethylformamide (1 ml) were added to m-nitro-α-methylcinnamic acid (80.4 g, 0.388 mole) and the mixture was stirred at 60° C. for 2 hours. After concentration of the resulting mixture under reduced pressure, the residue was mixed with dioxane (300 ml) and with pyridine (200 ml), and the mixture was allowed to react with cycloartenol (125.9 g, 0.295 mole), cyclobranol (130.0 g, 0.295 mole), or 24-methylenecycloartanol (130.0 g, 0.295 mole) at 60° C. for 2 hours. Then the mixture was evaporated to dryness under reduced pressure, and the residue was extracted with chloroform. The extracts were washed successively with water and saturated aqueous solution of sodium bicarbonate, then dried, and evaporated to dryness under reduced pressure. The residual crystals were recrystallized from chloroformethanol (1:4, v/v), giving each of the title compounds. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample m-nitro-α-methyl- Yield point rotationNo. cinnamate (%) (°C.) [α].sub.D.sup.25______________________________________208 Cycloartenyl ester 92.4 161-162 +43.0°209 Cyclobranyl ester 91.7 193-194 +42.3°210 24-Methylene- 90.9 172-173 +42.7° cycloartanyl ester______________________________________
EXAMPLES 211-213
Preparation of cycloartenyl, cyclobranyl, and 24-methylenecycloartanyl esters of m-amino-α-methylcinnamic acid
Each of cycloartenyl-, cyclobranyl-, and 24-methylenecycloartanyl esters of m-nitro-α-methylcinnamic acid (16.6 g, 17.0 g, and 17.0 g, respectively, 0.027 mole each) obtained in Examples 208-210, respectively, was suspended in a mixture of acetic acid (150 ml) and tetrahydrofuran (200 ml). 6N-hydrochloric acid-dioxane (12.5 ml) and zinc powder (16.5 g) were added to the suspension and the mixture was stirred at 20° C. for 2 hours. After the reaction, zinc powder was removed by filtration. The filtrate was concentrated under reduced pressure, and extracted with chloroform. The extracts were washed successively with water and saturated aqueous solution of sodium bicarbonate, then dried, and evaporated to dryness. The residual crystals were recrystallized from chloroform-ethanol (1:2, v/v), giving each of the title compounds. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows.
______________________________________ Triterpenyl ester of Melting SpecificExample m-amino- -methyl- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________211 Cycloartenyl ester 85.2 171-172 +44.2°212 Cyclobranyl ester 86.3 198-199 +42.8°213 24-Methylene- 84.2 177-178 +43.4° cycloartanyl ester______________________________________
EXAMPLES 214 AND 215
Preparation of cycloartenyl and cyclobranyl esters of p-nitro-α-ethylcinnamic acid
Thionyl chloride (6 ml, 2.0 equivalent) and dimethylformamide (0.1 ml) were added to p-nitro-α-ethylcinnamic acid (8.9 g, 0.040 mole) and the mixture was stirred at 60° C. for 2 hours. Then the resulting mixture was concentrated under reduced pressure. The residue was mixed with dioxane (30 ml) and with pyridine (20 ml), and the mixture was allowed to react with cycloartenol (12.8 g, 0.030 mole) or cyclobranol (13.2 g, 0.030 mole) at 60° C. for 2 hours. Then the resulting mixture was concentrated under reduced pressure, and the residue was extracted with chloroform. The extracts were washed successively with water and saturated aqueous solution of sodium bicarbonate, then dried, and evaporated to dryness under reduced pressure. The residual crystals were recrystallized from chloroform-ethanol (1:3, v/v), giving each of the title compounds. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample p-nitro-α-ethyl- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________214 Cycloartenyl ester 92.1 178-179 +44.8°215 Cyclobranyl ester 91.8 204-205 +43.7°______________________________________
EXAMPLES 216 AND 217
Preparation of cycloartenyl and cyclobranyl esters of p-amino-α-ethylcinnamic acid
Each of cycloartenyl and cyclobranyl esters of p-nitro-α-ethylcinnamic acid (17.0 g and 17.4 g, respectively, 0.027 mole each) obtained in Examples 214 and 215, respectively, was suspended in a mixture of acetic acid (150 ml) and tetrahydrofuran (200 ml). 6N-Hydrochloric acid-dioxane (12.5 ml) and zinc powder (16.5 g) were added to the suspension and the mixture was stirred at 22° C. for 2 hours. After the reaction, zinc powder was removed by filtration. The filtrate was evaporated to dryness under reduced pressure, and the residue was extracted with chloroform. The extracts were washed successively with water and saturated aqueous solution of sodium bicarbonate, then dried, and evaporated to dryness under reduced pressure. The residual crystals were recrystallized from chloroformethanol (1:3, v/v), giving each of the title compounds. The yield (%), m.p. (°C.), and specific rotation {[α] D 25 (C 1.00, CHCl 3 )} of each product were as follows:
______________________________________ Triterpenyl ester of Melting SpecificExample p-amino-α-ethyl- Yield point rotationNo. cinnamic acid (%) (°C.) [α].sub.D.sup.25______________________________________216 Cycloartenyl ester 80.6 160-161 +45.2°217 Cyclobranyl ester 79.3 200-201 +44.3°______________________________________
EXAMPLE 218
Preparation of 24-methylenecycloartanyl ester of 3-methoxy-4-nitrobenzoic acid
The title compound was prepared according to following the procedure of Example 168 where 24-methylenecycloartanol (93.0 g, 0.211 mole) was used. The yield was 93.7 g (71.6%). m.p. 205°-206° C.
Specific rotation [α] D 25 .5 +56.5° (C 1.00, CHCl 3 )
Analysis, Calcd. for C 39 H 57 NO 5 (M.W.619.85): C 75.57, H 9.27, N 2.26. Found: C 75.51, H 9.38, N 2.28.
EXAMPLE 219
Preparation of 24-methylenecycloartanyl ester of 4-amino-3-methoxybenzoic acid
The title compound was prepared according to the procedure of Example 169 where 24-methylenecycloartanyl ester of 3-methoxy-4-nitrobenzoic acid was used (92.2 g, 0.149 mole) obtained in Example 218. The yield was 62.8 g (71.5%). m.p. 222°-223° C.
Specific rotation [α] D 25 +63.2° (C 1.00, CHCl 3 )
Analysis, for C 39 H 59 NO 3 (M.W.589.86): Calcd. (%): C 79.41, H 10.08, N 2.37. Found (%): C 79.38, H 10.14, N 2.35.
EXAMPLE 220
Preparation of cycloartenyl ester of 4-amino-3-methoxybenzoic acid
4-Acetamido-3-methoxybenzoic acid (6.5 g, 0.031 mole) in dioxane (110 ml) was allowed to react with thionyl chloride (21.0 ml) and then pyridine (0.5 ml) at 20° C., and the mixture was stirred at 50° C. for 5 minutes. Then the resulting mixture was evaporated to dryness under reduced pressure, and to the residue a solution of cycloartenol (10.0 g, 0.023 mole) in a dioxane (50 ml)-benzene (50 ml) mixture was added and further pyridine (20 ml). After the mixture was heated at 70° C. for 3 hours, the solvents were distilled off under reduced pressure. The residue was dissolved in chloroform (100 ml), and the chloroform solution was washed with saturated aqueous solution of sodium bicarbonate. The aqueous solution was extracted with chloroform (5×10 ml). The whole chloroform solution was dried and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography [solvent: chloroform-ethyl acetate (1:1, v/v)], giving cycloartenyl ester of 4-acetamido-3-methoxybenzoic acid (10.8 g) in a 76.5% yield. m.p. 224°-225° C.
Specific rotation [α] D 25 +61.5° (C 1.00, CHCl 3 ).
Cycloartenyl ester of 4-acetamido-3-methoxybenzoic acid (10.0 g, 0.016 mole) thus obtained was allowed to react with 30% HCl (20 ml) in tetrahydrofuran (200 ml) under reflux for 2 hours. Then the solvent was distilled off under reduced pressure, and the residue was dissolved in chloroform (300 ml), and the chloroform layer was washed successively with 1N aqueous NaOH (200 ml) and saturated saline water. The aqueous solutions were extracted with chloroform 3 times. The combined chloroform solution was dried and concentrated and the residue was purified by silica gel column chromatography [solvent: ethyl acetate-hexane (1:4, v/v)], giving cycloartenyl ester of 4-amino-3-methoxybenzoic acid (5.4 g) in a 58.7% yield. m.p. 186°-187° C.
Specific rotation [α] D 26 +64.4° (C 1.00, CHCl 3 ).
EXAMPLE 221
Preparation of cyclobranyl ester of 4-amino-3-methoxy-α-methylcinnamic acid
4-Acetamido-3-methoxy-α-methylcinnamic acid (21.93 g, 0.088 mole) dissolved in dioxane (150 ml) was allowed to react with thionyl chloride (25.7 ml) at 60° C. for 2 hours with stirring. Then the solvent was distilled off under reduced pressure. The residue was dissolved in dioxane (150 ml) and pyridine (50 ml), and allowed to react with cyclobranol (30 g, 0.068 mole) at 60° C. for 2 hours with stirring. The resulting mixture was concentrated under reduced pressure, and ethyl acetate (300 ml) was added to the residue. The resulting crystals were purified by silica gel column chromatography [solvent: chloroform-ethyl acetate (1:1, v/v)], giving cyclobranyl ester of 4-acetamido-3-methoxy-α-methylcinnamic acid (38.5 g) in a 84.2% yield, m.p. 248°-249° C.
Specific rotation [α] D 26 +38.2° (C 1.00, CHCl 3 ).
Cyclobranyl ester of 4-acetamido-3-methoxy-α-methylcinnamic acid (34.4 g, 0.051 mole) thus obtained was dissolved in tetrahydrofuran (300 ml), and was allowed to react with 30% HCl (60 ml) at 70° C. for 2 hours with stirring. The resulting mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography [solvent: chloroform-ethyl acetate, (1:1, v/v)], giving cyclobranyl ester of 4-amino-3-methoxy-α-methylcinnamic acid (18.9 g) in a 58.8% yield. m.p. 225°-226° C.
Specific rotation [α] D 25 +42.0° (C 1.00, CHCl 3 ).
EXAMPLE 222
Preparation of 24-methylenecycloartanyl ester of 4-amino-3-methoxycinnamic acid
24-Methylenecycloartanyl ester of 4-propionamido-3-methoxycinnamic acid was prepared according to the procedure of Example 221 where 4-propionamido-3-methoxycinnamic acid (21.93 g, 0.088 mole) and 24-methylenecycloartanol (30 g, 0.068 mole) were used in place of 4-acetamido-3-methoxy-α-methyl cinnamic acid and cyclobranol, respectively. The yield was 38.4 g (83.8%). m.p. 210°-211° C.
Specific rotation [α] D 26 +39.4° (C 1.00, CHCl 3 ).
Then 24-methylenecycloartanyl ester of 4-amino-3-methoxycinnamic acid (18.7 g) was prepared according to the procedure of Example 221 where 24-methylenecycloartanyl ester of 4-propionamido-3-methoxycinnamic acid was used (35.2 g, 0.052 mole) in place of cyclobranyl ester of 4-acetamido-3-methoxy-α-methylcinnamic acid. The yield was 18.7 g (57.1%). m.p. 227°-228° C.
Specific rotation [α] D 25 +41.8° (C 1.00, CHCl 3 ).
FORMULA EXAMPLE 1
______________________________________Tablets ACompound of Example 43:Cyclobranyl ester of p-aminobenzoic acid 100 mgMannitol 123 mgHydroxypropoxymethylcellulose 7 mgTalc 5 mgMicrocrystalline cellulose 60 mgHydrogenated castor oil 5 mgTotal 300 mgTablets BCompound of Example 86:24-Methylenecycloartanyl ester of 150 mg4-hydroxy-3-methoxybenzoic acidCorn starch 160 mgLactose 180 mgTalc 7 mgMagnesium stearate 3 mgTotal 500 mgTablets CCompound of Example 100-2:Cyclobranyl ester of 4-hydroxy-3- 100 mgmethoxycinnamic acidSoluble starch 20 mgCorn starch 125 mgMicrocrystalline cellulose 45 mgSilicon dioxide 6 mgMagnesium stearate 4 mgTotal 300 mgTablets DCompound of Example 60:Cycloartenyl ester of 3-ethoxy-4- 100 mghydroxybenzoic acidLactose 147 mgCorn starch 62.1 mgMicrocrystalline cellulose 90 mgMagnesium stearate 0.9 mgTotal 400 mgTablets ECompound of Example 71:Cyclobranyl ester of 3-ethoxy-4- 50 mghydroxycinnamic acidLactose 10 mgMicrocrystalline cellulose 85.5 mgCarboxymethyl cellulose calcium 2 mgMagnesium stearate 1.5 mgStearic acid 1 mgTotal 150 mg______________________________________
According to the above prescriptions, various weights tablets were made of thoroughly uniformly mixed powders with a tableting machine.
In addition, tablets were prepared according to the recipe above but substituting, cycloartenyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid of Example 114 for cyclobranyl ester of p-aminobenzoic acid of Example 43; 24-methylenecycloartanyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid of Example 118 for 24-methylenecycloartanyl ester of 4-hydroxy-3-methoxybenzoic acid of Example 86; cyclobranyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid of Example 116 for cyclobranyl ester of 4-hydroxy3-methoxycinnamic acid of Example 100-2; cycloartenyl ester of p-amino-α-methylcinnamic acid of Example 205 for cycloartenyl ester of 3-ethoxy-4-hydroxybenzoic acid of Example 60; and cyclobranyl ester of 5-amino-2-methoxybenzoic acid of Example 173 for cyclobranyl ester of 3-ethoxy-4-hydroxycinnamic acid of Example 71.
FORMULA EXAMPLE 2
______________________________________Granules ACompound of Example 19:______________________________________Cycloartenyl ester of p-aminobenzoic acid 100 mgLactose 22 mgMicrocrystalline cellulose 60 mgCorn starch 15 mgHydroxypropylcellulose 3 mgTotal 200 mg______________________________________
According to the above prescription, cycloartenyl ester of p-aminobenzoic acid, lactose, microcrystalline cellulose, and corn starch were mixed together. The mixture was sprayed with a 5% aqueous solution of hydroxypropylcellulose as a binder, dried and granulated by using a fluidized bed granulator.
Another granules were prepared in the same method as the above recipe but substituting cycloartenyl ester of 4-amino-3-methoxybenzoic acid of Example 167 for cycloartenyl ester of p-aminobenzoic acid of Example 19.
FORMULA EXAMPLE 3
______________________________________Granules BCompound of Example 43:______________________________________Cyclobranyl ester of p-aminobenzoic acid 100 mgMannitol 38 mgMicrocrystalline cellulose 48 mgPotato starch 10 mgPolyvinylpyrrolidone 2 mgHydroxypropylcellulose 2 mgTotal 200 mg______________________________________
According to the above prescription, the cyclobranyl ester, mannitol, microcrystalline cellulose, potato starch and polyvinylpyrrolidone were mixed together, then the mixture was sprayed with 5% aqueous solution of hydroxypropylcellulose as a binder, dried and granulated, by using a fluidized bed granulator.
Another granules were prepared in the same method as the above recipe but substituting cycloartenyl ester of 5-amino-2-propoxy-α-methylcinnamic acid of Example 195 for cyclobranyl ester of p-aminobenzoic acid of Example 43.
FORMULA EXAMPLE 4
______________________________________Granules CCyclobranol 100 mgMannitol 10 mgMicrocrystalline cellulose 85 mgCarboxymethyl cellulose calcium 2 mgMagnesium stearate 1.5 mgHardened oil 1.5 mgTotal 200 mgGranules DCompound of Example 24:Cycloartenyl ester of nicotinic acid 100 mgCorn starch 29 mgMicrocrystalline cellulose 50 mgCarboxymethyl cellulose calcium 21 mgTotal 200 mgGranules ECompound of Example 49:Cyclobranyl ester of m-aminobenzoic acid 100 mgLactose 53 mgCorn starch 39 mgPotato starch 2 mgTalc 3 mgMagnesium stearate 3 mgTotal 200 mg______________________________________
According to the above prescriptions, the ingredients were mixed uniformly and granulated with an extruder.
In addition, another granules were prepared in the same method as the above recipe but substituting; cycloartenyl ester of 4-hydroxy-α-ethylcinnamic acid of Example 130 for cyclobranol; cycloartenyl ester of 4-amino-3-methoxycinnamic acid of Example 177 for cycloartenyl ester of nicotinic acid of Example 24 and cycloartenyl ester of 5-amino-2-methoxybenzoic acid of Example 171 for cyclobranyl ester of m-aminobenzoic acid of Example 49.
FORMULA EXAMPLE 5
______________________________________Capsules ACompound of Example 100-2:______________________________________Cyclobranyl ester of 4-hydroxy-3-methoxy- 100 mgcinnamic acidLactose 28 mgMicrocrystalline cellulose 47 mgMannitol 10 mgCorn starch 10 mgPolyvinylpyrrolidone 2 mgHydroxypropylcellulose 3 mgTotal 200 mg______________________________________
According to the above prescription, cyclobranyl ester of 4-hydroxy-3-methoxycinnamic acid, lactose, microcrystalline cellulose, mannitol, corn starch and polyvinylpyrrolidone were mixed together, then the mixture was sprayed with a 5% aqueous solution of hydroxypropylcellulose as a binder, dried and granulated, by using a fluidized bed granulator. No. 3 hard capsules were each filled with 200 mg of these granules.
Another hard capsules were prepared in the same method as the above recipe but substituting cycloartenyl ester of 4-hydroxy-3-methoxy-α-methylcinnamic acid of Example 114 for cyclobranyl ester of 4-hydroxy-3-methoxycinnamic acid of Example 100-2.
FORMULA EXAMPLE 6
Capsules B
Hard capsules were prepared by filling each of No. 3 hard capsules with 160 mg of granules A prepared according to Formula Example 2.
FORMULA EXAMPLE 7
Capsules C
Hard capsules were prepared by the following procedure. No. 2 hard capsules were filled with 200 mg of granules D prepared in Formula Example 4.
FORMULA EXAMPLE 8
______________________________________Capsules DCompound of Example 12:______________________________________Cycloartenyl ester of m-hydroxybenzoic acid 100 mgMannitol 98 mgCarboxymethyl cellulose calcium 2 mgTotal 200 mg______________________________________
According to the above prescription, the ingredients were mixed uniformly. Gelatin capsules of No. 2 were filled with 200 mg of the mixed powder each. Then the capsules were enteric-coated to give enteric capsules.
Another enteric capsules were prepared by the same method as the above recipe but substituting cyloartenyl ester of 4-hydroxy-3-propoxy-α-methylcinnamic acid of Example 146 for cycloartenyl ester of m-hydroxybenzoic acid of Example 12.
FORMULA EXAMPLE 9
______________________________________Capsules ECompound of Example 58:______________________________________Cyclobranyl ester of p-hydroxybenzoic acid 200 gSodium laurylsulfate 9 mgDisodium hydrogen phosphate 1 mgMannitol 188 mgMagnesium stearate 2 mgTotal 400 g______________________________________
According to the above prescription, ingredients were uniformly mixed. Gelatin capsules of No. 1 were filled with 300 mg of the mixture each. Another capsules were prepared by the same method as the above recipe but substituting cyclobranyl ester of m-amino-α-methylcinnamic acid of Example 212 for cyclobranyl ester of p-hydroxybenzoic acid.
FORMULA EXAMPLE 10
______________________________________Enteric granulesCompound of Example 25:______________________________________Cycloartenyl ester of linoleic acid 100 gMannitol 16 mgMicrocrystalline cellulose 65 mgCorn starch 15 mgHydroxypropylmethylcellulose 3 mgVinylpyrrolidone-vinyl acetate 1 mgcopolymer (supplied by General Aniline& Film Corp.)Total 200 g______________________________________
According to the above prescription, the ingredients were uniformly mixed and then granulated into spherical granules by an extruder. These granules were coated with material composed of hydroxypropylmethylcellulose phthalate (74%), glyceryl triacetate (11.6%), stearic acid (11.6%) and light silicon dioxide (2.8%), to give enteric granules.
Another enteric granules were prepared in the same method as the above recipe but substituting cycloartenyl ester of 5-amino-2-methoxybenzoic acid of Example 171 for cycloartenyl ester of linoleic acid of Example 25.
FORMULA EXAMPLE 11
______________________________________Enteric tabletsCompound of Example 54:______________________________________Cyclobranyl ester of m-hydroxybenzoic acid 100 mgMannitol 10 mgMicrocrystalline cellulose 85 mgCarboxymethyl cellulose calcium 2 mgMagnesium stearate 1.5 mgHardened oil 1.5 mgTotal 200 mg______________________________________
According to the above prescription, the ingredients were mixed uniformly. The mixture was compressed into tablets with a tabletting machine, followed by coating with the substance for enteric coating below.
______________________________________ Coating substance:______________________________________Hydroxypropylmethylcellulose phthalate 14.8 mgDioctyl phthalate 2.3 mgStearic acid 2.3 mgLight silicon dioxide 0.6 mgTotal 20 mg______________________________________
In addition, enteric tablets were prepared in the same method as the above recipe but substituting cycloartenyl ester of 5-amino-2-ethoxycinnamic acid of Example 183 for cyclobranyl ester of m-hydroxybenzoic acid of Example 54.
FORMULA EXAMPLE 12
______________________________________GranulesCompound of Example 16:Cycloartenyl ester of o-nitrobenzoic acid 100 mgCorn starch 32.5 mgHydroxypropylcellulose 3.5 mgTotal 136 mg______________________________________
According to the above prescription, the ingredients were uniformly mixed, the mixture was nucleated by tumbling or centrifugal methods. Then these nuclei were diluted with the uniformly mixed excipient below. The diluted nuclei were allowed to adhere each other with a usual binder; then coated and granulated. The granules (230 mg) were coated with the same enteric coating substance (30 mg) as shown in Formula Example 11. No. 3 gelatin capsules were each filled with 260 mg of the enteric granules.
______________________________________ Excipient:______________________________________sugar 33.0 mgCorn starch 58.5 mgHydroxypropylcellulose 2.5 mgTotal 94 mg______________________________________
FORMULA EXAMPLE 13
______________________________________Powders ACompound of Example 100-1:Cycloartenyl ester of 4-hydroxy-3- 100 mgmethoxycinnamic acidMannitol 50 mgCorn starch 50 mgTotal 200 mgPowders BCompound of Example 46:Cyclopranyl ester of o-amino- 100 mgbenzoic acidCorn starch 100 mgTotal 200 mg______________________________________
Powders were prepared by mixing the above ingredients uniformly in a double cone type blender.
FORMULA EXAMPLE 14
______________________________________CapsulesCompound of Example 93:______________________________________24-Methylenecycloartanyl ester of 260 glinoleic acidVitamin C 10 mgCitric acid 5 mgCarboxymethyl cellulose calcium 20 mgSodium laurylsulfate 10 mgPolyoxyethylene monostearate 5 mgMethylene chloride 300 ml______________________________________
The above ingredients were thoroughly mixed to make a suspension. Aerosil 200 - 400 (tradename) (180 g) was added to the suspension, then the mixture was stirred and dried. The resulting solid mass was ground to a powder, and a chlorothene-ethanol solution (300 ml) which contains 20 g of vinylpyrrolidone and 2-methyl-5-vinylpyridine-methacrylic acid - methyl acrylate copolymer as a binder was added to the powder. The mixture was kneaded and granulated with a pelleter according to the ordinary method, and the granules were dried at about 50° C. (containing about 51% 24-methylenecycloartanyl ester of linoleic acid). Hard capsules were filled with 200 mg of the granules with mixing a small amount of magnesium stearate each by using an automatic capsule-filling machine.
FORMULA EXAMPLE 15
______________________________________Suppositorys ACompound of Example 74:Cycloartenyl ester of 4-hydroxy-3- 200 mgpropoxycinnamic acidWitepsol E-85 540 mgWitepsol W-35 1454 mgMethyl-p-hydroxybenzoate 3 mgButyl-p-hydroxybenzoate 3 mgTotal 2200 mgSuppositorys BCompound of Example 29:Cycloartenyl ester of 4-hydroxy-3- 200 mgmethoxybenzoic acidAscorbic acid 20 mgPolyethylene glycol 2080 mgTotal 2300 mgSuppositorys CCompound of Example 39:Cyclobranyl ester of 3,4-dihydroxybenzoic 200 mgacidButylhydroxyanisole 6 mgSemisythetic glyceride 2900 mgTotal 3106 mgSuppositorys DCompound of Example 27:Cycloartenyl ester of 3,4-dihydroxybenzoic 200.0 mgacidGelatin 1152.0 mgGlycerol 454.0 mgMethyl-p-hydroxybenzoate 2.0 mgPropyl-p-hydroxybenzoate 0.4 mgEthylvanillin 2.8 mgTitanium dioxide 24.0 mgDC yellow lake No. 5 12.0 mgDistilled water 352.8 mgTotal 2200.0 mg______________________________________
According to the above prescriptions, the ingredients were thoroughly mixed and melted. And the melts were cast in aluminum molds, and cooled to give suppository.
FORMULA EXAMPLE 16
Emulsion
Polysolvate 80 (tradename, 1 g) and DK Ester F-160 (tradename, 1 g) were dissolved in a 50% aqueous solution of (100 ml) sorbitol. Cyclobranyl ester of 4-acetoxy-3-methoxycinnamic acid (50 g) was added thereto and the mixture was emulsified by stirring at 80° C. for 30 minutes. Sodium benzoate (0.25 g) and citric acid (1 g) were dissolved therein, then the volume was adjusted to 500 ml with distilled water. The whole was stirred again, giving the emulsion (containing about 10% cyclobranyl ester of 4-acetoxy-3-methoxycinnamic acid).
FORMULA EXAMPLE 17
______________________________________Tablets FCompound of Example 102:Cycloartenyl ester of p-aminocinnamic 100 mgacidMannitol 123 mgHydroxypropoxymethylcellulose 7 mgTalc 5 mgMicrocrystalline cellulose 61 mgMagnesium stearate 4 mgTotal 300 mgTablets GCompound of Example 104:Cyclobranyl ester of p-aminocinnamic 100 mgacidLactose 147 mgCorn starch 62 mgMicrocrystalline cellulose 86 mgMagnesium stearate 5 mgTotal 400 mgTablets HCompound of Example 108:Cycloartenyl ester of m-aminocinnamic 100 mgacidSoluble starch 20 mgCorn starch 125 mgMicrocrystalline cellulose 45 mgSilicon dioxide 6 mgMagnesium stearate 4 mgTotal 300 mg______________________________________
According to the each prescription above, the ingredients were uniformly mixed and compressed into the tablets of each weight by using a tabletting machine.
FORMULA EXAMPLE 18
______________________________________Granules FCompound of Example 112:______________________________________24-Methylenecycloartanyl ester of 100 mgm-aminocinnamic acidLactose 22 mgMicrocrystalline cellulose 60 mgCorn starch 15 mgHydroxypropylcellulose 3 mgTotal 200 mg______________________________________
According to the prescription, 24-methylenecycloartanyl ester of m-aminocinnamic acid, lactose, microcrystalline cellulose, and corn starch were mixed. The mixture sprayed with a 5% aqueous hydroxypropylcellulose solution as a binder was dried and granulated with a fluidized bed granulator.
FORMULA EXAMPLE 19
______________________________________Granules GCompound of Example 102:______________________________________Cycloartenyl ester of p-aminocinnamic 100 mgacidLactose 53 mgCorn starch 39 mgPotato starch 2 mgTalc 3 mgMagnesium stearate 3 mgTotal 200 mg______________________________________
According to the above prescription, the ingredients were uniformly mixed and granulated with an extruder.
FORMULA EXAMPLE 20
Capsules F
Hard capsules of No. 2 were filled with granules G prepared according to Formula Example 19. One capsule contained 200 mg of granules G.
FORMULA EXAMPLE 21
______________________________________Capsules GCompound of Example 102:______________________________________Cycloartenyl ester of p-aminocinnamic 150 mgacidSodium laurylsulfate 4 mgDisodium hydrogen phosphate 1 mgMannitol 93 mgMagnesium stearate 2 mgTotal 250 mg______________________________________
According to the above prescription, the ingredients were uniformly mixed. No. 1 gelatin capsules were filled with 250 mg of the mixed powder each.
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A triterpenyl ester of organic acid other than triterpenyl esters of ferulic acid and of monobasic and dibasic saturated fatty acids. A process for producing a triterpenyl ester of organic acid other than esters of ferulic acid and of monobasic and dibasic saturated fatty acids, which comprises the reaction of a triterpenyl alcohol with an acid halide of the corresponding organic acid. A pharmaceutical composition for treatment of hyperlipidemia comprising a pharmaceutical carrier and an effective amount of a triterpenyl ester of organic acid other than triterpenyl esters of dibasic saturated fatty acids. A pharmaceutical composition for treating hyperlipidemia which comprises a pharmaceutical carrier and an effective amount of cyclobranol as an active ingredient.
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FIELD OF THE INVENTION
[0001] The invention concerns a method of refractive surgical treatment by means of a laser, in which a succession of laser pulses is produced and a material region to be divided is irradiated with the succession of laser pulses. A further aspect of the invention is an apparatus for refractive surgical treatment including
means for producing a succession of laser pulses, and means for guiding the laser pulses on to a material region to be divided.
BACKGROUND OF THE INVENTION
[0004] The use of laser pulses, in particular ultrashort laser pulses with a laser pulse duration in the range of between approximately 10 −15 s and 5×10 −10 s for the purposes of high-precision laser microstructuring operations is known.
[0005] G Mourou, in U.S. Pat. No 5,656,186 (EP 0 754 103 B1, application filing date 8.4.94 ‘Method for controlling configuration of laser induced breakdown and ablation’), describes the basic suitability of individual ultrashort laser pulses for material processing.
[0006] In his dissertation relating to ‘Mikromaterialbearbeitung mit ultrakurzen Laserpulsen’, Cuvillier Verlag Gottingen, 1999, S Nolte discusses aspects of material processing using femtosecond laser pulses.
[0007] The treatment of vision defects in the human or animal eye by means of short laser pulse treatment is also previously known.
[0008] Thus in U.S. Ser. No. 005984916A (application filing date 20.4.93, ‘Ophthalmic surgical laser and method’) Shui T Lai describes the advantages of ultrashort pulses for refractive surgery on the eye.
[0009] In an article relating to ‘Application of ultrashort laser pulses for intrastromal refractive surgery’, Graefe's Arch Clin Exp Ophthalmol 238:33-39, 2000, H Lubatschowski et al describe the use of laser systems which produce ultrashort laser pulses of a duration of 100-200 femtoseconds, in the area of intrastromal refractive surgery.
[0010] Kurtz et al, ‘Optimal Laser Parameters for Intrastromal Corneal Surgery’, SPIE, Vol 3255, 56-66, January 1998, also use ultrashort laser pulses for tissue treatment.
[0011] For the treatment of vision defects, for example short-sightedness (myopia), various surgical interventions on the eye are employed to correct or at least reduce such defective vision. For example, in a first surgical treatment method (referred to as the ‘LASIK’ method), in a first step a cut is made with a special mechanical cutting device along a frontal plane through the cornea in order in that way to be able to lift off a flap of the cornea and fold it back.
[0012] Subsequently in a second step, usually starting from the cut surface of the body of the eye, a material removal operation is carried out in order to remove a lens-shaped piece of tissue. That material removal operation is either executed with the same mechanical cutting device as the first step in order to cut out the piece of tissue. In another operative procedure a second step involves material ablation by means of an excimer laser, which does not involve a cut but material vaporisation.
[0013] Then in a third step the corneal flap which had been folded away is folded back into place again and thus with its cut surface joins the surface produced by the lens-shaped cuffed-out configuration/the lens-shaped removal. The two wound surfaces are then joined together as they heal.
[0014] The optical properties of the cornea are changed by removal of the lens-shaped piece of tissue from the cornea. It is possible to achieve specifically targeted optical correction by virtue of a specific contour in respect of that lens-shaped piece of tissue.
[0015] In another procedure for treating vision defects the lens of the eye is removed and replaced by an artificial lens affording different optical properties. For that purpose it is also necessary in a first step to make an incision in the cornea of the eye in order to permit removal of the lens and fitment of the artificial lens.
[0016] Basically mechanical operating instruments are used for the first step in both of the above-mentioned methods as such instruments ensure an acceptable level of cutting performance and precision. The use of known laser cutting methods on the eye is limited as the cut surface quality is frequently not sufficiently high for the optical demands and the healing process is slowed down by virtue of thermal damage in the adjoining region of the cut surface or indeed complications can arise in regard to definitive healing of the operative incisions.
[0017] In general, that is to say also in accordance with the present invention, ultrashort laser pulses can be used for cutting, removing and structuring material (for example biological tissue) and for modifying material properties (for example for modifying the refractive index in glass).
[0018] The particular advantages of material processing with ultrashort laser pulses (fs-laser pulses) are found in particular in relation to the extremely precise cutting and/or ablation of materials, involving less damage both thermally and also mechanically, than in a series of other material processing methods. Due to focusing of the ultrashort laser pulses, energy is deposited at the focus in a very limited space by triggering of a microplasma and a cutting effect or material ablation is achieved by so-called photodisruption. It is possible to achieve removal rates in the sub-μm range with cutting widths of less than 500 nm. By virtue of a non-linear interaction mechanism involved in photodisruption, material removal is in that case substantially independent of the properties of the material. In particular, when using fs-laser pulses, it is also possible to deal with materials involving a high level of thermal conductivity (such as for example metals) and materials involving a low degree of laser light absorption (such as for example polymers or certain biological tissues).
[0019] As an alternative to ablation on the surface of a material to be treated, focusing into materials which are transparent for laser radiation (such as for example the cornea of an eye) also makes it possible to achieve a cutting effect in the interior of the transparent material (tissue).
[0020] One problem in material processing by means of laser is that material division is achieved by the laser energy in the irradiated region and in addition material changes are caused in adjoining regions, and such changes are generally undesirable. Those changes in material are decisively dependent in extent and magnitude on how high the energy of the laser beam and its temporal distribution is.
[0021] EP 1 284 839 A1 and U.S. Pat. No 6,787,733 W2 describe a method of laser processing of materials, involving online control of the processing result in order to optimise material processing and to minimise unwanted side-effects. Admittedly, online control of the processing operation is possible with that method and in that case also any side-effects which occur can be observed, but it is not possible with that method to avoid surrounding regions of material being influenced by the laser radiation, besides the region which is to be treated thereby.
[0022] The interaction mechanism in tissue treatment by means of short intensive laser pulses is based on so-called photodisruption. Photodisruption occurs when light is focused to intensities of the order of magnitude of 10 11 to 10 12 W/cm 2 . At such high levels of intensity, almost any kind of material is abruptly ionised by virtue of multi-photon absorption (plasma generation). If that process takes place in transparent material (water, glass, cornea) it is referred to as ‘optical’ breakdown.
[0023] The explosive expansion of the laser-induced plasma causes the development of a strong pressure front and—if the process takes place in a fluid environment—a cavitation bubble. The pressure front as well as the cavitation bubbles can represent a considerable mechanical damage potential for surrounding material/tissue. That damage potential of an individual laser pulse scales however with the laser pulse energy.
[0024] A high level of intensity however is necessary to trigger optical breakdown. The shorter a laser pulse, the correspondingly less energy it transports, at the same level of intensity. Consequently, short laser pulses are a necessary prerequisite in order to implement photodisruption at a high level of precision and with slight mechanical side-effects.
[0025] The laser pulse duration, that is to say the time for which the laser radiation acts, is however also of crucial significance in regard to thermal damage to the irradiated material. If the radiation duration of the laser is so short that, during the irradiation procedure, no significant amount of thermal energy is lost due to heat diffusion from the absorption volume, that situation is referred to as ‘thermal confinement’. The maximum irradiation time (laser pulse duration) at which the conditions of ‘thermal confinement’ are maintained is also referred to as the thermal relaxation time τ R and is given by the following relationship:
τ R = δ 2 4 κ
In that relationship:
[0026] δ: denotes the optical depth of penetration into the irradiated material/tissue, in the case of disruption in transparent media δ corresponds to the expansion in the non-linear absorption zone; and
[0027] κ: denotes the thermal diffusion constant of the irradiated material/tissue.
[0028] If the time of action (laser pulse duration) is markedly shorter than τ R , the zone of thermal influence which the laser pulse exerts on the irradiated material is determined primarily by the optical depth of penetration δ. In the case of a laser pulse duration which is markedly longer than τ R , the zone of thermal influence acts beyond the optical depth of penetration by virtue of thermal diffusion.
[0029] When dealing with metals in respect of which an optical depth of penetration of only a few nanometers is involved and a comparatively high level of thermal diffusion prevails the use of pico- or even femtoseconds is therefore essential in order also to minimise the zone of thermal influence. Organic substances or biological tissue with a substantially lower level of thermal diffusion and with very much higher optical depths of penetration in contrast have thermal relaxation times in the region of nanoseconds or even microseconds.
[0030] However the reduction in the laser pulse duration is subject to technological limits at the present time and also does not prevent the surrounding regions being subjected to unwanted influences.
[0031] In principle to achieve material division it is necessary to introduce a certain amount of energy into the region to be divided, with the laser pulse. The level of that energy is dependent on the material. In the case of material division along a line or a surface, a plurality of laser pulses are used in mutually juxtaposed relationship, with the appropriate laser pulse energy, in order to achieve a division line or division surface. The disruptive effect of the individual laser pulses can give rise to unwanted mechanical changes in the material, depending on the respective nature of the material. Such changes include tearing effects in the tissue, which causes an irregular cut surface, or the formation of gas bubbles which can also detrimentally influence the geometry of the cut. In that case the extent of the unwanted changes in the material scales with the energy of the individual laser pulses.
[0032] By virtue of the versatile possible forms of use and the possibility of incisions which are controlled in an automated mode, lasers are already used for a series of incision procedures and removal procedures on the eye. A limitation in terms of possible forms of use is however imposed for example due to thermal tissue damage and the in part still unsatisfactory quality of the cut surface. There is therefore a need for improvement to the effect that the cleanness of the cut is increased, that is to say the degree of roughness of the cut surface is reduced and the evenness thereof is enhanced. There is also a need to provide a precise cutting method for refractive surgery, which allows the tissue surrounding the cut surface to be dealt with as gently and carefully as possible. The aim of the invention is to meet that need.
[0033] In a German patent application which has not yet been laid open, Lubatschowski describes a method of material and tissue division by means of irradiation of a region of the material with a succession of laser pulses, in which the laser pulse energy of an individual laser pulse of the succession of laser pulses is less than the laser pulse energy which is used to produce material division with an isolated laser pulse in the region irradiated with the individual laser pulse of the succession of laser pulses. That method is suitable for precision cutting of materials with laser pulses.
[0034] The merit of the inventor of this patent application is to recognise the advantageous use of that method for refractive surgery. In refractive surgery a deliberate cut is made in the corneal tissue of a human being or animal in order in that way to be able to correct a vision defect. Actual correction of the vision defect is effected in the case of the surgical treatment methods referred to hereinbefore by way of example, by cutting out in a lens form a part of the cornea or by removal and replacement of the lens. There is a need for treatment methods with which such a treatment can be carried out as gently and carefully as possible for the surrounding tissue and at the same time safely and effectively.
SUMMARY OF THE INVENTION
[0035] In accordance with the invention that need is met by a method of the kind set forth in the opening part of this specification, in which the laser pulse energy of an individual laser pulse of the succession of laser pulses is less than the laser pulse energy which is required for producing material division with an isolated laser pulse in the region irradiated with the individual laser pulse of the succession of laser pulses.
[0036] The invention capitalises on the realisation that, for cutting the cornea, it is not necessarily required for the total energy necessary for the division operation to be introduced at one location with an individual laser pulse. Instead that total energy can be applied by a plurality of laser pulses which are produced for example by one and the same laser and which are successively introduced at the same location in the division region. In that way it is possible to achieve material treatment by means of a plurality of successive laser pulses involving a low level of laser pulse energy and in that case to avoid damage to the irradiated material in the surrounding region.
[0037] It has been found that the energy for material division, that is to say that total energy which is at least required to achieve material division, falls with a rising repetition frequency. Consequently with high repetition rates material division can be achieved with a substantially lower level of laser pulse energy than when low repetition rates are used.
[0038] The invention provides a treatment method which is suitable both for effecting the first cut in the cornea of the eye with a pulsed laser and also for other incisions in the cornea, for example for cutting out a lens-shaped piece of tissue from the previously produced cut surface. The thermal and mechanical damage to the surrounding tissue is reduced and the quality of the cut surface is increased.
[0039] In particular the laser pulse energy can be reduced by reducing the laser pulse intensity and/or the laser pulse duration. This means that the laser pulse intensity and/or the laser pulse duration in the method according to the invention is lower than the laser pulse intensity and/or the laser pulse duration which is required in conventional technology to achieve tissue division. It is possible in that fashion to achieve a reduction in laser pulse energy in a simple manner.
[0040] It is particularly advantageous if the irradiated region is spatially overlapped by two or more laser pulses, which occur in succession in respect of time, of the succession of laser pulses. By virtue of that spatial overlap, the laser pulse energy of two or more laser pulses is introduced into the overlap region and thus when added can afford a total energy which achieves material division. That realisation is a departure from the previous approach of spacing the laser pulses from each other as far as possible in respect of time and space in order to separate the thermal influence of each individual laser pulse from that of a subsequent laser pulse, and it achieves a reduction in the unwanted mechanical and thermal influence by virtue of the overlap, insofar as at the same time the laser pulse energy of each individual laser pulse is reduced.
[0041] In that respect it is particularly advantageous if the irradiated region is spatially overlapped by two or more laser pulses, which occur in succession in respect of time, of the succession of laser pulses at 100% or in the range of between 10% and 100%, preferably around 70% to 99%, in particular 92%-99%. The overlap of the laser pulses basically depends on the diameter of the laser beam at the focus (focus beam diameter), the laser pulse repetition frequency and the relative advance speed between the material to be cut and the laser. The overlap in percent is defined in this connection as:
Overlap = 100 × ( 1 - advance speed laser pulse repetition frequency × focus beam diameter )
[0042] The specified values are suitable for material division of a large number of different materials. The spatial overlap of 100% can be for example of such a nature that two or more laser pulses 100% overlap, thereupon the laser beam is displaced relative to the material being worked and then once again two or more laser pulses are discharged, which 100% overlap. As an alternative to that discontinuous advance, it is advantageous in many uses if a continuous advance movement takes place and if the movement is so adjusted that, with a given laser pulse repetition frequency and laser beam diameter at the focus, an overlap of 70-99%, in particular 92%-99%, is achieved.
[0043] It is further advantageous if the laser pulse energy, the laser pulse intensity, the dimensions of the focus area, the laser pulse duration of an individual laser pulse, the laser pulse repetition frequency of the succession of laser pulses and/or the advance speed between the laser beam and the material to be processed is preset in dependence on the properties of the material. An important dimension of the focus area, which is to be preset, is frequently for example the diameter of the laser beam at the focus or the length of the focus area in the beam direction, which is influenced inter alia by the aperture. The optimum parameters depend on the properties of the material to be processed, in particular the thermal diffusion constant and the relaxation time of the material. In principle it is for example advantageous to set higher laser pulse repetition frequencies, when high thermal diffusion constants are involved, than when low thermal diffusion constants are employed. There is an inverse relationship between relaxation time and laser pulse repetition frequency: with long relaxation times, usually lower laser pulse repetition frequencies can be selected than when the relaxation times are short.
[0044] It is further advantageous if the laser pulse repetition frequency of the succession of laser pulses is so high that, within a material-specific duration of the material to be divided, for example the thermal relaxation time, at least two laser pulses are delivered on to the material to be divided. In that way the laser pulse energy of the two laser pulses delivered within the material-specific period can be accumulated and cause division of the material. In that case the thermal and mechanical damage can be reduced by a large number of laser pulses being delivered on to a region of the material to be divided, within the material-specific period, and by the energy of each of those laser pulses being selected at a suitably low level in order to introduce the total accumulated energy required for material division, precisely by means of that large number of laser pulses.
[0045] It has proven to be particularly advantageous in this respect if the laser pulse repetition frequency is greater than 10 Hz, in particular greater than 50 Hz and is preferably between 100 Hz and 50 MHz. Those laser pulse repetition frequency ranges already cause a marked reduction in the required laser pulse energy per laser beam and can thus significantly reduce the mechanical damage.
[0046] With the above-mentioned embodiments, it is particularly to be noted that there is a mathematical relationship between overlap, laser pulse repetition frequency, the dimensions of the focus area, for example the diameter of the laser beam at the focus, and the advance speed. The ultimately decisive parameter, that is to say the number of laser pulses introduced at a material processing location or the overlap, can be influenced by a variation in the corresponding other parameters. Thus that number can be individually increased in each case by reducing the advance speed, increasing the diameter of the laser beam at the focus or increasing the laser pulse repetition frequency, if the corresponding two other parameters are kept constant. A reduction in the diameter of the laser beam at the focus, an increase in the advance speed and a reduction in the laser pulse repetition frequency make it possible to achieve a reduction in the number of laser pulses per location point on the line along which material processing is effected.
[0047] In addition it is advantageous if the laser pulse energy, the laser pulse intensity, the dimensions of the focus area, the laser pulse duration of an individual laser pulse, the laser pulse repetition frequency of the succession of laser pulses and/or the advance speed between the laser beam and the material to be processed is changed during the processing operation. With that embodiment it is for example possible to set the laser pulse energy of the individual laser pulses in such a way that, in dependence on the overlap of the laser pulses, precisely the energy required for material division at the location just being processed is introduced into the material. In that respect it may be advantageous if the laser pulse energy is set in dependence on the predetermined or set laser pulse repetition frequency and/or advance speed. Such setting can be effected automatically or manually by the user.
[0048] In the case of developments of the method involving an adjustable laser pulse repetition frequency and an adjustable laser pulse energy, it is particularly advantageous if a first laser pulse energy is set in the case of a first laser pulse repetition frequency and a second laser pulse energy which is lower than the first laser pulse energy is set in the case of a second laser pulse repetition frequency which is higher than the first laser pulse repetition frequency. That provides for automatic adaptation of the laser pulse energy to the laser pulse repetition frequency and in that respect in each case the required accumulated total energy for achieving material division is introduced.
[0049] In that respect it is particularly advantageous if
[0050] the laser pulse repetition frequency is set automatically in dependence on the laser pulse energy, or
[0051] the laser pulse energy is set automatically in dependence on the laser pulse repetition frequency,
[0052] the laser pulse energy and/or the laser pulse repetition frequency are set automatically in dependence on the advance speed, or
[0053] the laser pulse repetition frequency, the laser pulse energy and/or the advance speed are set automatically in dependence on at least one material property of the material to be divided.
[0054] This development in the method permits the method parameters which are primarily crucial for material division to be set in dependence on each other or to be automatically correctly set in dependence on the material to be processed. Thus, in the case of the method according to the invention, it is possible to have recourse to a database which provides the ideal method parameters for respectively typical materials and those method parameters are then set by material selection. Alternatively, the total energy required for material division can be taken from a database and then, on the basis of method parameters selected by the user, the correspondingly other method parameters are so selected that that required total energy is achieved.
[0055] A further aspect of the invention lies in a method of the kind set forth in the opening part of this specification or the kind referred to above, wherein, in the start region of the dividing operation, the total energy introduced at a location of the material to be processed is higher than in a region in the further course of the dividing operation.
[0056] That development is based on the realisation that, to achieve initial material division in a material, a higher level of total energy is required in order to achieve a first material division effect and subsequently a lower level of total energy is required for maintaining and enlarging that initial material division effect. It is therefore advantageous for the laser pulse energy, after an initially high level in the start region of the dividing operation to achieve initial material division, to be subsequently reduced to a lower level which is sufficient to maintain and continue with the initial material division effect in order in that way to minimise damage along the division line or the division surface.
[0057] In particular it is advantageous if, in the start region, the laser pulse energy, the laser pulse repetition frequency and/or the number of laser pulses delivered on to a location on the material is higher and/or the advance speed between the laser beam and the material to be processed is lower than in the further course of the dividing operation. The laser pulse energy is composed of the laser pulse intensity and the laser pulse duration. Therefore, to achieve an initial dividing operation in the start region, it is possible to set a higher level of laser pulse intensity than in the region of the further course of the dividing operation, for maintaining and continuing with the division effect.
[0058] In the same manner, with a constant laser pulse intensity, the laser pulse duration could be increased in the start region and reduced in the further course of the procedure and/or the laser pulse repetition frequency could be increased in the start region and reduced in the further course of the procedure.
[0059] A further development provides that the laser pulse intensity and/or the laser pulse duration of an individual laser pulse is higher in the start region of the dividing operation than in a region in the further course of the dividing operation. That development can in the same manner implement initial division with a high level of laser pulse energy and further division with a lower level of laser pulse energy, but with a variation in other parameters than in the above-described embodiment.
[0060] In particular, for the method according to the invention, it is advantageous if the laser pulse duration is less than ten picosecond, and in particular less than one picosecond. The laser beam treatment which is achieved in that way, in the femtosecond range, permits particularly advantageous laser pulse energy rates and laser pulse repetition frequencies, for a large number of materials, and generally avoids unwanted damage.
[0061] It is further advantageous for the method according to the invention if the laser beam is focused, preferably with an optical system having a numerical aperture which is at least so large that material division is achieved beneath the surface of a semi-transparent or completely transparent material without regions of material which are above or beneath the division region being damaged. That makes it possible to produce a laser beam focus and, upstream and downstream of that laser beam focus in the direction of the beam, to avoid division of or damage to the material, whereas such a material division effect is achieved at the laser beam focus.
[0062] Finally it is further advantageous for the method according to the invention if the dividing operation is observed and, if the division performance drops off, the total energy introduced is increased by modifying one of the parameters which are relevant in terms of division performance, as set forth hereinbefore. In this connection the term observation is intended to denote direct optical or sensor observation of the cut or also observation or monitoring of technical parameters, for example equipment performance data, by a user or automatically, in order to infer an altered division performance from a change in those parameters.
[0063] The method can be used in particular to perform a first cut for opening up the cornea by irradiating a region of the cornea with the succession of laser pulses. That first cut can either only partially open up the cornea in order for example to apply the LASIK operative technique or the first cut can completely cut through the cornea in order to afford access to the lens.
[0064] It is further preferred if a second cut for removal of a lens-shaped piece of tissue from the cornea is implemented by irradiating a region of the cornea with the succession of laser pulses.
[0065] The first and second cuts are performed in the state of the art in the form of planar cuts. The method according to the invention makes it possible for the first time to achieve a precise geometry in respect of the cut surface, which can be geometrically freely selected by the surgeon, by means of laser division. In addition the method provides a high surface quality for the cut surfaces as well as a low level of thermal and mechanical damage to the tissue adjacent to the cut surfaces. The laser cutting technique which is possible by the method according to the invention, for cutting out a lens-shaped piece of tissue, permits an incision to be made with more precision than when using a mechanical cutting technique which, in the state of the art, is always performed as a planar cut on a deliberately (elastically) deformed portion of cornea (referred to as applanation).
[0066] A further aspect of the invention is an apparatus of the kind set forth in the opening part of this specification, which is developed in accordance with the invention in that the means for producing a succession of laser pulses are so adapted that the laser pulse energy of an individual laser pulse of the succession of the laser pulses is less than the laser pulse energy which is required for producing material division with an isolated laser pulse in the region irradiated with the individual laser pulse of the succession of laser pulses. In that way it is possible to keep the laser pulse energy of an individual laser pulse in a low range and thereby to achieve material division with the method according to the invention. In regard to the advantages and effects of the apparatus designed in that way attention is directed to the foregoing description of the corresponding method.
[0067] A development of the apparatus according to the invention can provide that the means for producing the succession of laser pulses is adapted to reduce the laser pulse energy by a reduction in the laser pulse intensity and/or the laser pulse duration.
[0068] A further development of the apparatus according to the invention can include advance means for producing a relative movement between the laser beam and the material to be divided and means for producing a laser pulse repetition frequency, which co-operate in such a way that the irradiated region is spatially overlapped by two laser pulses, which occur in succession in respect of time, of the succession of laser pulses. That achieves the overlap, which is advantageous in accordance with the invention, of at least two successive laser pulses. In that case the advance means are preferably so designed that they are operable in dependence on the laser pulse repetition frequency.
[0069] It is further advantageous if the advance means and the means for producing a laser pulse repetition frequency co-operate in such a way that the irradiated region is spatially overlapped by two laser pulses, which occur in succession in respect of time, of the succession of laser pulses at 100% or in the range of between 10% and 100%, preferably around 70% to 99%, preferably from 92% to 99%. In that respect attention is directed to the preceding description of the corresponding form of the method.
[0070] Preferably, the apparatus according to the invention has control means for setting the laser pulse energy, the laser pulse intensity and/or the laser pulse duration of an individual laser pulse, the laser pulse repetition frequency of the succession of laser pulses, the dimensions of the focus area of the laser beam at the processing location, for example the diameter of the laser beam at the focus and/or the advance speed between the laser beam and the material to be processed, in dependence on the material properties. The control means can be actuated automatically by the apparatus in respect of one of the parameters in dependence on other parameters or can be actuated manually by a user.
[0071] In that respect it is particularly advantageous if the control means are so adapted that the laser pulse repetition frequency of the succession of laser pulses is so high that, within a material-specific period of time, for example the thermal relaxation time of the material to be divided, at least two laser pulses are delivered to the material to be divided. That achieves the advantageous accumulation of two or more laser pulses within the material-specific period of time and in that way attains particularly gentle and careful division of the material.
[0072] In particular in that case the control means can be so adapted that the laser pulse repetition frequency is greater than 10 Hz, in particular greater than 50 Hz and preferably between 100 Hz and 50 MHz. In that respect attention is directed to the foregoing corresponding form of the method.
[0073] It is further advantageous if the control means are adapted to alter at least one of the six above-listed parameters during the processing operation. In that way the total energy and/or the laser pulse energy can be set in dependence on the material properties or in dependence on other parameters of the cutting operation.
[0074] The control means can preferably be so adapted that
[0075] the laser pulse repetition frequency is set automatically in dependence on the laser pulse energy, or
[0076] the laser pulse energy is set automatically in dependence on the laser pulse repetition frequency,
[0077] the laser pulse energy and/or the laser pulse repetition frequency are set automatically in dependence on the advance speed, or
[0078] the laser pulse repetition frequency, the laser pulse energy and/or the advance speed are set automatically in dependence on the at least one material property of the material to be divided.
[0079] In particular it is advantageous for the apparatus according to the invention if the control means are adapted to control at least one of the six above-listed parameters (laser pulse repetition frequency, laser pulse energy, laser pulse intensity, laser pulse duration, focus dimension and advance speed) in such a way that in the start region of the division operation the total energy introduced into a location of the material to be processed is higher than in a region in the further course of the division operation.
[0080] It is further preferred in a development of the apparatus according to the invention that the control means are adapted in the start region to set the laser pulse energy, the laser pulse repetition frequency and/or the number of laser pulses delivered to a location of the material higher and/or the advance speed between the laser beam and the material to be processed lower than in the further course of the division operation.
[0081] Preferably the control means are adapted to set the laser pulse intensity and/or the laser pulse energy of an individual laser pulse higher in the start region of the division operation than in the further course of the division operation.
[0082] In particular it is advantageous if the means for producing a succession of laser pulses are adapted to produce a laser pulse duration of less than 10 picoseconds, preferably less than 1 picosecond.
[0083] The apparatus according to the invention can be further developed by focusing means for focusing the laser beam, preferably with an optical system with a numerical aperture which is at least so great that material division is achieved under the surface of a semitransparent or completely transparent material without material regions above or below the division region being damaged.
[0084] Finally a further development of the apparatus according to the invention provides an observation device for observing the division operation, which co-operates with the means for producing a succession of laser pulses, the means for guiding the laser pulses on to a material region to be divided and/or the advance means in such a way that if the division performance drops off the total energy introduced is increased by altering at least one of the six above-listed parameters. In this respect attention is directed to the preceding description relating to the method involving observation of the division operation.
[0085] In regard to the developments of the apparatus according to the invention, in terms of their advantages, modes of operation and preferred variants, attention is directed to the foregoing description of the respective properties of the corresponding development of the method.
DESCRIPTION OF THE DRAWINGS
[0086] The invention is described hereinafter by means of specific embodiments and test results with reference to the drawings in which:
[0087] FIG. 1 shows a diagram illustrating the relationship between the pulse energy to be introduced for material division and the laser pulse repetition frequency,
[0088] FIG. 2 shows a diagram illustrating the relationship between the laser pulse energy required for the beginning of material division and the laser pulse energy required at least for continuing with material division, with a laser pulse overlap in the range of −100% to +100%,
[0089] FIG. 3 shows a diagram illustrating the relationship between a laser pulse energy required for material division, with the laser pulse overlap in the range of 92% to 100%,
[0090] FIG. 4 shows a diagrammatic representation of line material division with a laser pulse overlap of 50%, and
[0091] FIG. 5 shows a diagrammatic representation of line material division with a variable laser pulse overlap in the start region and in the further course of the division operation.
DETAILED DESCRIPTION
[0092] Referring to FIG. 1 it can be seen from this diagram which in the region A was determined with a laser pulse duration of 150 fs, a wavelength of 780 nm and an aperture of 0.6 and in the region B with a laser pulse duration of about 15 fs, a wavelength of 800 nm and an aperture of 0.5, that, with a laser pulse repetition frequency of 1 Hertz, an energy of about 45 nJ is required to achieve material division. That required level of energy falls with an increasing laser pulse repetition frequency and reaches a value of below 5 nJ at a laser pulse repetition frequency of 1 MHz.
[0093] FIG. 2 shows the dependency of the laser pulse energy required for beginning a material division operation (‘beginning of the cut’) and the laser pulse energy at least required for continuing with the material division (‘breaking off the cut’) with the laser pulse overlap in the range of −100% to +100%. In that respect a negative pulse overlap signifies that between two adjacent pulses there remains a non-irradiated region of material which, with a −100% pulse overlap, for example precisely corresponds to the focus diameter.
[0094] It can be seen that, with adequate spacing in respect of the individual pulses from each other (negative pulse overlap) the beginning and the break-off of the cutting effect occur with the same pulse energy, that is to say there is no mutual influencing of the pulses. The greater the pulse overlap that is adopted however, the correspondingly lower is on the one hand the pulse energy which is required for beginning the cut and the pulse energy at which the cut is broken off. In addition the pulse energy which is required for beginning the cut and the pulse energy at which the cut is broken off are correspondingly further apart, the higher the degree of pulse overlap. Consequently, division can be initially effected with a correspondingly lower level of pulse energy and the cutting operation can be continued with a corresponding lower level of pulse energy, the greater the degree of pulse overlap that is adopted.
[0095] FIG. 3 shows the measurement results for the cutting operation with high levels of pulse overlap. The diagram plots the results of five series of measurements with different degrees of overlap and a compensating straight line through those series of measurements. It can be seen that, with an overlap of 92%, the method must be operated with an individual laser pulse energy of about 19 nJ. That required level of individual laser pulse energy falls with an increasing degree of overlap and, with an overlap of about 99.5%, reaches a value of just 2 nJ.
[0096] Referring to FIG. 4 , shown therein is a material 10 to be divided and a succession of individual laser pulses 1 - 9 which serve to divide that material. The individual laser pulses are diagrammatically shown in the configuration of their focus area. The individual laser pulses 1 - 9 are applied to the material in succession in respect of time from left to right. In that case the laser pulses each overlap in the regions 1 - 8 a. In the procedure of the method as illustrated in FIG. 4 the laser pulse repetition frequency, the advance speed and the focus diameter are so set that there is an overlap of 50%, that is to say the laser pulses 1 and 2 overlap in the region 1 a, the laser pulses 2 and 3 overlap in the region 2 a and so forth. In that way, each region along the line of cut is irradiated by two laser pulses.
[0097] Referring to FIG. 5 , shown therein is a succession of laser pulses 11 - 22 serving to divide a block of material 30 .
[0098] The laser pulses 11 - 22 are applied in a rising sequence from left to right. It can be seen that the laser pulses 11 - 14 involve a greater degree of overlap than the following laser pulses 15 - 22 . That serves to introduce, in the left-hand start region of the division operation, a higher level of total energy which is sufficient for initial division, than in the further course of the procedure towards the right along the division line where only a lower level of total energy is required for the division region in order to continue with initial division.
[0099] The accumulation of laser pulses 11 - 14 shown in FIG. 5 can be achieved for example by selecting an increased laser pulse repetition frequency in that start region or by setting a reduced advance speed in that start region.
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A method and apparatus for a refractive surgical treatment that uses a laser which produces a succession of laser pulses applied to a material region. The laser pulses irradicates the material region to be divided where the energy of the individual pulse in less than the energy required to produce the material division or cutting.
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FIELD OF THE INVENTION
The present invention generally relates to a fusing device used in reproduction apparatus for fixing a toner image to a receiver, such as a sheet of copy paper. More specifically, the present invention relates to a fusing device which is movable in a lateral direction to reduce or eliminate fuser roller defects, such as swelling, stepping and grooving.
BACKGROUND OF THE INVENTION
Generally, a fusing unit for fixing toner images in a reproduction apparatus has a heated fuser roller. The fuser roller is of cylindrical shape with a metallic core over which is formed an elastomeric layer. The elastomeric layer of the fuser roller makes contact with a pressure roller to form a fusing nip through which a receiver, carrying the toner images is passed to fuse the toner images to the receiver. This type fusing unit is known to have high thermal efficiency with minimal danger of causing a fire if receiver jamming occurs. A problem, however, with this type of fusing unit is the elastomeric layer has a tendance to swell, step or groove over a period of use, typically in the range of 100,000 or more copies, resulting in wrinkling or other unacceptable fusing performance. This swelling and grooving occurs at the portion of the fuser roller near the ends of the receiver and outward therefrom where the fuser roller is not protected, during fusing, from the pressure roller by the presence of the receiver between the fuser roller and the pressure roller. Accordingly, in such end portions of the fuser roller, high stresses are created between the directly contacting surfaces of the fuser roller with the pressure roller. As a net result, the thin outer layer or coating, of the fuser roller, in the unprotected area tends to fail. This failure is hastened by continued use of the same width receiver or large volume runs of the same width receiver constantly moving across the same area of the fuser roller.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a fusing station that minimizes swelling, stepping or grooving of the fuser roller.
The above object is accomplished by a fusing station installable in a reproduction apparatus for fusing a toner image to a receiver as the receiver moves through a nip formed by rotating rollers, the fusing station comprising:
means for mounting the rollers in rotational and pressure contact with each other;
means for laterally moving at least one of the rollers relative to the movement of the receiver through the nip;
guide means for guiding the lateral movement of at least one of the rollers relative to the movement of the receiver through the nip;
drive means for imparting lateral movement to at least one of the rollers; and
means for controlling the activation and de-activation of the drive means.
The invention, and its objects and advantages, will become more apparent in the detailed description of the preferred embodiment presented below.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic front view of the fuser station in accordance with the present invention.
FIG. 2 is a schematic side view of the fuser station in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In describing the preferred embodiment of the present invention, reference is made to the drawings, wherein like numerals indicate like parts and structural features in the various views, diagrams and drawings.
While this invention is susceptible of embodiment in many different forms, there are shown in the drawings and will herein be described, in detail, a preferred embodiment of the invention. It should be understood, however, that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the embodiments illustrated and/or described.
The precise shapes and sizes of the components herein described are not essential to the invention unless otherwise indicated, since the invention is described with only reference to an embodiment which is simple and straightforward.
For ease of description, the apparatus will be described in a normal operation position, and terms such as upper, lower, horizontal, etc. . . . , will be used with reference to this normal operation position. It will be understood, however, that this apparatus may be manufactured, stored, transported and sold in an orientation other than the normal operation position described.
Much of the apparatus disclosed herein has certain conventional drive and control mechanisms the details of which, though not fully illustrated or described, will be apparent to those having skill in the art and an understanding of the necessary functions of such drive mechanisms.
Referring now to FIG. 1 a fusing station 1 is provided of the type having a pressure roller 2 and a heated fuser roller 3, in pressure contact with each other, to form a fusing nip 4. A receiver 5, carrying an image to be fused, is delivered to fusing nip 4, by a series of transport rollers 26, see FIG. 2, subsequent to receiver 5 leaving a typical transfer station, of a reproduction apparatus, not shown, but known in the art.
Fusing station 1 is mounted, on a stationary base plate 6, of the reproduction apparatus, for lateral movement, of fusing station 1, relative to the direction of travel of receiver 5 through nip 4. As shown in FIG. 2, stationary base plate 6 has two grooves 7. Tracks 8 located on bottom plate 15, of fusing station 1, are inserted into grooves 7 so that the lateral movement of fusing station 1 over base plate 6 is parallel to fusing nip 4, thereby preventing fusing station 1 from becoming skewed relative to receiver 5. While a track and groove system has been shown and described for guiding the lateral movement of fusing station 1, other methods of guiding lateral movement, which are known in the art, but not shown, such as roller slides may be used to guide the lateral movement of fusing station 1.
As shown in FIG. 1, shaft 16 of fuser roller 3 and shaft 9 of pressure roller 2 are mounted for rotational movement within a bracket system containing roller brackets 10 and 11 secured to bottom plate 15. Connected to roller bracket 11 is a drive linkage 30, such as a lead screw/nut linkage. A nut 12, of lead screw/nut linkage 30, is located within or attached to bracket 11. One end of a lead screw 13 is in threaded mating contact with nut 12 and the other end of lead screw 13 is connected to a motor 14. Lead screw/nut linkage 30 converts the rotation output of motor 14 into a linear drive that moves fusing station 1, within guide grooves 7, laterally over stationary plate 6. While the above description and drawings portray a lead screw/nut drive system, other drive systems, known in the art, but not shown, for imparting linear motion, such as a crank and slider system, cam drive, belt drive, cable drive or a chain drive system may be used to impart lateral movement to fusing station 1.
To activate and deactivate motor 14, connected to lead screw/nut linkage 30, and thereby impart or cease lateral drive to fusing station 1, a logic and control circuit 17, known in the art, is connected to motor 14. Logic and control circuit 17 is also connected to a receiver sensing device, typically located in a receiver supply tray, which is known in the art, but not shown, that senses the size of receiver 5 to be used in a copying cycle. Logic and control unit 17 is further connected to an operator control panel, known in the art, but not shown, so when the number of copies to be run is selected on the operator control panel, that information may be conveyed to logic and control circuit 17. Logic and control circuit 17, upon receipt of the information from the receiver sensor device and the control panel, compares the information received to a known number. The known number being a representation of the ideal volume for the size receiver that is to be run, through a specified area of nip 4, without risk of fuser roller 3 swelling or grooving. Depending on the results of the comparison, control and logic circuit 17 either activates motor 14, prior to the start of the copy cycle, for a set interval of time, to laterally move fuser station 1 a pre-set distance or maintains motor 14 deactivated and fuser system 1 in a stationary position relative to stationary base plate 6. When comparisons such as the above are capable of being made, by a logic and control circuit, prior to logic and control circuit 17 activating motor 14, such a logic and control circuit is considered, in the art, a smart system. As opposed to using the smart system, above described, logic and control circuit 17 may be programmed to activate motor 14, after a pre-set volume of copies have been fused, say every 10,000, to laterally move fusing station 1. This activation after every 10,000 copies, while normally resulting in fusing station 1 moving more often, has the same end results as with the smart system, in that receiver 5 is not always fused in the same area of fuser roller 3.
The activation, of motor 14, for a pre-set period of time, by either of the above described methods, causes lead screw 13 to rotate and laterally drive fuser station 1, a pre-set distance, toward or away from motor 14. While this lateral movement, of fusing station 1, may be preformed at any time, the comparison by logic and control circuit 17, of information regarding the size of receiver 5 and the amount of receiver 5 to be run, or the monitoring of the total amount of copies run since the last lateral movement of fusing station 1, is preferably performed before each receiver 5 copy cycle. Depending on the outcome of the comparison or the tally of copies already run, motor 14 may or may not be activated, for a period of time, to provide lateral movement to fusing station 1. By performing the comparison or copy run count prior to each receiver 5 copy cycle and restricting lateral movement of fusing station 1, to either between copy runs or during interframes, this avoids adverse effects in the fusing process, that could result from movement of fusing station 1 while receiver 5 is in fusing nip 4.
FIG. 1 illustrates the effects of such lateral movement. If the lateral movement of fusing station 1, is away from motor 14, such lateral movement causes receiver 5, which during the last copy cycle was fused in the area where receiver 5 is shown in solid lines, to now be fused in the area where receiver 5 is shown in dotted lines. As a result of this lateral movement of fusing station 1, the point at which the lateral ends of receiver 5 meet fuser roller 3 is periodically changed thereby reducing the chance of fuser roller 3 swelling or grooving near the location of the lateral ends of receiver 5.
To prevent excessive lateral travel, which would result in fuser station 1 not being positioned to accept receiver 5, as it is conveyed to fusing station 1 by transport rollers 26, the lateral travel of fuser station 1 is limited, by reversing sensors, not shown, but known in the art, connected to lead screw 13. Upon nut 12 of bracket 11 making contact with a reversing sensor, the reversing sensor signals for motor 14 to be de-activated and its rotation reversed. Upon re-activation, of motor 14, the sliding movement of fusing station 1 will be opposite to its previous sliding movement thereby maintaining fusing station 1 in a position to receive receiver 5.
In operation, as an operator places an original document on the reproduction apparatus and selects the amount of copies to be made and the size of receiver to be used, depending on whether logic and control system 17 is a smart system, this information is either conveyed to logic and control circuit 17 for comparison purposes or for tallying the copies that have been made since the last lateral movement of fusing station 1. If either the comparison or the tally indicates fusing station 1 should be laterally moved to prevent possible swelling or grooving of fuser roller 3, logic and control circuit 17 activates motor 14 to laterally move fusing station 1 a pre-determined amount. Once the lateral movement is completed, receiver 5 is processed by the reproduction apparatus and sent, to the now stationary fusing station 1 for fusing. The fusing of receiver 5, however, now takes place in a different area, as shown by the representation of receiver 5 in dotted lines in FIG. 1, of fusing station 1 than the place receiver 5 had been previously fused, as shown by the representation of receiver 5 in solid lines in FIG. 1. This minimizes the swelling or grooving of fuser roller 3 in the location of the lateral edges of receiver 5.
While the invention has been described in detail with particular reference to a preferred embodiment thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
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In a reproduction apparatus, such as a copier, having a fusing station which includes a heated coated fuser roller and a pressure roller forming a nip for fusing a receiver passing through said nip, the fusing station is mounted for lateral movement in relation to the movement of the receiver through the nip.
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BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0001] The present invention relates to a building panel used in the field of building construction; and, in particular, to a synclastic double hull arch truss panel adapted to be assembled into a spherical or dome-shaped structure and a method of making the same.
[0002] Domes can be used, inter alia, for human habitats in locations where extreme weather conditions exist and conventional structures are not suitable, such as artic and desert areas, or high wind terrains. Domes are also used for planetariums, observatories, greenhouses, and capping grain silos. They can make an architectural statement in cities, corporate parks, atriums, houses of worship, government buildings, science and university buildings, among others.
[0003] Spheres can prove useful where great pressure is exerted on the outer surface of the structure, as in underwater habitats, or subterranean structures. In the vacuum of space, spheres or dome-like structures can serve as orbiting space platforms, but are not limited to these conditions.
[0004] Sections of a sphere, when used for constructing three quarter spheres, hemispheres, or quarter spheres typically connect to conventional buildings structures at 180° or 90° on flat roof tops, building side walls, inside and outside right angle corners and the like to expand interior open space and make an architectural statement.
[0005] Previously, spherical or dome like structures were generally built from prefabricated panels supported on a framework. Such panels were typically flat triangles or tetrahedrons in shape and were assembled about a central axis. Such structures employing flat panels required a plurality of different shapes in order to construct a spherical structure, thus requiring complex fabricating steps which have proven very costly. In addition, such flat panels require framing, support units and finishing of interior surfaces when assembling into a final structure. Proposals have been made to use flat panels supported on a frame and interconnected with hubs for proper structural support. Such framing must carry the load of the interior and exterior panels, which limit the load carry strength of the structure. Typical prior art patents illustrating such different panel shapes, framing and/or hubs includes U.S. Pat. Nos. 2,736,072; 3,026,651; 3,296,755; 3,977,138; 4,009,548; 4,330,969; and 5,628,154.
SUMMARY OF THE INVENTION
[0006] The present invention includes panels that will provide spheres, three-quarter spheres, hemispheres, quarter spheres, eighth spheres and the like. To build a sphere structure of the invention two basic, synclastic panels, Panel A and Panel B are generally employed that can be pre-cast or molded in structural plastic, carbon fiber, fiberglass, polycarbonate or other such structural materials. The panels, due to their synclastic curves, are much stronger than flat panels made of the same material. The inventive panels are designed to be used together in building modules. A plurality of these panels will provide a sphere, or a section of a sphere that is lightweight and, at the same time, extremely strong.
[0007] The panel and module shapes are based on a dodecahedron, or, more particularly, a disdyakis triacontahedron, that has been projected onto a sphere forming great circles. Since only two types of panels need to be manufactured, cost is reduced. Since the panels do not require additional framing, then labor costs, as well as shipping and storage costs are reduced. In addition, a synclastic sphere is quite aesthetically pleasing, due to the smooth, uninterrupted curved surface. Synclastic curves are curved toward the same side in all directions. Workers with only the basic assembly skills can construct a sphere or hemisphere using these panels.
[0008] As defined herein the term panel means a synclastic, double-hull, arch truss panel. The outer surface of the panel is the outer hull; the inner surface of the panel is the inner hull.
[0009] Each of the structural building panels is a one piece, synclastic double-hull, arch truss panel, triangular in shape, that can be pre-cast or molded from various materials. Such panels are self-supporting panels that do not require any kind of additional framing for building spheres, hemispheres or the like; the panels themselves are the frame. Both the exterior hull and interior hull of these panels can be pre-finished on a factory assembly line. The arch trusses, which are integrated into the panel along the edges of the hulls, connect the outer hull to the inner hull seamlessly, to provide a hollow core inside the panel for the inclusion of mechanicals and insulation, as will as for providing a surface for connecting the panels together through the arch trusses. This feature makes the panels more cost-effective then other systems, which require separate framing and more assembly at the construction site.
[0010] The basic components of both panels A and B generally include five sides: a synclastic triangular outer hull, a synclastic triangular inner hull, and three arch trusses. The hulls are connected by the arch trusses, typically integrally incorporated seamlessly into a casting, to form a hollow core panel. Each panel has arch truss sides of different lengths, designated a, b, and c, which lie on a theoretical geodesic plane that passes through the center axis of the assembled sphere. This feature allows the panels to fit together as building modules. These building modules are assembled symmetrically only on a theoretical geodesic plane along their arch truss edges.
[0011] When skylight portals, egress portals, and sphere foundation footing portals are required in the structure, Panels A and B are substituted at the required locations by transparent or translucent panels for skylight portals, hinge, pivoting, or sliding panels for egress portals and reinforced foundation footings for the sphere foundation portals.
[0012] The hulls or panel surfaces disperse the load of the structural weight, synclastically. The synclastic curve of the outer and inner hulls carries the load of the structure, thereby dispersing the weight evenly throughout each panel, which keeps the entire structure in compression. The panel trusses, which connect the inner hull to the outer hull seamlessly, serve as spacers between the hulls. Each panel is designed to be cast as one piece. After casting is complete, access holes are cut into the trusses and the inner hull, so that if desired, insulation and/or mechanicals can be installed inside the hollow core of the panel; that is between the inner and outer hulls, at the factory.
[0013] The arch trusses serve three functions: They act as spacers between the outer hull and the inner hull for running mechanical systems such as ventilation, electrical, fluid supplies and returns. They bond the outer hull to the inner hull seamlessly to form one hollow core, synclastically curved, integrated unit. They supply the surface area necessary for connecting the panels together. The panels themselves perform the function of a conventional frame; therefore, the structure does not require separate framing. If a panel is damaged, it can be replaced without endangering the integrity of the structure.
[0014] A building panel of the invention adapted to form an element of a dome structure comprises: a synclastic triangular outer hull; a synclastic triangular inner hull sharing the same axis as the outer hull; and a supporting arch truss structure sandwiched therebetween and connecting a periphery of the inner hull to a periphery of the outer hull to provide a hollow core, wherein respective sides of the arch truss structure are of different lengths which lie on a plane passing through a center axis of the dome structure.
[0015] A building module adapted to form an element of a dome structure comprises: first and second symmetric building modules, each said building module comprising a synclastic triangular outer hull; a synclastic triangular inner hull sharing the same axis as the outer hull; and a supporting arch truss structure sandwiched therebetween and connecting a periphery of the inner hull to a periphery of the outer hull to provide a hollow core, wherein respective sides of the supporting arch truss structure are of different lengths which lie on a plane passing through a center axis of the dome structure and wherein the first and second building modules are joinable along congruent sides of the respective arch trusses.
[0016] In one aspect a dome structure comprises a plurality of joined triangular shaped building modules, each building module comprising a set of four building panels. Module A- 1 , containing four A panels and module B- 1 , containing four B panels, said building modules which are mirror images of each other, each said building panel A and B comprises (a) a synclastic triangular outer hull, (b) a synclastic triangular inner hull sharing the same axis point as the outer hull and (c) a supporting arch truss structure sandwiched therebetween and connecting a periphery of the inner hull to a periphery of the outer hull to form a hollow core, wherein respective sides of the supporting arch truss structure are of different lengths which lie on a plane passing through a center axis of the dome structure, wherein each said pair of building modules are joined along congruent sides of the respective arch trusses of the same length.
[0017] The invention in another embodiment includes two building modules, each building module comprising a set of sixteen building panels. Module A- 1 , containing sixteen A panels and module B- 1 containing sixteen B panels each panel being a one piece molded or cast structural panel, having a synclastic triangular shape. Panels A and B are symmetrical mirror images of each other along their arch truss edges. The two basic building modules A- 1 and B- 1 , can be placed together along their corresponding arch truss edges to form a module pair. Thus, module A- 1 connected to its mirror image, module B- 1 , produces a two-part symmetrical pair that serves as a building module suitable for assembly with similar building modules. For example, thirty A- 1 modules together with thirty B- 1 modules will complete a hemisphere, while sixty A- 1 modules together with sixty B- 1 modules will complete a sphere.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] In the drawings the arch truss sides of the panels are labeled with two letters; the first letter indicates the panel to which the arch truss belongs and the second letter indicates the arch truss side of the panel. For example, aa or Aa represents panel A, arch truss side a.
[0019] FIG. 1 is a representation of a great circle with a regular pentagon at the top;
[0020] FIG. 2 is a drawing showing the great circle of FIG. 1 with an inner arc and outer arc of the arch trusses;
[0021] FIG. 3 is a drawing showing radial lines of the arch trusses;
[0022] FIG. 4 is a geometric drawing showing the development of the three basic arch trusses, arch truss a, arch truss b, and arch truss c as well as arch truss a- 4 , b- 4 , c- 4 and a- 16 , b- 16 , c- 16 , on the great circle;
[0023] FIG. 5 is a perspective drawing of arch truss triangle (a, b, c) for panel B, and arch truss triangle (a, b, c) for panel A;
[0024] FIG. 6 is a geometric drawing showing the ratio of the arch trusses arc cord lengths and arc lengths (a, b, c) for module A- 1 , and module B- 1 , as well as their placement on a geodesic plane of the sphere;
[0025] FIG. 7 shows the formation of the arch truss triangles, where cords (a, b, c) of the great circle form triangle (a, b, c) for module A- 1 and a mirror image triangle (a, b, c) for module B- 1 ;
[0026] FIG. 8 shows four A triangles and four B triangles, forming an A- 1 triangular module and a B- 1 triangular module from the arc cords (a, b, c) of the great circle;
[0027] FIG. 9 shows the ratio of the arc cord lengths of the sides of the arch truss triangle A- 1 , mirror image arch truss triangle B- 1 , and the dihedral angles of arch truss triangle B- 1 , which are the same dihedral angles as triangle A- 1 ;
[0028] FIG. 10 shows both the dihedral angles and the ratio of the arc cord lengths of triangle module A- 1 and mirror image triangle module B- 1 ,and the placement of triangles A and triangles B into modular form;
[0029] FIG. 11 shows the dihedral angles and the ratio of the arc cord lengths of panel A and mirror image panel B;
[0030] FIG. 12 is a perspective drawing which shows a grouping of four arch truss triangles A with sides (Aa, Ab, Ac) and mirror image of four arch truss triangles B with sides (Ba, Bb, Bc) showing modular formation;
[0031] FIG. 13 is a perspective drawing which shows the arch truss triangle A with sides (Aa, Ab, Ac) and mirror image arch truss triangle B with sides (Ba, Bb, Bc);
[0032] FIG. 14 is a perspective drawing showing three A arch truss triangles with sides (Aa, Ab, Ac) and mirror image of three B arch truss triangles with sides (Ba, Bb, Bc),
[0033] FIG. 15 is a perspective view of panel templates (At) and (Bt) as a pair showing their mirror image symmetry;
[0034] FIG. 16 is a perspective drawing showing three A panels together forming a trapezoidal module and mirror image symmetry to three B panels together forming a trapezoidal module;
[0035] FIG. 17 is a perspective drawing of panels A and panels B in modular pairs showing their mirror image symmetry;
[0036] FIG. 18 is a perspective view of casting plate ap 3 showing its convex bottom surface and vacuum ports;
[0037] FIG. 19 is a perspective view of casting plate, ap 2 showing its concave top surface with an empty cavity for casting panel A;
[0038] FIG. 20 is a perspective view of casting plate, ap 1 showing its concave top surface;
[0039] FIG. 21 is a perspective top view of panel A;
[0040] FIG. 22 is a perspective view of a casting plate, bp 3 showing its convex bottom and vacuum ports for casting panels;
[0041] FIG. 23 is a perspective view of casting plate, bp 4 showing its concave top surface and the empty cavity for casting panel B;
[0042] FIG. 24 is a perspective view of casting plate, bp 1 showing a casting form band CFB around its circumference;
[0043] FIG. 25 is a perspective view of panel B showing an arch truss edge and interior hull;
[0044] FIG. 26 is a perspective view of panel vacuum bladders with vacuum tubes connected for use in the casting molds of B panels and A panels;
[0045] FIG. 27 is a sectional view of three casting plates in an open position with vacuum ports and showing the cavity for panel A;
[0046] FIG. 28 is a sectional view of three casting plates in a closed position with vacuum ports and showing the cavity for panel B;
[0047] FIG. 29 is an exterior and interior perspective view of panel A and panel B illustrating exterior and interior hull surfaces and arch truss sides;
[0048] FIG. 30 is an exterior and interior perspective view of a four in one A 1 -module of A panels and a four in one B 1 -module of B panels together as building modules, to illustrate their symmetry;
[0049] FIG. 31 is an exterior and interior perspective view of a sixteen in one A 1 -module of A-panels and a sixteen in one B 1 -module of B-panels;
[0050] FIG. 32 is a perspective view of modules B 1 , A 1 as a modular pair, showing sectional slice 20 as a dashed line section;
[0051] FIG. 33 is sectional slice cut away 20 showing sectional slice through B panels and A panels with threaded grommet connectors 21 and 22 in truss access holes;
[0052] FIG. 34 shows a close up view of how the panels are connected with grommet connector 21 and 22 through the arch truss access holes;
[0053] FIG. 35 is a perspective view of a theoretical geodesic plane passing through the center of a sphere on a geodesic line;
[0054] FIG. 36 is a perspective view of three theoretical geodesic planes ( 16 , 17 and 18 ) passing through the center of a sphere on geodesic lines, geodesic plane ( 18 ) is represented as a strait line;
[0055] FIG. 37 is a perspective view of a geodesic hemisphere showing A panels and B panels used as egress portal and showing an open skylight portal;
[0056] FIG. 38 shows five panel pairs joined to form a portal;
[0057] FIG. 39 shows a geodesic sphere supported on one footing portal;
[0058] FIG. 40 shows a geodesic sphere with three footing portals, FP 1 , FP 2 and FP 3 , viewed from below;
[0059] FIG. 41 shows the geodesic sphere of FIG. 40 supported through the three footing portals.
[0060] FIG. 42 is a exploded perspective view of panel A, showing its basic compositional makeup;
[0061] FIG. 43 is an exploded perspective view of panel B showing its basic compositional makeup.
DETAILED DESCRIPTION OF THE INVENTION
[0062] As shown in FIGS. 9 , 12 , 17 , 30 , 31 and 32 , Panel module A- 1 has a synclastic outer hull, a synclastic inner hull and three arch truss sides with dihedral angles, angle bc=34°26′11.49″, angle ac=58°24′8.46″, and angle ab=87°9′40.05″. As shown in FIG. 6 , the arch truss arc length ratios of the outer hull arc curve are: a=182.4319, b=276.7871, and c=326.1791 respectively, and the radial line length between the outer hull and inner hull is in direct proportion to the radius of the outer hull and radius of the inner hull. Also in FIGS. 9 , 12 , 17 , 30 , 31 and 32 , Panel module B- 1 has a synclastic outer hull, a synclastic inner hull and three arch truss sides with dihedral angles, angle cb=34°26′11.49″, angle ac=58°24′8.46″, and angle ab=87°9′40.05″. Panel module B- 1 arch truss arc length ratios of the outer hull arc curve are the same as Panel module A- 1 ; a=182.4319, b=276.7871, and c=326.1791 respectively, and the radial line length between the outer hull and inner hull is in direct proportion to the radius of the outer hull and radius of the inner hull.
[0063] To make panel templates; first the size of the sphere or dome structure is selected, then the dimensions of panel modules A- 1 and panel module B- 1 are determined, once this is done, panel template (At) and panel template (Bt) can be sized to (. 25 ) of panel module A- 1 and panel module B- 1 .creating (A- 1 module- 4 ) and (B- 1 module- 4 ). this is done by bisecting arch trusses (a, b, c) and increasing the inner hulls radial arc to that of (0.5) of the radial line segment of the arch trusses enabling the creation of four A panels which fit into one A- 1 module and four B panels that fit into one B- 1 module. For very large geodesic domes this process can be repeated on A panels and B panels to keep the panel size manageable, as in a (A- 1 module- 16 ) and (B- 1 module- 16 ) in which 16 A panels and 16 B panels are used in A- 1 modules and B- 1 modules. This can be better understood when viewing FIGS. 4-12 , 29 - 31 . Panel template At and Bt are used in the process of casting panels A and B. Arch truss triangle A with sides a, b, c and mirror image arch truss triangle B with sides a, b, c, which share (1) the same dihedral angles, and (2) the same arc length ratios of the outer arc arch truss sides, a=182.4219, b=276.7871, c=326.1791, are each filled in with a rigid, light-weight plastic material and machined to the arc curve of the outer hull along its outer arch truss edge and machined to the arc curve of the inner hull along its inner arch truss edge for respective panels A and B.
[0064] Four different casting plates are formed to prepare panels A and B. Plate (p 1 ) has a concave top surface machined to the arc curve of the outer hull of the sphere. Plate (p 2 ) has a convex bottom surface machined to the arc curve of the outer hull or surface of the sphere, and a concave top surface machined to the arc curve of the inner hull of the sphere, with a cavity in the center of the plate being the negative of panel template (At). Plate (p 3 ) has a convex bottom surface machined to the arc curve of the inner hull of the sphere. Plate (p 4 ) has a convex bottom surface machined to the arc curve of the outer hull of the sphere, and a concave top surface machined to the arc curve of the inner hull of the sphere, with a cavity in the center of the plate being the negative of panel template (Bt).
[0065] Panel A is formed preferably by casting as shown in FIGS. 18-21 , and 27 . Panel B is preferably formed by the same procedure, as shown in FIGS. 22-25 and 28 . Casting plate ap 2 is seated onto casting plate ap 1 , and a polymer impregnated carbon fiber, or other suitable material is then wrapped around panel A vacuum bladder Avb and fitted into the casting mold plate ap 2 . A vacuum tube vt 2 ( FIG. 34 ) is then connected to the vacuum bladder Avb with tube vt 2 passing through a vacuum port v 2 in plate ap 3 . As shown in FIG. 36 for Panel A, plate ap 3 is then lowered into place to seat on ap 2 and then all three plates are locked together, sealing the vacuum bladder and casting material inside. Negative pressure is then applied to the vacuum ports v 1 , v 2 and v 3 allowing positive pressure down into the vacuum bladder Avb through the vacuum tube vt 2 , thus expanding bladder Avb and forcing the casting material tight to the inside of the casting cavity. The casting plates are then heated to the curing temperature of the polymer. Once cured, the vacuum bladder is decompressed, the casting plates are then separated and panel A is removed form casting plate ap 2 in the direction of plate apt. The panel casting is then complete.
[0066] Panel A is transferred to the cutting station where access holes ( 12 and 14 ) as seen in FIG. 42 , are then cut into the inner hull and the arch truss sides, and the vacuum bladder is then removed. At this stage the panel is conducted to an insulation station, where insulation is sprayed onto the inside surface of the outer hull and then to a station where mechanicals can be added, such as ventilation ducts, fluid supplies and returns, and electrical wiring.
[0067] As shown in FIGS. 22-25 , and 28 , panel B is cast using casting plate bp 4 which is seated onto casting plate bp 1 , a polymer-impregnated carbon fiber or other suitable material is then wrapped around panel B vacuum bladder Bvb and fitted into the casting mold plate bp 4 . Vacuum tube vt 2 is then connected to the vacuum bladder Bvb, with tube vt 2 passing through vacuum port v 2 in plate bp 3 . Plate bp 3 is lowered into place seating onto plate bp 4 , and all three plates are locked together sealing the vacuum bladder and casting material inside, see FIG. 28 . Negative pressure is applied to the vacuum ports v 1 , v 2 , v 3 allowing positive pressure down into the vacuum bladder through tube vt 2 , expanding the bladder and forcing the casting material tight to the inside of the casting cavity. The casting plates are then heated to the curing temperature of the polymer. Once the polymer has cured, the vacuum bladder is decompressed, the casting plates are separated and panel B is removed from casting plate bp 4 in the direction of plate bp 1 . The panel is conducted to a cutting station where access holes ( 12 and 14 ), FIG. 43 , are cut into the inner hull and arch truss sides, the vacuum bladder is removed. At this stage the panel is ready for any additional modifications. If required, the panel is transferred to an area where insulation is sprayed onto the inside surface of the outer hull. If desired, mechanicals can be added, such as ventilation ducts, fluid supplies, returns and electrical wiring.
[0068] Casting plates ap 3 , bp 3 . are identical. Likewise, casting plates ap 1 , bp 1 , are identical.
[0069] The arch trusses used for the templates are preferably formed from a conventional rigid material which can be reinforced, if need be, so the trusses maintain dimensional stability and do not change shape when used in casting the mold plates. Such a rigid material can include structural plastic, carbon fiber, fiberglass, polycarbonate and the like.
[0070] The arch trusses are formed based on two formulas which describe a dodecahedron inscribed in a sphere: (1) r u =a/4(√5+√3) and formula (2) r m =a/4(3+√5), wherein r u is the radius of the outer hull, r m is the radius of the inner hull and (a) is the length of one side of a regular pentagon.
[0071] As illustrated in FIGS. 1-4 the circumference of the great circle 1 and the outer hull or shell of the sphere, have the same arc curve as the outer arc of the arch trusses. Line ( 3 , 4 ) represents one side of pentagon 2 with vertex point 3 and vertex point 4 on the great circle parallel to the diameter of the great circle. Inner circle 5 has the same arc curve as the inner hull and the inner arc curve of the arch trusses. Zenith point 5 z of inner circle 5 is tangent to the center point of line ( 3 , 4 ). Axis point 1 c of inner circle 5 is the same as the axis point of the great circle 1 . Projecting a radial line from the axis 1 c to the zenith point 9 z of the great circle 1 provides the first radial line of arch truss a, which is the radial line segment ( 9 z, 5 z ). See FIG. 4 The radial line projected to point 4 on line ( 1 c, 4 ) provides a second radial line of arch truss a, and the first radial line of arch truss c. Projecting a circle 6 with its axis point at 4 and tangent to the center point 7 c of the pentagon, a radial line 1 c, 8 t, is further projected onto the great circle to point 8 , which provides the second radial line for arch truss c and the first radial line for arch truss b. The radial line projected from axis point 1 c along the diameter of the great circle to point 10 on the great circle provides the second radial line for arch truss b, thus forming the proportional dimensions of arch trusses a, b, and c. Attaching these arch trusses together along their radial line edges forms arch truss triangle A. To form arch truss triangle B, identical arch trusses a, b and c, are rotated 180° and joined along their radial line edges thus forming arch truss triangle B, the mirror image of arch truss triangle A.
[0072] As illustrated in FIGS. 12-17 arch truss triangles are formed from arch trusses a, b, and c, assembled along their radial line edges 4 , 8 , 10 to form arch truss triangle A having sides Aa, Ab, Ac, and its mirror image, arch truss triangle B, having sides Ba, Bb, Bc ( FIG. 12 ). Arch truss triangle A and arch truss triangle B, are then seated onto a concave surface that has been treated with a form release lubricant and has the same arc curve as that of the outer hull. The arch truss triangles are then filled with a rigid lightweight plastic material that is tooled to the arc curve of the inner hull along its screed edge to form solid panel templates At and Bt, see FIG. 15 . These panel templates are used for forming casting plates ap 2 and bp 4 , respectively.
[0073] To make egress portals in the dome structure, panels A and B are adapted to except door hardware. To make skylight portals panels A and B are replaced with transparent or translucent panels of the same dimensions
[0074] As exemplified in FIGS.18-20 for panel A, casting mold plate ap 1 is made of a conventional material for casting mold plates, with top surface A 1 machined and polished to a concave arc radius identical to that of the outer hull.
[0075] Casting mold plate ap 3 is made of a conventional material for casting mold plates, with bottom surface B 3 machined and polished to a convex arc radius identical to that of the inner hull. Casting mold plate ap 2 is made of a conventional material for making casting mold plates.
[0076] Panel template At ( FIG. 15 ) is centered with its outer arc truss edges resting on the surface of casting mold plate ap 1 , which has been treated with a form release lubricant. A casting form band CFB (shown in FIG. 24 ), that has also been treated with a form release lubricant is set around the circumference edge of casting mold plate ap 1 , extending a distance above the surface of plate apt to the inner arc curve of the panel template At. Then cast-forming material is poured into the casting form and is machined to be smooth with a tool that has the same arc curve as the inner hull along the screed edge of the casting form band and the screed edge of the panel template At.
[0077] As seen in FIGS. 22-24 , for panel B, casting mold plate bp 4 is made of a conventional material for making casting mold plates. Panel template Bt is centered with its outer arch truss edges resting on the concave surface of casting mold plate bp 1 which has been treated with a form release lubricant. A casting form band (CFB) that has been treated with a form release lubricant is set around the circumference edge of casting mold plate bp 1 , extending a distance above the surface of plate bp 1 to the inner arc curve of the panel template Bt. Cast forming material is poured into the casting form and machined smooth with a tool that has the same arc curve of the inner hull along the screed edge of the casting form band and the screed edge of panel template Bt.
[0078] As shown in FIGS. 18-20 , the first casting mold plate for panel A, plate ap 1 , has a concave top surface side A 1 with a radius arc identical to that of the sphere or outer hull. The second casting plate for panel A is plate ap 2 which is convex and has the curvature radius arc of the outer hull on side A 2 , and is seated on the first plate ap 1 . Plate side B 2 has a concave surface radius arc identical to the inner hull radius. The thickness of plate ap 2 is directly proportional to the radius arc of the outer hull and the radius arc of the inner hull. Plate ap 3 side B 3 has a convex surface radius arc identical to that of the inner hull, and is seated on the concave surface side B 2 of plate ap 2 .
[0079] Triangular panel A is cast using plates ap 1 , ap 2 and ap 3 , see FIGS. 18-21 . Triangular panel B is cast using plates bp 1 , bp 4 and bp 3 , see FIGS. 22-25 . Casting plates ap 1 and bp 1 are identical plates. Casting plates ap 3 and bp 3 , are identical plates, the letter in front of plate p 3 identifies the panel being cast.
[0080] The vacuum bladders are made from a balloon-type material that is flexible as well as expandable. The vacuum bladders are the same size and shape when expanded as the casting cavity in the casting plate in which they are to be used in the casting of panels FIGS. 26-28 .
[0081] When assembling the dome-like structure, arch truss sides (a, b, c) of panels A and B only line up with like lettered sides. Side (a) only lines up with an (a) arch truss side, (b) only lines up with a (b) arch truss side and (c) only lines up with a (c) arch truss side. A- 1 panel modules are made up of only A panels. B- 1 panel modules are only made up of B panels.
[0082] Foundation footing portals are only used in sphere applications and do not require panels A and B, see drawings FIGS. 39 , 40 and 41 . As seen in FIGS. 38 and 39 when skylight, egress or sphere foundation footing portals are employed, panels A and B are substituted at the required locations by the appropriate portal panel of the same dimensions.
[0083] As shown in FIGS. 42 and 43 mechanicals and/or insulation for the above dome structure can also be installed during or after construction through access holes 12 on the inner hull, which also provide access to the threaded grommet system shown in FIGS. 33 and 34 for connecting the panels together. The access holes 12 in the inner hull have cover plates 13 that match the synclastic curve of the inner hull. Since a panel module can only be used with its mirror image, rapid final assembly of the structure is possible.
[0084] As shown in FIG. 42 arch truss 11 a connecting outer hull 1 a to inner hull 5 a has access holes 14 , while the inner hull 5 a of Panel A has access holes 12 with matching cover plates 13 . In FIG. 43 for Panel B outer hull 1 b is connected to inner hull 5 b via arch truss 11 b which has access holes 14 Inner hull 5 b has access holes 12 coverable by synclastic access covers 13 .
[0085] Other modifications will be obvious to those skilled in this art. The invention is not to be limited except as set forth in the following claims. in plate ap 3 . As shown in FIG. 36 for Panel A, plate ap 3 is then lowered into place to seat on ap 2 and then all three plates are locked together, sealing the vacuum bladder and casting material inside. Negative pressure is then applied to the vacuum ports v 1 , v 2 and v 3 allowing positive pressure down into the vacuum bladder Avb through the vacuum tube vt 2 , thus expanding bladder Avb and forcing the casting material tight to the inside of the casting cavity. The casting plates are then heated to the curing temperature of the polymer. Once cured, the vacuum bladder is decompressed, the casting plates are then separated and panel A is removed from casting plate ap 2 in the direction of plate ap 1 . The panel casting is then complete.
[0086] Panel A is transferred to the cutting station where access holes ( 12 and 14 ) as seen in FIG. 42 , are then cut into the inner hull and the arch truss sides, and the vacuum bladder is then removed. At this stage the panel is conducted to an insulation station, where insulation is sprayed onto the inside surface of the outer hull and then to a station where mechanicals can be added, such as ventilation ducts, fluid supplies and returns, and electrical wiring.
[0087] As shown in FIGS. 22-25 , and 28 , panel B is cast using casting plate bp 4 which is seated onto casting plate by 1, a polymer-impregnated carbon fiber or other suitable material is then wrapped around panel B vacuum bladder Bvb and fitted into the casting mold plate bp 4 . Vacuum tube vt 2 is then connected to the vacuum bladder Bvb, with tube vt 2 passing through vacuum port v 2 in plate bp 3 . Plate bp 3 is lowered into place seating onto plate bp 4 , and all three plates are locked together sealing the vacuum bladder and casting material inside, see FIG. 28 . Negative pressure is applied to the vacuum ports v 1 , v 2 , v 3 allowing positive pressure down into the vacuum bladder through tube vt 2 , expanding the bladder and forcing the casting material tight to the inside of the casting cavity. The casting plates are then heated to the curing temperature of the polymer. Once the polymer has cured, the vacuum bladder is decompressed, the casting plates are separated and panel B is removed from casting plate bp 4 in the direction of plate bp 1 . The panel is conducted to a cutting station where access holes ( 12 and 14 ), FIG. 43 , are cut into the inner hull and arch truss sides, in plate ap 3 . As shown in FIG. 36 for Panel A, plate ap 3 is then lowered into place to seat on ap 2 and then all three plates are locked together, sealing the vacuum bladder and casting material inside. Negative pressure is then applied to the vacuum ports v 1 , v 2 and v 3 allowing positive pressure down into the vacuum bladder Avb through the vacuum tube vt 2 , thus expanding bladder Avb and forcing the casting material tight to the inside of the casting cavity. The casting plates are then heated to the curing temperature of the polymer. Once cured, the vacuum bladder is decompressed, the casting plates are then separated and panel A is removed [form] from casting plate ap 2 in the direction of plate ap 1 . The panel casting is then complete.
[0088] Panel A is transferred to the cutting station where access holes ( 12 and 14 ) as seen in FIG. 42 , are then cut into the inner hull and the arch truss sides, and the vacuum bladder is then removed. At this stage the panel is conducted to an insulation station, where insulation is sprayed onto the inside surface of the outer hull and then to a station where mechanicals can be added, such as ventilation ducts, fluid supplies and returns, and electrical wiring.
[0089] As shown in FIGS. 22-25 , and 28 , panel B is cast using casting plate bp 4 which is seated onto casting plate bp 1 , a polymer-impregnated carbon fiber or other suitable material is then wrapped around panel B vacuum bladder Bvb and fitted into the casting mold plate bp 4 . Vacuum tube vt 2 is then connected to the vacuum bladder Bvb, with tube vt 2 passing through vacuum port v 2 in plate bp 3 . Plate bp 3 is lowered into place seating onto plate bp 4 , and all three plates are locked together sealing the vacuum bladder and casting material inside, see FIG. 28 . Negative pressure is applied to the vacuum ports v 1 , v 2 , v 3 allowing positive pressure down into the vacuum bladder through tube vt 2 , expanding the bladder and forcing the casting material tight to the inside of the casting cavity. The casting plates are then heated to the curing temperature of the polymer. Once the polymer has cured, the vacuum bladder is decompressed, the casting plates are separated and panel B is removed from casting plate bp 4 in the direction of plate bp 1 . The panel is conducted to a cutting station where access holes ( 12 and 14 ), FIG. 43 , are cut into the inner hull and arch truss sides,
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Synclastic hollow core building panels are employed to form dome-like structures. The synclastic curve allows the panels to be lightweight, yet capable of carrying the weight of the structural loads. When combined, the panels create a sphere or a section of a sphere for enclosing space, with optional egress, skylight, and foundation portals incorporated into the structure without disturbing the spherical curvature of the interior or exterior surfaces. The spheres or sphere sections require no additional framing; the panels themselves are the frame. Workers with only the basic assembly skills can construct a sphere or sphere sections using these panels.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to and the benefit of Korean Patent Application No. 10-2009-0110773, filed on Nov. 17, 2009, in the Korean Intellectual Property Office, the entire content of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the invention
[0003] An embodiment of the present invention relates to a preferential oxidation reactor having excellent carbon monoxide reduction performance while providing for self-ignition of the reformate.
[0004] 2. Discussion of Related Art
[0005] In modern society, because concern about environmental pollution is increasing, the development of alternative energy sources such as fuel cells which are non-pollutive and excellent in energy efficiency, etc. is in active progress.
[0006] Protons used as fuel for a fuel cell are typically acquired from reformate, i.e., reforming ethanol, methanol, liquefied petroleum gas (LPG), gasoline, etc., due to the various difficult problems caused by storage and transportation of hydrogen. The reformate acquired in the reforming process contains carbon dioxide, carbon monoxide, etc., in addition to protons. Carbon monoxide deteriorates electrode activation by poisoning electrode active materials of a polyelectroytic fuel cell, e.g., platinum (Pt). Accordingly, in order to use the reformate, carbon monoxide contained in the reformate needs to be reduced to 10 ppm or less.
[0007] A method for removing carbon monoxide from the reformate includes a method using palladium (Pd) or a palladium alloy membrane, a method using methanation or preferential oxidation or selective oxidation, etc.
SUMMARY OF THE INVENTION
[0008] An embodiment of the present invention provides a preferential oxidation reactor which can reduce carbon monoxide in reformate (hereinafter, referred to as hydrogen mixed gas) to 10 ppm or less, while providing for self-ignition of the reformate.
[0009] According to an embodiment of the present invention, a preferential oxidation reactor includes: a first reaction unit including a first internal space connected with a first opening portion and a first catalyst, capable of spontaneously igniting hydrogen mixed gas at a predetermined atmospheric temperature of the first internal space; a second reaction unit including a second internal space connected to a second opening portion and a second catalyst contained in the second internal space; and a separation layer that is positioned between the first and second catalysts so as to separate the first catalyst and the second catalyst from each other, and which connects the first internal space and the second internal space to each other to be in fluid communication.
[0010] In the embodiment, the entire volume of the first catalyst is 0.004 times or more of the flow rate per minute of hydrogen mixed gas supplied to the first internal space.
[0011] In the embodiment, the first catalyst includes transition metal. The first catalyst may contain platinum or one selected from palladium (Pd), rhenium (Re), rhodium (Rh), cerium (Ce), ruthenium (Ru), and iridium (Ir) or a combination thereof in addition to platinum (Pt).
[0012] In the embodiment, the first catalyst contains a ceramic carrier, a metallic carrier, or a carbon carrier that have a granule shape, or a combination thereof.
[0013] In the embodiment, the second catalyst includes a granule-type carrier.
[0014] In the embodiment, the size of each of the granule-type second catalysts is larger than the size of each of the granule-type first catalysts.
[0015] In the embodiment, the second catalyst includes non-metal. The second catalyst may contain copper (Cu), iron (Fe), cobalt (Co), cerium (Ce), aluminum (Al), or one selected from an oxide thereof, or a combination thereof.
[0016] In the embodiment, the first catalyst contains a ceramic carrier, a metallic carrier, or a carbon carrier that have a granule shape, or a combination thereof.
[0017] In the embodiment, the entire volume of the first catalyst is smaller than the entire volume of the second catalyst.
[0018] In the embodiment, the separation layer includes a porous plate member.
[0019] In the embodiment, the second reaction unit is positioned lower than the first reaction unit in the direction of gravitational force field lines.
[0020] In the embodiment, the preferential oxidation reactor further includes a water receiving unit lower than the first reaction unit in the gravitational force line direction.
[0021] In the embodiment, the second opening portion is positioned in an upper part of the water receiving unit in the direction of gravitational force field lines.
[0022] In the embodiment, the preferential oxidation reactor includes a pipe-type discharge unit that: connects the water receiving unit and the second opening portion to each other to be in fluid communication.
[0023] In the embodiment, the first reaction unit, the second reaction unit, and the discharge unit have a dual-pipe structure.
[0024] According to the embodiments, it is possible to reduce the concentration of carbon monoxide in hydrogen mixed gas to several ppm in a normal state while providing for self-ignition of the hydrogen mixed gas. Further, by separately arranging two kinds of catalysts having different sizes in a predetermined order, the pressure in the reactor is increased only a little. Therefore, to address an increase in pressure caused by using two mixed catalysts, an additional device, i.e., a pressurizing means, such as a pump, etc., does not need to be additionally installed. That is, it is possible to provide a preferential oxidation reactor having excellent performance with self-ignition of the hydrogen mixed gas. Moreover, since an igniter may be omitted, it is possible to achieve miniaturization of the device.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] The accompanying drawings, together with the specification illustrate exemplary embodiments of the present invention, and, together with the description, serve to explain the principles of the present invention.
[0026] FIG. 1 is a schematic block diagram of a fuel cell system having a preferential oxidation reactor according to an embodiment.
[0027] FIG. 2 is a schematic cross-sectional view of a preferential oxidation reactor according to an embodiment.
[0028] FIG. 3 is a schematic cross-sectional view of a preferential oxidation reactor according to another embodiment.
[0029] FIG. 4 is a schematic cross-sectional view for describing a preferential oxidation reactor according to a comparative example.
[0030] FIG. 5 is a schematic cross-sectional view for describing a preferential oxidation reactor according to another comparative example.
[0031] FIG. 6 provides Table 1 which shows the results of measurements of the content of carbon monoxide in hydrogen mixed gas discharge from a PROX device.
DETAILED DESCRIPTION OF THE INVENTION
[0032] In the following detailed description, only certain exemplary embodiments of the present invention have been shown and described, simply by way of illustration. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature and not restrictive. in addition, when an element is referred to as being “on” another element, it can be directly on the another element or be indirectly on the another element with one or more intervening elements interposed therebetween. Also, when an element is referred to as being “connected to” another element, it can be directly connected to the another element or be indirectly connected to the another element with one or more intervening elements interposed therebetween. Hereinafter, like reference numerals refer to like elements.
[0033] In describing the embodiment, well-known functions or constructions will not be described in detail since they may unnecessarily obscure the understanding of the present invention. In addition, it will be appreciated that like reference numerals refer to like elements throughout even though they are shown in different figures. Further, when a first element is described as being coupled to a second element, the first element may be not only directly coupled to the second element but may also be indirectly coupled to the second element via a third element. Moreover, when a first layer is provided on a second layer, the first layer may he provided directly on the second layer or a third layer may be interposed therebetween. Besides, in the figures, the thickness and sizes of each layer may be exaggerated for convenience of description and clarity and may be different from the actual thickness and size.
[0034] FIG. 1 is a schematic block diagram of a fuel cell system having a preferential oxidation reactor according to an embodiment
[0035] Referring to FIG. I, the fuel cell system 100 includes a fuel storage device 110 , a fuel reformer 120 , a carbon monoxide reducer 130 , and a fuel cell 160 . The carbon monoxide reducer 130 includes a high-temperature water-gas shift reaction unit 140 a, a low-temperature water-gas shift reaction unit 140 b, and a preferential oxidation reaction unit 150 . Air and/or water may be suitably supplied to each reactor or reaction unit. The fuel cell 160 generates electricity and water by electrochemical reaction of hydrogen in hydrogen mixed gas and oxygen in air received from the preferential oxidation reaction unit 150 . The generated water may be reutilized.
[0036] Each component will be described in more detail below. The fuel storage device 110 may include a fuel tank coupled with another fuel tank or a fuel pump. Methanol, liquid natural gas (LNG), liquid petroleum gas (LPG), gasoline, diesel, etc. may be used as fuel.
[0037] The reformer 120 generates reformate (hydrogen mixed gas) by reforming the fuel. The hydrogen mixed gas generated from the fuel reformer 120 contains carbon monoxide at approximately 10 to 13%. As a reforming method, a steam reforming method and/or a partial oxidation method may be used.
[0038] The water-gas shift reaction units 140 a and 140 b receive the hydrogen mixed gas from the fuel reformer 120 and decrease the content of carbon monoxide in the hydrogen mixed gas to approximately 0.5 to 1%. The water-gas shill reaction may be divided into a high-temperature water-gas shift reaction in which the concentration of carbon monoxide is decreased to approximately 4% at approximately 400° C. and a low-temperature water-gas shift reaction in which the concentration of carbon monoxide is decreased to approximately 0.5 to 1% at approximately 200° C. as a first step.
[0039] The preferential oxidation reaction unit ISO receives the hydrogen mixed gas from the water-gas shift reaction unit 140 b and decreases the content of carbon monoxide in the hydrogen mixed gas to 10 ppm or below. In the preferential oxidation reaction, only carbon monoxide in the hydrogen mixed gas is selectively removed by injecting a predetermined amount of air in the reaction unit. The preferential oxidation reaction preferentially oxidizes and removes only carbon monoxide to 0.5 to 1% in the hydrogen mixed gas in which hydrogen of approximately 65 to 75% exists. The preferential oxidation reaction unit 150 of the embodiment may be designed on the basis of the preferential oxidation reactor to be described below.
[0040] FIG. 2 is a schematic cross-sectional view of a preferential oxidation reactor according to an embodiment.
[0041] Referring to FIG, 2 , the preferential oxidation reactor 50 (hereinafter, referred to as PROX device) includes a first reaction unit 10 , a separation layer 20 , and a second reaction unit 30 . Further, the PROX device 50 may selectively include a discharge unit 35 and a water receiving unit 40 .
[0042] In the embodiment, the separation layer 20 is interposed between the first and second reaction units 10 and 30 in a single internal space of a housing 11 and the first and second reaction units 10 and 30 are disposed at both sides of the separation layer 20 . The separation layer 20 is provided in an inner space of the housing to prevent a first catalyst 13 having a granule shape and a second catalyst 33 having a granule shape from being mixed. Hereinafter, spaces where the first catalyst 13 and the second catalyst 33 are positioned, which are portioned by the separation layer 20 in the internal space of the housing 11 are referred to as a first internal space 11 and a second internal space 31 .
[0043] It is relatively simple to manufacture the reactor by using the first catalyst 13 having a granule shape and the second catalyst 33 having a granule shape. That is, when the first and second catalysts 13 and 33 having a granule shape are just filled in a predetermined position in the inner space of the housing 11 , manufacture of the reactor is substantially completed.
[0044] A first opening portion 12 is provided at one side of the first internal space 11 . The hydrogen mixed gas containing hydrogen and carbon monoxide are introduced into the first opening portion 12 under predetermined pressure. A suitable component 14 for preventing the first catalyst 13 having a granule shape from being dispersed may be provided in the first opening portion 12 . The component 14 may be a component having a mesh shape.
[0045] The first catalyst 13 is, of itself, heated by reaction of the hydrogen mixed gas and a predetermined amount of air (not shown) that are introduced into the first internal space 11 . In addition, the first catalyst 13 reaches temperature required for the reaction to be self-ignited. Thermal energy of the first catalyst 13 heats the hydrogen mixed gas and the housing 11 . That is, the second catalyst 33 is heated by the thermal energy of the first catalyst 13 . A platinum-based catalyst is used as the first catalyst 13 .
[0046] The separation layer 20 includes a plurality of channels through which the hydrogen mixed gas passing through the First internal space 11 passes. In the separation layer 20 , the size of the opening portion at a channel inlet adjacent to the first catalyst 13 is smaller than the size of a predetermined cross section of the first catalyst 13 . This is to prevent the first catalyst 13 from moving to the second internal space 33 through the separation layer 20 . Further, this is to prevent the first catalyst 13 from plugging the channel inlet of the separation layer 20 . A metallic porous plate member may be used as the separation layer 20 .
[0047] The hydrogen mixed gas flows into the second internal space 31 through the separation layer 20 in the first internal space 11 . The second catalyst 33 heated by the first catalyst 13 is provided in the second internal space 31 .
[0048] A non-metal catalyst is used as the second catalyst 33 . When the non-metal catalyst is primarily used as the PROX device 50 , it is possible to decrease the manufacturing cost of the reactor. Further, a non-metal catalyst may decrease the content of carbon monoxide in the hydrogen mixed gas to several ppm. Meanwhile, generally, a non-metal catalyst is not self-ignited by reaction of the hydrogen mixed gas and a predetermined amount of air. However, according to the embodiment, even though a non-metal catalyst is used as the second catalyst 33 , the second catalyst 33 is heated by the first catalyst 13 to be ignited at a temperature required for reaction.
[0049] The hydrogen mixed gas has a content of carbon monoxide that is decreased to several ppm by the first and second catalysts 13 and 33 and is discharged through a second opening portion 37 connected to the second internal space 31 .
[0050] As described above, in the embodiment, it is possible to easily provide a small-sized, high-performance PROX device which can decrease the content of carbon monoxide in the hydrogen mixed gas while providing for self-ignition, by separately installing the platinum-based first catalyst 13 and the non-metal-based second catalyst 33 in the internal space of the single housing 11 with the separation layer 20 interposed therebetween.
[0051] Additionally, in the PROX device 50 , the second reaction unit. 30 is configured to be positioned lower than the first reaction unit 10 . Herein, “lower” corresponds to a lower position based on substantially the direction of gravitational field lines or, in other words, a y-axis direction. A structure in which the second reaction unit 30 is positioned lower than the first reaction unit 10 effectively performs the function of supplying hydrogen-containing gas under predetermined internal pressure. Further, such a structure allows water generated when the PROX device 50 starts or stops to be normally discharged.
[0052] Further, the PROX device 50 of the embodiment may have the water receiving unit 40 lower than the second reaction unit 30 . The water receiving unit 40 may be provided in a predetermined space lower than the second reaction unit 30 . In this case, a partition 42 having at least one opening portion may be provided between the second reaction unit 30 and the water receiving unit 40 . The partition 42 may have a structure and a shape in which the hydrogen mixed gas in the second reaction unit 30 can easily pass through the partition 42 . The partition 42 may have a structure and a shape similar to the separation layer 20 .
[0053] Further, the PROX device 50 of the embodiment may have a pipe-type discharge unit 35 which connects the water receiving unit 40 and the second opening portion 37 to each other to he in fluid communication. The discharge unit 35 serves to guide the hydrogen mixed gas discharged through at least one opening portion of the partition 42 to a second opening portion 27 in an upper part of the housing 11 or in an upper part of the water receiving unit 40 . One end of the discharge unit 35 may be connected to the water receiving unit 40 to be in fluid communication. The discharge unit 35 can be modified into various structures and shapes having a channel through which fluid can flow in addition to the pipe shape.
[0054] FIG. 3 is a schematic cross-sectional view of a preferential oxidation reactor according to another embodiment.
[0055] Referring to FIG. 3 , the PROX device 50 a of the embodiment includes a first reaction unit 60 , a separation layer 70 , and a second reaction unit 80 . Further, the PROX device 50 a may include a discharge unit 35 a and a water receiving unit 40 a.
[0056] Further, the PROX device 50 a may include a dual-pipe structure formed by a housing 51 a and a discharge unit 35 a. That is, when the housing 51 a has a cylinder structure, the pipe-type discharge unit 35 a is provided to extend close to the bottom of the housing 51 a crossing the center in a longitudinal direction of the housing 51 a in an upper part of the housing 51 a. One end portion of the discharge unit 35 a is spaced from an inner surface of a bottom wall 51 c of the housing 51 a by a predetermined gap.
[0057] In the dual-pipe structure, a first catalyst 63 , the separation layer 70 , and a second catalyst 83 are sequentially laminated in an internal space formed between an outer surface of the discharge unit 35 a and an inner surface of the housing 51 a. Herein, a first internal space 61 of the housing 51 a where the first catalyst 63 is positioned is a first reaction unit 60 and a second internal space of the housing 51 a where a second catalyst 83 is positioned is a second reaction unit 80 with the separation layer 70 interposed therebetween.
[0058] Further, the dual-pipe structure, the water receiving unit 40 a is provided between the inner surface of the bottom wall 51 c of the housing 51 a and one end portion of the discharge unit 35 a. One end portion of the discharge unit 35 a may be slightly inserted into the water receiving unit 40 a. A porous member such as a metal foam, a ceramic foam, etc., may be used as the water receiving unit 40 a.
[0059] In the embodiment, the hydrogen mixed gas is introduced into the first internal space 61 of the first reaction unit 60 through the first opening portion 62 provided in the upper part of the housing 51 a. In addition, the hydrogen mixed gas flows into the second internal space 81 of the second reaction unit 80 through the separation layer 70 in the first internal space 61 . Next, the hydrogen mixed gas flows via the water receiving unit 40 a and the discharge unit 35 a and is discharged through a second opening portion 37 a. The second opening portion 37 a may correspond to an opening portion of one end of the upper part of the pipe-type discharge unit 35 a.
[0060] In the embodiment, the platinum-based catalyst or transition metal is used as the first catalyst 63 . A catalyst in which platinum (Pt) is supported on a predetermined carrier may be used as the first catalyst 63 . further, a bi-functional catalyst or a three way catalyst which includes palladium (Pd), rhenium (Re), rhodium (Rh), cerium (Ce), ruthenium (Ru), or iridium (Ir), or a combination thereof, and platinum, are supported on a predetermined carrier may be used as the first catalyst 63 .
[0061] The non-metal catalyst is used as the second catalyst 83 . Copper (Cu), iron (Fe), cobalt (Co), cerium (Ce), aluminum (Al), an oxide thereof or a combination thereof supported on a predetermined carrier, may be used as the second catalyst 83 .
[0062] As the carrier of the first or second catalyst, a ceramic carrier, a metallic carrier, or a carbon carrier that have a. granule shape, or a combination thereof may be used. For example, as the carrier, aluminum oxide, cerium oxide, or a combination thereof may be used.
[0063] FIG. 6 , Table 1, shows the results of measuring the content of carbon monoxide in hydrogen mixed gas discharge from the PROX device, while hydrogen mixed gas of approximately 22 liters per minute is supplied to each of the reactors of the first to eighth examples. Each of the reactors of the first to eighth examples basically corresponds to the PROX device 50 a shown in FIG. 3 except for the volumes of the first and second catalysts.
[0064] In Table 1, examples displayed as “(self)” in a column representing a start time are those which are self-ignited and examples displayed as “(heater)” are those which are ignited by a heater.
[0065] In this experiment, the self-ignited examples include one experiment displayed as No. 04, four examples displayed as No. 07, and one experiment displayed as No. 08. These six examples are all self-ignited within 10 minutes. When the start time exceeds 60 minutes, it is determined that the examples are not self-ignited.
[0066] In Table 1 four examples represented as No. 07 show a slight difference in the supplied amount of air (slpm: standard liters per minute) to a burner (not shown), the supplied amount of air (seem: standard cubic centimeter per minute) to the PROX device, and the supplied amount of water to the steam reforming reactor in the fuel reforming system (see FIG. 1 ) having a fuel reformer and a carbon monoxide reducer and has the same reactor structure. In Table 1 reactors of four examples displayed as No. 07 have a pipe shape having a diameter (D) of 50 mm, a height/length (H) of 180 mm, and volume of 300 cc. In addition, in the column (SR water) representing the supplied amount of water to the steam reforming reactor in each example, the steam to carbon ratio (S/C: steam/carbon) is also displayed.
[0067] In Table 1, an example displayed as No. 01 has an annular reactor structure. This example (No. 01) represents a case where the second catalyst is not displayed adjacent to the lower part in the direction of gravitational field lines of the first catalyst and is not self-ignited. Example No. 03 represents a case where the volume of the first catalyst is larger than the volume of the second catalyst. In this example (No. 03), the concentration of carbon monoxide in the hydrogen mixed gas exceeds 10 ppm. Example No. 02 represents a case using only the first catalyst and in this case, although the concentration of carbon monoxide in the hydrogen mixed gas unexpectedly is less than 10 ppm, the internal pressure of the device is largely increased. Examples No. 05 and No. 06 represent cases where the volume of the first catalyst is 50 cc and 65 cc, and smaller than 80 cc, respectively. These examples (Nos. 05 and 06) are not self-ignited. One reason why the examples Nos. 05 and 06 are not self-ignited is that the volume of the first catalyst is smaller than approximately 80 cc.
[0068] As described above, in the PROX device 50 a of the embodiment, the volume of the first catalyst 63 is smaller than the volume of the second catalyst 83 . Moreover, it is preferable that the volume of the first catalyst 63 is equal to or larger than 80 cc.
[0069] Further, the volume of the first catalyst 63 is approximately 0.004 times the flow rate per unit time (minute) of the hydrogen containing gas supplied to the first internal space 61 through the first opening portion 62 . This value is the minimum volume for self-ignition by the first catalyst 63 of the hydrogen containing gas passing through the first catalyst 63 .
[0070] FIG. 4 is a schematic cross-sectional view showing a preferential oxidation reactor according to a comparative example.
[0071] The PROX device of the comparative example is used to represent characteristics of the PROX device of the embodiment more clearly. Except that the separation layer and the second catalyst are not provided, the PROX device of the comparative example has substantially the same structure and shape as the PROX device of FIG. 3 . Further, the PROX device of the comparative device may correspond to example No. 02 of Table 1.
[0072] Referring to FIG. 4 , the PROX device 50 b of the comparative example has a granule-type catalyst 63 charged in the internal space 52 of the housing 51 b. In a case where the catalyst 63 is a granule-type platinum-based catalyst, the catalyst 63 corresponds to the first catalyst of the embodiment.
[0073] When the catalyst 63 is a platinum-based catalyst, the PROX device 50 b may be self-ignited. However, when only a platinum-based catalyst is used as the catalyst 63 , the content of carbon monoxide in hydrogen mixed gas containing carbon monoxide of approximately 0.5 to 1% cannot he decreased to the range of dozens of ppm. When the hydrogen mixed gas containing carbon monoxide in the range of dozens of ppm is used for the fuel cell, the electrode of the fuel cell is poisoned by carbon monoxide and thus, activation thereof is remarkably decreased. As such, the hydrogen mixed gas produced from the PROX device 50 b of the comparative example is not suitable to be used in a fuel cell.
[0074] On the other hand, the catalyst 63 may be a granule-type non-metal catalyst. In this case, the catalyst 63 may correspond to the second catalyst of the embodiment. When the catalyst 63 is the non-metal catalyst, the PROX device 50 b is not self-ignited. Therefore, there is a disadvantage in that an additional ignition device should be additionally installed.
[0075] Further, the internal pressure of the PROX device Sob charged with the platinum-based catalyst 63 is approximately 5 kPa. The internal pressure is much higher than the internal pressure of the PROX device which is approximately 0.2 kPa, and the internal pressure of the PROX device shown in FIG. 3 which is approximately 1.0 kPa. When the internal pressure of the PROX device is high, the shift rate of carbon monoxide is decreased by limiting smooth flow of the hydrogen mixed gas in the device. Moreover, in the fuel reforming system, since an increase in the output of the components supplying fuel, steam, and air is required, the efficiency of the fuel reforming system or the PROX device may be deteriorated.
[0076] The internal pressure of the PROX device of the comparative example is higher than the internal pressure of the PROX device of the embodiment shown in FIG. 3 because the granule-type platinum-based catalyst (corresponding to first catalyst) having the smaller size than the second catalyst are charged in the internal space having the same volume.
[0077] FIG. 5 is a schematic cross-sectional view for describing a preferential oxidation reactor according to another comparative example.
[0078] The PROX device of the comparative example is used to represent characteristics of the PROX device of the embodiment more clearly. Except that the separation layer is not provided, (which provides that the first catalyst and the second catalyst are not mixed in a partial area), the PROX device of the comparative example has substantially the same structure and shape as the PROX device of FIG. 3 .
[0079] Referring to FIG. 5 , the PROX device 50 cb of the comparative example includes a granule-type first catalyst 63 and a granule-type second catalyst 83 which is larger than the first catalyst 63 , that are charged in the internal space 52 of the housing 51 b. The granule-type first and second catalysts 63 and 83 correspond to the first and second catalysts of the PROX device shown in FIG. 3 .
[0080] When the second catalyst 83 is partially charged in the internal space 52 of the housing 51 b and thereafter, the first catalyst 63 is charged the upper part of the internal space 52 , and the separation layer is not provided, such that the granule-type first catalyst 63 is inserted between the granule-type second catalysts 83 , which are larger than the first catalyst 63 . Therefore, the internal pressure of the PROX device 50 c reaches approximately 12 kPa. That is, when the granule-type platinum-based first catalyst 63 and the granule-type non-metal second catalyst 83 , larger than the first catalyst, are sequentially charged in the internal space 52 of the housing 51 b without the separation layer, the internal pressure is too large, and it is difficult to use them.
[0081] According to another embodiment, in the case of using the granule-type platinum-based first catalyst 63 and the granule-type non-metal second catalyst 83 having substantially the same size as the first catalyst 63 , the internal pressure of the device is undesirably increased similarly to the case shown in FIG. 4 . Further, in the above-mentioned case, it is difficult for the catalyst to be self-ignited.
[0082] While the present invention has been described in connection with certain exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims, and-equivalents thereof.
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There is provided a preferential oxidation reactor having excellent carbon monoxide reducing performance while providing for self-ignition of mixed hydrogen gas. The preferential oxidation reactor includes: a first reaction unit including a first internal space connected with a first opening portion and a first catalyst capable of spontaneously igniting hydrogen mixed gas at a predetermined atmospheric temperature of the first internal space; a second reaction unit including a second internal space connected to a second opening portion and a second catalyst contained in the second internal space; and a separation layer that is positioned between the first and second catalysts so as to separate the first catalyst and the second catalyst from each other and which connects the first internal space and the second internal space to each other to be in fluid communication.
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This is a division of application Ser. No. 197,985 filed Oct. 14, 1980, now U.S. Pat. No. 4,383,115.
TECHNICAL FIELD
This invention relates to a novel group of cyanoguanidine derivatives characterized by the following imino-alkyl and amino-nitrile structural formula: ##STR2## wherein R 1 is a 2-mercapto-ethyl, a 2-hydroxy-ethyl, a 2-((4-methyl-5-imidazolyl)thio-methyl)ethyl, or a 2-((4-methyl-5-imidazolyl)dithioformyloxy-methyl)ethyl radical, and R 2 represents a methyl radical.
A particularly advantageous compound of the invention: N-methyl-N'-cyano-N"-imino-[2-((4-methyl-5-imidazolyl)thio-methyl) ethyl] guanidine is a histamine antagonist in the H 2 receptors which inhibits the secretion of gastric acid, and can be used therapeutically for the treatment of gastric and duodenal ulcers.
This invention also relates to processes for the production of these novel cyanoguanidine derivatives.
BACKGROUND OF THE INVENTION
Cyanoguanidine derivatives synthesized by known processes are characterized by imino-nitrile guanidine structures having the following formula: ##STR3##
The stable conformations of the cyanoguanidines of formula II are represented by the following structures: ##STR4##
Structures IIa and IIb represent the anti(--NHR 2 ) and syn(--NHR 2 ) geometrical isomers of the formula II cyanoguanidines. These isomers do not demonstrate the phenomenon of tautomery and thus, are not intermediates for the production of amino-nitrile and imino-alkyl cyanoguanidines having the following formula: ##STR5## In solution, the IIa and IIb isomers do not transform into each other. A high energy barrier prevents establishment of either a tautomeric or an E to Z isomeric equilibrium. This high energy barrier results from the rapidity of inversion of the --NCN group (probably by a rotational-bond mechanism) which is greater than the rate of rotation of the --NHR 1 and --NHR 2 groups.
SUMMARY OF THE INVENTION
This invention discloses a group of cyanoguanidine derivatives characterized by the following imino-alkyl and amino-nitrile formula: ##STR6## wherein R 1 and R 2 may or may not be identical. The invention also relates to a method for producing these novel cyanoguanidines.
Cyanoguanidines conforming to structure IV are unique, and their intermediate guanidines of structure I do not represent tautomers of either of the known formula II cyanoguanidines. The phenomenon of tautomery involves the establishment of an equilibrium between the tautomers. If the formula I and II cyanoguanidines were in fact tautomers, upon dissolving the formula II cyanoguanidine in a suitable solvent, the corresponding formula I cyanoguanidine would also be found in the solution. It may be hypothesized that the absence of the formula I cyanoguanidine is due to an equilibrium situation in which the quantity of the formula I cyanoguanidine is reduced to a level at which its presence cannot be detected. If this were the case however, upon dissolving a formula I cyanoguanidine in the same solvent, it would be expected that it would be transformed into the corresponding formula II cyanoguanidine until it no longer existed in the solution above a trace amount. This does not occur, and it has been established that:
(1) in solutions of formula II cyanoguanidines, the presence of the corresponding formula I cyanoguanidine is not detected;
(2) in solutions of formula I cyanoguanidines, the presence of the corresponding formula II cyanoguanidine is not detected.
DETAILED DESCRIPTION OF THE INVENTION
Stable conformations which can be isolated from the formula I cyanoguanidines are the following: ##STR7##
The absence of a demonstrated tautomery phenomenon between the formula Ia, Ib, Ic cyanoguanidines and the formula IIa or IIb cyanoguanidines is due to the respective molecular stability of each of these cyanoguanidine groups. The molecular stability of formula Ia and Ib cyanoguanidines is, most likely, caused by an interaction of the amino-nitrile component with the imino-alkyl component; within a planar structure. This interaction leads to a considerable decrease in the electrical moment of the nitrile component, as reflected by the disappearance of its infra-red absorption. The molecular stability of the formula Ia and Ib cyanoguanidines is also attributed to the basicity of the imino-alkyl and the amino-nitrile guanidine functional groups, allowing the formation of, for example, stable salts such as a hydrochloride of the particular guanidine. This interaction, and the effected molecular stability are no longer manifested when, for example, a formula I cyanoguanidine is dissolved in acetonitrile or dimethylformamide at temperatures between about 50° and 80° C. and, consequently, infra-red absorption is demonstrated by the amino-nitrile component. The disappearance of the molecular stability characteristic leads to the establishment of an equilibrium with new tautomers. This phenomenon can be effected using the hydrochloride of the chosen guanidine, but it appears more rapidly when the corresponding base of the guanidine is used. Neutralization of the hydrochloride by an equivalent quantity of alkaline alkoxide permits development of the infra-red absorption described above. The established equilibrium can be depicted as follows: ##STR8##
As demonstrated above, it is seen that compounds having the Ia or Ib formulas are tautomers of formula III compounds (imino-nitrile tautomers demonstrating less stability.)
The rapidity of inversion of the C═NR 1 (R 2 ) group of formula Ia and Ib structures is less than that of the rotation of the --NHR 2 (R 1 ) and --NHCN groups. This represents an opposite phenomenon to that observed with formula IIa and IIb cyanoguanidines. This difference in dynamic behavior is the reason why the Ia and Ib cyanoguanidines demonstrate tautomery, while formula IIa and IIb cyanoguanidines do not.
For these reasons, formula I cyanoguanidines cannot be obtained from formula II cyanoguanidines by a displacement of equilibrium. Instead, the existence of formula I cyanoguanidines depends upon: (1) the invention of a reactant which will provide, stereospecifically, the desired configuration or (2) the discovery of a reaction characterized by the irreversible displacement of the double bond of the guanidine functional group.
According to this invention, a guanidine derivative of the following formula, is provided: ##STR9## which is characterized by an imino-alkyl and amino-nitrile components and wherein R 1 is a 2-mercapto-ethyl, a 2-hydroxy-ethyl, 2-((4-methyl-5-imidazolyl)thio-methyl) ethyl, or a 2-((4-methyl-5-imidazolyl)dithioformyloxymethyl)ethyl radical, and R 2 represents a methyl radical.
The compounds of the invention are:
N-methyl-N'-cyano-N"-imino-(2-mercapto-ethyl) guanidine, N-methyl-N'-cyano-N"-imino-(2-hydroxy-ethyl) guanidine, N-methyl-N'-cyano-N"-imino-[2-((4-methyl-5-imidazolyl)-thio-methyl) ethyl] guanidine, N-methyl-N'-cyano-N"-imino-[2-((4-methyl-5-imidazolyl)-di-thioformyl-oxymethyl) ethyl] guanidine.
The process for the preparation of the cyanoguanidine compounds of this invention includes the irreversible transformation of formula II cyanoguanidines into formula I cyanoguanidines by means of an intermediate HX reactant, in which X represents Cl - , Br - , I - , PO 4 H 2 - , SO 4 H - , 4CH 3 C 6 H 4 SO 3 - . The elimination of HX leads to the novel amino-nitrile and imino-alkyl structure of formula I cyanoguanidines: ##STR10##
A compound having the following formula: ##STR11## may be prepared according to any of the following processes:
(1) condensing a reactant which already possesses the desired tautomery form, N-methyl-N'-cyano-N"-imino (2-mercapto-ethyl)guanidine, for example, with 4-methyl-5-chloromethyl-imidazole. or,
(2) condensing a sodium or potassium xanthogenate of N-methyl-N'-cyano-N"-imino(2-hydroxy-ethyl)guanidine with 4-methyl-5-chloromethyl-imidazole and subjecting the obtained xanthate to a Chugaev-type transformation. or,
(3) reacting a compound having the following formula: ##STR12## with a hydrogenated mineral, such as HCl for example, to give an addition intermediary, from which the mineral is then eliminated, to yield, for example, a dihydrochloride of the formula V compound.
Formula V compounds, as well as the therapeutically suitable salts of these compounds, antagonize the activity of histamine in the H 2 receptors, thus blocking the histamine's stimulation of hydrochloric acid production in the stomach. Formula V compounds are also advantageously used for the therapeutic treatment of gastric and duodenal ulcers. Suitable excipients for pharmaceutical forms of formula V compounds are, for example, lactose, saccharose, talcum, gelatine, arabic gum or olive oil.
EXAMPLES
The following examples are set forth for the purpose of illustration only and are not to be construed as limiting the scope of the invention in any manner.
EXAMPLE 1
Preparation of N-methyl-N'-cyano-N"-imino-(2-mercapto-ethyl) guanidine
0.76 g of HCl in ether is added to a solution of 2.42 g of N-methyl-N'-cyano-N"-imino-(2-tetrahydropyranylthio-ethyl) guanidine in dry ethanol. After a reaction time of 40 minutes, infra-red spectrophotometry indicates the absence of absorptions by the nitrile component and the presence of absorption activity by the addition intermediary. The intermediary is precipitated by an ether and the imino-(2-mercapto-ethyl)guanidine is crystallized as hydrochloride by rubbing. The imino-(2-mercapto-ethyl)guanidine is then transformed in water by AgNO 3 into the Ag mercaptide derivative of N-methyl-N'-cyano-N"-imino (2-mercapto-ethyl)guanidine as hydrochloride. The following are observed:
______________________________________Chloride ion titration 99.5%IR (film): 1710, 1655(cm.sup.-1) 1590, 1455, 1380, 1300______________________________________
EXAMPLE 2
Preparation of N-methyl-N'-cyano-N"-imino-(2-hydroxy-ethyl)guanidine as hydrochloride
Two equivalents of HCl in dry ether are added to a solution of 4.26 g of N-methyl-N'-cyano-imino-N"-(2-hydroxy-ethyl)guanidine in dry methanol. After 30 minutes, there is no infra-red absorption by the nitrile component and the IR absorptions of the addition intermediary are as follows: 1670, 1630, 1580, 1565 (cm -1 ). The intermediary is precipitated by an ether and the resulting oil is taken up by methanol. The hydrochloride of N-methyl-N'-cyano-N"-imino-(2-hydroxy-ethyl)guanidine is crystallized out by rubbing, m.p. 184°-186° C. The following are observed:
______________________________________C.sub.5 H.sub.10 N.sub.4 O.HCl (178.5) % C % H % N______________________________________Calculated 33.61 5.60 31.37Found 33.43 5.72 31.25IR (nujol) 3250, 3120, 1720 (doublet),(cm.sup.-1) 1665, 1600 (doublet), 1510, 1400, 1290, 1260, 1105, 995, 950, 900, 850 (doublet), 700.______________________________________
EXAMPLE 3(a)
Preparation of N-methyl-N'-cyano-N"-imino[2-((4-methyl-5-imidazolyl) thio-methyl)ethyl]guanidine as dihydrochloride
3 equivalent parts of HCl in ether are added to a solution of 2.52 g of N-methyl-N'-imino-cyano-N"-2-((4-methyl-5-imidazolyl)ethyl guanidine in dry ethanol. After 30 minutes, IR absorption activity of the nitrile component disappears, and IR absorption activity of the addition intermediary is apparent (1665, 1630, 1570 cm -1 .) The intermediary is precipitated with ether and the resulting oil is washed by the ether and taken up by methanol, from which, by rubbing, the dihydrochloride of the N-methyl-N'-cyano-N"imino[2-((4-methyl-5-imidazolyl) thio-methyl)ethyl]guanidine is crystallized; m.p. 120°-122° C. The following are observed:
______________________________________IR (nujol) 3300, 3200, 3100, 2700, 2650, 1700,(cm.sup.-1) 1665, 1590, 1410, 1400, 1360, 1315, 1290, 1260, 1245, 1210, 1165 (doublet), 1100, 1025, 935, 870, 780, 700______________________________________
EXAMPLE 3(b)
Preparation of N-methyl-N'-cyano-N"-imino-[2-((4-methyl-5-imidazolyl) thio-methyl)ethyl]guanidine as monohydrochloride
The dihydrochloride of N-methyl-N'-cyano-N"-imino-[2-((4-methyl-5-imidazolyl)thio-methyl)ethyl]guanidine as prepared in Ex. 3(a), is mixed with a molar excess of triethylamine. A small amount of methanol is added to the mixture in order to dissolve it completely. After 20 minutes, the solvent is evaporated under reduced pressure and the monohydrochloride of N-methyl-N'-cyano-N"-imino-[2-((4-methyl-5-imidazolyl)thio-methyl)ethyl]guanidine is crystallized in acetonitrile; m.p. 174°-176° C.
The following results are recorded:
______________________________________C.sub.10 H.sub.16 N.sub.6 S.HCl (288.5) % C % H % N % S______________________________________Calculated 41.59 5.85 29.11 11.09Found 41.46 5.95 29.04 11.12IR (nujol) 3200, 3080, 1710, 1644, 1605, 1570,(cm.sup.-1) 1480, 1395, 1340, 1305, 1230, 1150 (doublet), 1080, 1065, 1040, 1010, 1005, 960, 845, 780 (doublet), 690, 660______________________________________
EXAMPLE 4
Preparation of N-methyl-N'-cyano-N"-imino[2-((4-methyl-5-imidazolyl)thio-methyl)ethyl]guanidine as monohydrochloride
0.68 g of sodium hydride and 8 ml of carbon disulfide are added to a suspension of 1.80 g of N-methyl-N'-cyano-N"-imino-(2-hydroxy-ethyl) guanidine as hydrochloride in dry tetrahydrofuran. After a reaction time of 15 hours, 1.52 g of 4-methyl-5-chloro-methylimidazole in dry ethanol is introduced into the medium under agitation. The mixture is taken to reflux and carbon oxysulfide is liberated. After the solvent is evaporated, the residue is neutralized with an equivalent part of HCl and crystallized in acetonitrile as a monohydrochloride with a m.p. 174°-176° C.
EXAMPLE 5
Preparation of N-methyl-N'-cyano-N"-imino [2-((4-methyl-5-imidazolyl)thio-methyl)ethyl] guanidine as monohydrochloride
1.95 g of N-methyl-N'-cyano-N"-imino-(2-mercapto-ethyl) guanidine, as hydrochloride, followed by 1.95 g of sodium ethoxide are added to a solution of 1.30 g of 4-methyl-5-chloromethyl-imidazole in dry ethanol, under inert gas such as argon. After a reaction time of 5 hours, the NaCl is separated by filtration and the product is isolated by evaporation of the solvent. The monohydrochloride is crystallized after neutralization by an equivalent part of HCl in acetonitrile. F. 174°-176°.
EXAMPLE 6
Preparation of N-methyl-N'-cyano'-N"-imino [-2((4-methyl-5-imidazolyl)thio-methyl)-ethyl] guanidine as dihydrochloride
1.95 g of hydrochloride of N-methyl-N'-cyano-N"-imino-(2-mercapto-ethyl) guanidine is added to a solution of 1.90 g of hydrochloride of 4-methyl-5-acetoxy-methyl-imidazole in dry ethanol. The mixture is refluxed for 12 hours. The dihydrochloride product is crystallized out in methanol, m.p. 120°-122° C.
EXAMPLE 7
Preparation of N-methyl-N'-imino-cyano-N"-[2-((4-methyl-5-imidazolyl)thio-methyl)-ethyl] guanidine
The monohydrochloride of N-methyl-N'-cyano-N"-imino-2-((4-methyl-5-imidazolyl)thio-methyl)ethyl guanidine is refluxed for 16 hours in acetonitrile containing a small amount of methanol. After neutralization, the base is isolated as an oil. The following are observed:
______________________________________IR (film) 3200, 3100, 2150, 1580-1560, 1475, 1440,(cm.sup.-1) 1390, 1285, 1225, 1170, 1080, 790______________________________________
EXAMPLE 8
Preparation of N-methyl-N'-cyano-imino-N"[-2-((4-methyl-5-imidazolyl)thio-methyl)-ethyl] guanidine
3.2 g of the monohydrochloride or 3.6 g of the dihydrochloride of N-methyl-N'-cyano-N"-imino-2-((4-methyl-5-imidazolyl)thio-methyl)ethyl guanidine is neutralized in ethanol. The NaCl is separated by filtration, the solvent is evaporated and the residue is taken up with dimethylformamide. This solution is maintained at 62° for 7 hours. The solvent is then evaporated under 0.02 T.
The residue is extracted with acetonitrile and after evaporation under reduced pressure, an oil is obtained. The following are observed:
______________________________________IR (film) 3200, 3100, 2150, 1580-1560, 1475, 1440(cm.sup.-1) 1390, 1285, 1170, 1080, 790______________________________________
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The invention relates to cyanoguanidine derivatives characterized by an imino-alkyl and amino-nitrile structure having the general formula: ##STR1## in which R 1 is a 2-mercapto-ethyl, 2-hydroxy-ethyl, a 2-((4-methyl-5-imidazoly)thio-methyl)ethyl, or a 2-((4-methyl-5-imidazolyl)dithioformyloxy-methyl)ethyl radical, and R 2 is the methyl radical. The invention relates to the manufacture of imino-methyl and amino-nitrile cyano-guanidines.
One compound of invention: N-methyl-N'-cyano-N"-imino-[2-((4-methyl-5-imidazolyl)thio-methyl) ethyl] guanidine is a histamine antagonist in the H 2 receptors and inhibits the secretion of gastric acid. It can be used thereapeutically for the treatment of gastric and duodenal ulcers.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. Ser. No. 09/715,380, filed Nov. 17, 2000, now U.S. Pat. No. 6,515,155, which claims benefit of priority from provisional applications 60/170,178, 60/170,177, and 60/170,175, all filed on Dec. 10, 1999.
FIELD OF THE INVENTION
This invention relates to a class of metal complexes, the ligands used to prepare these metal complexes, polymerization catalysts derived therefrom, and the resulting polymerization processes using the same. More particularly, such metal complexes are characterized by a nitrogen containing aliphatic or cycloaliphatic moiety that is substituted with one or more aryl groups, an aryl-substituted silane bridging group, or one or more Group 14 organometalloid substituents on the metal.
BACKGROUND
EP-A-923,589, which is equivalent to WO98/06727, published Feb. 19, 1998, disclosed Group 4 metal complexes containing a heteroatom substituent at the 3-position of the cyclopentadienyl, especially indenyl, ligand groups. Particular heteroatom containing substituents included dihydrocarbylamino substituents including dimethylamino, diethylamino, methylethylamino, methylphenylamino, dipropylamino, dibutylamino, piperidinyl, morpholinyl, pyrrolidinyl, hexahydro-1H-azepin-1-yl, hexahydro-1(2H)-azocinyl, octahydro-1H-azonin-1-yl, and octahydro-1(2H)-azecinyl.
EP-A-577,581 discloses unsymmetrical bis-Cp metallocenes containing a fluorenyl ligand with heteroatom substituents. E. Barsties; S. Schaible; M.-H. Prosenc; U. Rief; W. Roll; O. Weyland; B. Dorerer; H.-H. Brintzinger J. Organometallic Chem. 1996, 520, 63-68, and H. Plenio; D. Birth J. Organometallic Chem. 1996, 519, 269-272 disclose systems in which the cyclopentadienyl ring of the indenyl is substituted with a dimethylamino group in non-bridged and Si-bridged bis-indenyl complexes useful for the formation of isotactic polypropylene and polyethylene.
Disclosure of random heteroatom substitution in mono-Cp metallocenes is found in EP-A-416,815, WO 95/07942, WO 96/13529, and U.S. Pat. Nos. 5,096,867 and 5,621,126. Specific heteroatom substitution of the 3- and 2-position of indenyl complexes of group 4 metals was disclosed in WO98/06727 and WO/98/06728 respectively.
Despite the advance in the art, particular higher use temperature, obtained by such prior art metal complexes as were disclosed in the foregoing reference, there remains a desire for improved metal complexes capable of even further increase in use temperature that are still capable of forming catalyst compositions useful in producing polymers having high molecular weights and, for ethylene/higher α-olefin copolymers, high incorporation of comonomer. The subject compositions of this invention show unexpected improvement in these desirable features.
SUMMARY OF THE INVENTION
According to the present invention there are provided metal complexes corresponding to the formula:
where M is a Group 4 metal that is in the +2, +3 or +4 formal oxidation state;
R A independently each occurrence is hydrogen, or a hydrocarbyl, halohydrocarbyl, hydrocarbyloxyhydrocarbyl, dihydrocarbylaminohydrocarbyl, dihydrocarbylamino, hydrocarbyloxy, hydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl group of from 1 to 80 atoms, not counting hydrogen, or further optionally, two or more R A groups may be covalently linked together;
Z is (R D ) 2 Si═, wherein R D independently each occurrence is C 7-20 alkaryl or two R D groups together are alkyl- or polyalkyl-substituted arylene of up to 40 carbons; and
Y is bonded to M and Z and is selected from the group consisting of —O—, —S—, —NR E —, and —PR E —; wherein, R E independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R E having up to 20 nonhydrogen atoms
X is an anionic or dianionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, π-bound ligand groups;
X′ independently each occurrence is a neutral ligand having up to 40 atoms;
p is zero, 1 or 2, and is two less than the formal oxidation state of M when X is an anionic ligand, and when X is a dianionic ligand group, p is 1; and
q is zero, 1 or 2.
The above complexes may exist as isolated crystals optionally in pure form or as a mixture with other complexes, in the form of a solvated adduct, optionally in a solvent, especially an organic liquid, in the form of a dimer or chelated derivative thereof, wherein the chelating agent is an organic material, preferably a Lewis base, especially a dihydrocarbylether, cyclic aliphatic ether, trihydrocarbylamine, trihydrocarbylphosphine, or halogenated derivative thereof, or as a polymeric or crosslinked polymeric product, wherein one or more R A groups are polymerized with one another or copolymerized with an ethylenically unsaturated comomomer.
Also, according to the present invention, there is provided a catalyst composition, useful, inter alia, for the polymerization of addition polymerizable monomers, comprising the following components or the reaction product thereof:
(A) one or more metal complexes of formula (I) or (II); and
(B) an activating cocatalyst, wherein the molar ratio of (A) to (B) is from 1:10,000 to 100:1.
Another embodiment of this invention is the foregoing catalyst composition wherein the metal complex is in the form of a radical cation.
Further according to the present invention there is provided a polymerization process comprising contacting one or more addition polymerizable monomers under polymerization conditions with one of the aforementioned catalyst compositions.
A preferred process of this invention is a high temperature solution polymerization process comprising contacting one or more addition polymerizable monomers under polymerization conditions with one of the aforementioned catalyst systems at a temperature from 50° C. to 250° C., preferably from 150° C. to 250° C., most preferably from 175° C. to 220° C. Within the scope of this invention are the polymeric products produced by the aforementioned processes.
This invention also includes the precursor of the delocalized electron containing, cyclic moiety of the metal complex of formula (I), said precursor corresponding to the formula:
wherein, Y′ is —OR C , —SR C , —NR C R E , —PR C R E ;
R C independently each occurrence is hydrogen, an alkali metal cation, or a magnesium halide cation, or both R C groups together are an alkaline earth metal dication;
Z* is (R D ) 2 Si═, wherein R D independently each occurrence is C 7-20 alkaryl or two R D groups together are alkyl- or polyalkyl-substituted arylene of up to 40 carbons; and
R A and R E are as previously defined.
It is to be understood that the foregoing formulas (IA) and (IIA) depict one of several equivalent interannular, double bond isomers, and that all such isomeric structures are intended to be included by the formulas.
The final embodiment of the invention is the use of one of the foregoing compounds of formula (IA) or (IIA) in a synthesis to produce a Group 4 metal complex of formula (I) or (II).
The present catalysts and processes are especially suited for use in the production of high molecular weight polymers of olefin monomers, over a wide range of polymerization conditions, and especially at elevated temperatures, with exceptionally high catalyst efficiencies. They are especially useful for the solution polymerization of ethylene homopolymers, copolymers of ethylene with an α-olefin other than ethylene (ethylene/α-olefin copolymers), and ethylene/propylene/diene interpolymers (EPDM polymers) wherein the diene is ethylidenenorbornene, 1,4-hexadiene or similar nonconjugated diene. The use of elevated temperatures dramatically increases the productivity of such processes due to the fact that increased polymer solubility at elevated temperatures allows the use of increased conversions (higher concentration of polymer product) without exceeding solution viscosity limitations of the polymerization equipment as well as reduced energy costs needed to devolatilize the reaction product. In the preparation particularly of copolymers of ethylene and at least one α-olefin comonomer, the present catalyst compositions incorporate relatively large quantities of non-ethylene comomomer compared to catalysts comprising a conventional metal. In particular, ethylene/1-octene copolymers having reduced density due to increased incorporation of 1-octene therein, may be made using the present catalyst compositions.
The metal complexes of this invention may also be supported on a support material and used in olefin polymerization processes in a slurry or in the gas phase. Additionally, those complexes wherein R A is ethylenically unsaturated may be used to form polymeric reaction products via polymerization of copolymerization of such ethylenic unsaturation in the R A moiety. Such products may be employed in a slurry or gas phase polymerization without need for an additional support material. Such a polymeric catalyst may be formed by prepolymerization of the functionalized metal complex, optionally with one or more ethylenically unsaturated monomers, in situ in a polymerization reactor or in a separate reactor with recovery of the prepolymerized catalyst prior to the primary polymerization process.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the single crystal structure derived by X-ray analysis (ORTEP) of (N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-[(dimethylsilylene)bis(methylene)] titanium (Example 7).
FIG. 2 shows the single crystal structure derived by X-ray analysis (ORTEP) of (N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl) (Example 8).
DETAILED DESCRIPTION
All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1997. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. As used herein the term “comprising” is not intended to exclude any additional component, additive or step. For purposes of U.S patent practice, the contents of any patent, patent application or publication referenced herein are hereby incorporated by reference in their entirety, especially with respect to the disclosure of synthetic techniques and general knowledge in the art.
In a preferred embodiment of the invention, R D is C 1-10 alkyl substituted phenyl group, preferably a C 4-10 alkyl substituted phenyl group. In addition, it is independently highly desirable that R D is substituted in the para position or is a mixture of C 1-10 alkylphenyl substitution isomers. A most preferred R D group is p-n-butylphenyl.
Preferred compounds according to the invention are those compounds of formula (I) corresponding to the formula:
where R B′ corresponds to the formula N(R B ) 2 , wherein R B each occurrence is C 1-10 hydrocarbyl, or a halo- or tri(C 1-4 hydrocarbyl)silyl-substituted derivative thereof, or two R B groups together form a divalent hydrocarbon moiety, or a halo- or tri(C 1-4 hydrocarbyl)silyl-substituted derivative thereof, said divalent group containing from 4 to 40 atoms not counting hydrogen; and
R A , Z, M, X, X′, p and q are as previously defined.
Most preferably, N(R B ) 2 , is dibenzylamino or two R B groups together with the nitrogen atom form a cycloaliphatic group, optionally substituted with an aromatic group. In a most preferred embodiment, the cycloaliphatic group is substituted with an aromatic group, which more preferably still, is a benzannulated ligand, which, together with both R B groups forms a multiple ring, fused heteroatomic group. Thus, most preferably, —N(R B ) 2 is in the form of a multiple ring, fused, aza-cyclic group. Examples of the foregoing, —N(R B ) 2 groups include: 1,3-dihydro-2H-isoindol-2-yl, 1,2,3,4-tetrahydro-2H-isoquinoline-2-yl, 1,3-dihydro-2H-benzo[f]isoindol-2-yl, 1,3-dihydro-2H-benzo[e]isoindol-2-yl, 1,2,3,4-tetrahydro-2H-benzo[g]isoquinoline-2-yl, 1,2,3,4-tetrahydro-2H-benzo[f]isoquinoline-2-yl, 1,2,3,4-tetrahydro-2H-benzo[h]isoquinoline-2-yl, 1H-benzo[de]isoquinolin-2(3H)-yl, and dibenzylamino groups, corresponding to the following formulas:
A preferred Group 4 metal for all of the present metal complexes is titanium.
Preferred X groups are halo, C 1-10 hydrocarbyl or trialkylsilylalkyl groups of up to 20 caarbons, or two such X groups together form a divalent ligand group. Most preferred X groups are chloro, methyl, trimethylsilylmethyl, or two X groups together are (dimethylsilylene)bis-(methylene), most preferably trimethylsilylmethyl, or two X groups together are (dimethylsilylene)bis(methylene). In the embodiments wherein X is trimethylsilylmethyl the complexes possess improved catalytic activity. In the embodiments wherein two X groups together are (dimethylsilylene)bis(methylene) the metal complexes additionally are particularly stable (robust) under typical storage and use conditions.
Preferred R A groups (other than the —NR B groups previously disclosed at the 3 position of compounds of formula (I)) are hydrogen, or an alkyl, aryl or aralkyl group of up to 10 carbons.
Preferably in all embodiments of the invention, Y is —NR E — where R E is C 1-6 alkyl or cycloalkyl, preferably isopropyl, cyclohexyl, or t-butyl.
Preferred X′ groups in all of the foregoing embodiments of the invention are carbon monoxide; phosphines, especially trimethylphosphine, triethylphosphine, triphenylphosphine and bis(1,2-dimethylphosphino)ethane; P(OR K ) 3 , wherein R K , independently each occurrence, is hydrocarbyl, silyl or silylhydrocarbyl; ethers, especially tetrahydrofuran; amines, especially pyridine, bipyridine, tetramethylethylenediamine (TMEDA), or triethylamine; olefins; and conjugated dienes having from 4 to 40 carbon atoms. Complexes including the latter X′ groups, especially terminally hydrocarbyl substituted-1,3-butadienes, include those wherein the metal is in the +2 formal oxidation state.
In the foregoing compounds when p is 2, q is zero, M is in the+3 or +4 formal oxidation state, and X independently each occurrence preferably is chloride, methyl, benzyl, trimethylsilylmethyl, allyl, pyrollyl or two X groups together are 1,4-butane-diyl, 2-butene-1,4-diyl, 2,3-dimethyl-2-butene-1,4-diyl, 2-methyl-2-butene-1,4-diyl, xylyldiyl, or (dimethylsilylene)bis(methylene). Additionally, when p is 1, q is zero, M is in the +3 formal oxidation state, and X is preferably, 2-(N,N-dimethyl)aminobenzyl, 2-(N,N-dimethylaminomethyl)phenyl, allyl, or methallyl. Finally, when p is 0, q is 1, M is in the +2 formal oxidation state, and X′ is 1,4-diphenyl-1,3-butadiene, 1,3-pentadiene or 2,4-hexadiene.
Highly preferred complexes according to the invention correspond to the formulas:
where R F is C 1-10 alkyl substituted phenyl, preferably C 4-10 alkyl substituted phenyl, most preferably n-butylphenyl, most highly preferably para-n-butylphenyl;
R I is chloro, methyl, benzyl, trimethylsilylmethyl or two R I groups together are (dimethylsilylene)bis(methylene); and
R J is allyl, 2-(dimethylamino)benzyl, 1,4-pentadiene or 1,4-diphenyl-1,3-butadiene.
Illustrative metal complexes according to the present invention include:
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titaniumdimethyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-(tetramethyl-η-cyclopentadienyl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)—N)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(2,3,4,5-tetrahydro-1-pyridinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-7)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titaniumdimethyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl))-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-,4-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,2,3,4-tetrahydro-2(1H)-isoquinolinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-1)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[f]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-benzo[e]isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-,4-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)iphenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-indene-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl; and
(N-(cyclohexyl)-1,1-di(4-n-butyl)phenyl-1-((1,2,3,3a,7a-η)-3-(N,N-dibenzylamino)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene.
The complexes can be prepared by use of well known synthetic techniques. The reactions are conducted in a suitable noninterfering solvent at a temperature from −100 to 300° C., preferably from −78 to 100° C., most preferably from 0 to 50° C. Suitable reaction media for the formation of the complexes include aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, particularly branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, and xylene, C 1-4 dialkyl ethers, C 1-4 dialkyl ether derivatives of (poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoing are also suitable.
Optionally a reducing agent can be employed to produce the lower oxidation state complexes. By the term “reducing agent” herein is meant a metal or compound which, under reducing conditions causes the metal M, to be reduced from a higher to a lower oxidation state. Examples of suitable metal reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alloys of alkali metals or alkaline earth metals such as sodium/mercury amalgam and sodium/potassium alloy. Examples of suitable reducing agent compounds are sodium naphthalenide, potassium graphite, lithium alkyls, lithium or potassium alkadienyls; and Grignard reagents. Most preferred reducing agents are the alkali metals or alkaline earth metals, especially lithium and magnesium metal. Suitable techniques for preparing complexes of the present invention are well known to the skilled artisan and may be readily derived from techniques taught, for example, in the previously mentioned publication, WO98/06727 (U.S. Ser. No. 230,185, filed Jul. 28, 1997).
The complexes are rendered catalytically active by combination with an activating cocatalyst or use of an activating technique, such as those that are previously known in the art for use with Group 4 metal olefin polymerization complexes. Suitable activating cocatalysts for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane; neutral Lewis acids, such as C 1-30 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluorophenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts of compatible, noncoordinating anions, or ferrocenium salts of compatible, noncoordinating anions; bulk electrolysis (explained in more detail hereinafter); and combinations of the foregoing activating cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,064,802, U.S. Pat. No. 5,321,106, U.S. Pat. No. 5,721,185, U.S. Pat. No. 5,350,723, U.S. Pat. No. 5,425,872, U.S. Pat. No. 5,625,087, U.S. Pat. No. 5,883,204, U.S. Pat. No. 5,919,983, U.S. Pat. No. 5,783,512, WO 99/15534, and U.S. Ser. No. 09/251,664, filed Feb. 17, 1999.
Combinations of neutral Lewis acids, especially the combination of a trialkylaluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tri(hydrocarbyl)boron compound having from 1 to 20 carbons in each hydrocarbyl group, especially tris(pentafluorophenyl)borane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane are especially desirable activating cocatalysts. Preferred molar ratios of Group 4 metal complex:tris(pentafluoro-phenylborane:alumoxane are from 1:1:1 to 1:10:30, more preferably from 1:1:1.5 to 1:5:10.
Suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion, A − . As used herein, the term “noncoordinating” means an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base. A noncoordinating anion specifically refers to an anion which when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes. “Compatible anions” are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.
Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gallium, niobium or tantalum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.
Preferably such cocatalysts may be represented by the following general formula:
(L*−H) d + (A) d−
wherein:
L* is a neutral Lewis base;
(L*−H) + is a conjugate Bronsted acid of L*;
A d− is a noncoordinating, compatible anion having a charge of d−, and
d is an integer from 1 to 3.
More preferably A d− corresponds to the formula: [M′Q 4 ] − ;
wherein:
M′ is boron or aluminum in the +3 formal oxidation state; and
Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halo-substituted hydrocarbyl, halo-substituted hydrocarbyloxy, and halo-substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in U.S. Pat. No. 5,296,433.
In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A − . Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula:
(L*−H) + (BQ 4 ) − ;
wherein:
L* is as previously defined;
B is boron in a formal oxidation state of 3; and
Q is a hydrocarbyl-, hydrocarbyloxy-, fluorohydrocarbyl-, fluorohydrocarbyloxy-, hydroxyfluorohydrocarbyl-, dihydrocarbylaluminumoxyfluorohydrocarbyl-, or fluorinated silylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl. Most preferably, Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl group.
Preferred Lewis base salts are ammonium salts, more preferably trialkylammonium salts containing one or more C 12-40 alkyl groups.
Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are
tri-substituted ammonium salts such as:
trimethylammonium tetrakis(pentafluorophenyl)borate,
triethylammonium tetrakis(pentafluorophenyl)borate,
tripropylammonium tetrakis(pentafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,
tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate,
N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate,
N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate,
N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate,
dimethyltetradecylammonium tetrakis(pentafluorophenyl)borate,
dimethylhexadecylammonium tetrakis(pentafluorophenyl)borate,
dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate,
methylditetradecylammonium tetrakis(pentafluorophenyl)borate,
methylditetradecylammonium(hydroxyphenyl)tris(pentafluorophenyl)borate,
methylditetradecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl)borate,
methyldihexadecylammonium tetrakis(pentafluorophenyl)borate,
methyldihexadecylammonium(hydroxyphenyl)tris(pentafluorophenyl)borate,
methyldihexadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl)borate,
methyldioctadecylammonium tetrakis(pentafluorophenyl)borate,
methyldioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl)borate,
methyldioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl)borate,
mixtures of the foregoing,
dialkyl ammonium salts such as:
di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,
methyloctadecylammonium tetrakis(pentafluorophenyl)borate,
methyloctadodecylammonium tetrakis(pentafluorophenyl)borate, and
dioctadecylammonium tetrakis(pentafluorophenyl)borate;
tri-substituted phosphonium salts such as:
triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate;
di-substituted oxonium salts such as:
diphenyloxonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and di(octadecyl)oxonium tetrakis(pentafluorophenyl)borate;
di-substituted sulfonium salts such as:
di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, and methylcotadecylsulfonium tetrakis(pentafluorophenyl)borate.
Preferred (L*−H) + cations are methyldioctadecylammonium and dimethyloctadecylammonium. The use of the above Bronsted acid salts as activating cocatalysts for addition polymerization catalysts is known in the art, having been disclosed in U.S. Pat. Nos. 5,064,802, 5,919,983, 5,783,512 and elsewhere.
Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
(Ox e+ ) d (A d− ) e .
wherein:
Ox e+ is a cationic oxidizing agent having a charge of e+;
e is an integer from 1 to 3; and
A d− and d are as previously defined.
Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + , or Pb +2 . Preferred embodiments of A d− are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate. The use of the above salts as activating cocatalysts for addition polymerization catalysts is known in the art, having been disclosed in U.S. Pat. No. 5,321,106.
Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula:
Ĉ + A −
wherein:
Ĉ + is a C 1-20 carbenium ion; and
A − is as previously defined. A preferred carbenium ion is the trityl cation, that is triphenylmethylium. The use of the above carbenium salts as activating cocatalysts for addition polymerization catalysts is known in the art, having been disclosed in U.S. Pat. No. 5,350,723.
A further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula:
R 3 Si(X′) q + A −
wherein:
R is C 1-10 hydrocarbyl, and X′, q and A − are as previously defined.
Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof. The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is known in the art, having been disclosed in U.S. Pat. No. 5,625,087.
Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used according to the present invention. Such cocatalysts are disclosed in U.S. Pat. No. 5,296,433.
Another class of suitable catalyst activators are expanded anionic compounds corresponding to the formula:
(A 1+a 1 ) b 1 (Z 1 J 1 j 1 ) −c1 d 1 ,
wherein:
A 1 is a cation of charge +a 1 ,
Z 1 is an anion group of from 1 to 50, preferably 1 to 30 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites;
J 1 independently each occurrence is a Lewis acid coordinated to at least one Lewis base site of Z 1 , and optionally two or more such J 1 groups may be joined together in a moiety having multiple Lewis acidic functionality,
j 1 is a number from 2 to 12 and
a 1 , b 1 , c 1 , and d 1 are integers from 1 to 3, with the proviso that a 1 ×b 1 is equal to c 1 ×d 1 .
The foregoing cocatalysts (illustrated by those having imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) may be depicted schematically as follows:
wherein:
A 1+ is a monovalent cation as previously defined, and preferably is a trihydrocarbyl ammonium cation, containing one or two C 10-40 alkyl groups, especially the methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium-cation,
R 8 , independently each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, preferably C 1-20 alkyl, and
J 1 is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)aluminane.
Examples of these catalyst activators include the trihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium-salts of:
bis(tris(pentafluorophenyl)borane)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,
bis(tris(pentafluorophenyl)borane)imidazolinide,
bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,
bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,
bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,
bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,
bis(tris(pentafluorophenyl)alumane)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and
bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.
A further class of suitable activating cocatalysts include cationic Group 13 salts corresponding to the formula:
[M″Q 1 2 L′ 1′ ] + (Ar f 3 M′Q 2 ) −
wherein:
M″ is aluminum, gallium, or indium;
M′ is boron or aluminum;
Q 1 is C 1-20 hydrocarbyl, optionally substituted with one or more groups which independently each occurrence are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, or hydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen, or, optionally, two or more Q 1 groups may be covalently linked with each other to form one or more fused rings or ring systems;
Q 2 is an alkyl group, optionally substituted with one or more cycloalkyl or aryl groups, said Q 2 having from 1 to 30 carbons;
L′ is a monodentate or polydentate Lewis base, preferably L′ is reversibly coordinated to the metal complex such that it may be displaced by an olefin monomer, more preferably L′ is a monodentate Lewis base;
l′ is a number greater than zero indicating the number of Lewis base moieties, L′, and
Ar f independently each occurrence is an anionic ligand group; preferably Ar f is selected from the group consisting of halide, C 1-20 halohydrocarbyl, and Q 1 ligand groups, more preferably Ar f is a fluorinated hydrocarbyl moiety of from 1 to 30 carbon atoms, most preferably Ar f is a fluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms, and most highly preferably Ar f is a perfluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms.
Examples of the foregoing Group 13 metal salts are alumicinium tris(fluoroaryl)borates or gallicinium tris(fluoroaryl)borates corresponding to the formula: [M″Q 1 2 L′ 1′ ] + (Ar f 3 BQ 2 ) − , wherein M″ is aluminum or gallium; Q 1 is C 1-20 hydrocarbyl, preferably C 1-8 alkyl; Ar f is perfluoroaryl, preferably pentafluorophenyl; and Q 2 is C 1-8 alkyl, preferably C 1-8 alkyl. More preferably, Q 1 and Q 2 are identical C 1-8 alkyl groups, most preferably, methyl, ethyl or octyl.
The foregoing activating cocatalysts may also be used in combination. An especially preferred combination is a mixture of a tri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from 1 to 4 carbons in each hydrocarbyl group or an ammonium borate with an oligomeric or polymeric alumoxane compound.
The molar ratio of catalyst/cocatalyst employed preferably ranges from 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferably from 1:1000 to 1:1. Alumoxane, when used by itself as an activating cocatalyst, is employed in large quantity, generally at least 100 times the quantity of metal complex on a molar basis. Tris(pentafluorophenyl)borane, where used as an activating cocatalyst is employed in a molar ratio to the metal complex of form 0.5:1 to 10:1, more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. The remaining activating cocatalysts are generally employed in approximately equimolar quantity with the metal complex.
The catalysts, whether or not supported in any suitable manner, may be used to polymerize ethylenically unsaturated monomers having from 2 to 100,000 carbon atoms either alone or in combination. Preferred addition polymerizable monomers for use herein include olefins, diolefins and mixtures thereof. Preferred olefins are aliphatic or aromatic compounds containing vinylic unsaturation as well as cyclic compounds containing ethylenic unsaturation. Examples of the latter include cyclobutene, cyclopentene, norbornene, and norbornene derivatives that are substituted in the 5- and 6-positions with C 1-20 hydrocarbyl groups. Preferred diolefins are C 4-40 diolefin compounds, including ethylidene norbornene, 1,4-hexadiene, norbornadiene, and the like. The catalysts and processes herein are especially suited for use in preparation of ethylene/1-butene, ethylene/1-hexene, ethylene/styrene, ethylene/propylene, ethylene/1-pentene, ethylene/4-methyl-1-pentene and ethylene/1-octene copolymers as well as terpolymers of ethylene, propylene and a nonconjugated diene, such as, for example, EPDM terpolymers.
Most preferred monomers include the C 2-20 α-olefins, especially ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, long chain macromolecular α-olefins, and mixtures thereof. Other preferred monomers include styrene, C 1-4 alkyl substituted styrene, ethylidenenorbornene, 1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene, divinylbenzene, and mixtures thereof with ethylene. Long chain macromolecular α-olefins are vinyl terminated polymeric remnants formed in situ during continuous solution polymerization reactions. Under suitable processing conditions such long chain macromolecular units are readily polymerized into the polymer product along with ethylene and other short chain olefin monomers to give small quantities of long chain branching in the resulting polymer.
Preferred monomers include a combination of ethylene and one or more comonomers selected from monovinyl aromatic monomers, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidene-norbornene, C 3-10 aliphatic α-olefins (especially propylene, isobutylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 1-octene), and C 4-40 dienes. Most preferred monomers are mixtures of ethylene and styrene; mixtures of ethylene, propylene and styrene; mixtures of ethylene, styrene and a nonconjugated diene, especially ethylidenenorbornene or 1,4-hexadiene, and mixtures of ethylene, propylene and a nonconjugated diene, especially ethylidenenorbornene or 1,4-hexadiene.
In general, the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0-250° C., preferably 30 to 200° C. and pressures from atmospheric to 10,000 atmospheres. Suspension, solution, slurry, gas phase, solid state powder polymerization or other process condition may be employed if desired. A support, especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed when the catalysts are used in a gas phase polymerization process. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal):support from 1:10 6 to 1:10 3 , more preferably from 1:10 6 to 1:10 4 .
In most polymerization reactions the molar ratio of catalyst:polymerizable compounds employed is from 10 −12 :1 to 10 −1 :1, more preferably from 10 −9 :1 to 10 −5 :1.
Suitable solvents use for solution polymerization are liquids that are substantially inert under process conditions encountered in their usage. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C 4-10 alkanes, and alkyl-substituted aromatic compounds such as benzene, toluene, xylene, and ethylbenzene. Suitable solvents also include liquid olefins which may act as monomers or comonomers.
The catalysts may be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in the same reactor or in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties. An example of such a process is disclosed in WO 94/00500.
The catalysts of the present invention are particularly advantageous for the production of ethylene homopolymers and ethylene/α-olefin copolymers having high levels of long chain branching. The use of the catalysts of the present invention in continuous polymerization processes, especially continuous, solution polymerization processes, allows for elevated reactor temperatures which favor the formation of vinyl terminated polymer chains that may be incorporated into a growing polymer, thereby giving a long chain branch. The use of the present catalyst compositions advantageously allows for the economical production of ethylene/α-olefin copolymers having processability similar to high pressure, free radical produced low density polyethylene.
The present catalyst compositions may be advantageously employed to prepare olefin polymers having improved processing properties by polymerizing ethylene alone or ethylene/α-olefin mixtures with low levels of a “H” branch inducing diene, such as norbornadiene, 1,7-octadiene, or 1,9-decadiene. The unique combination of elevated reactor temperatures, high molecular weight (or low melt indices) at high reactor temperatures and high comonomer reactivity advantageously allows for the economical production of polymers having excellent physical properties and processability. Preferably such polymers comprise ethylene, a C 3-20 α-olefin and a “H”-branching comonomer. Preferably, such polymers are produced in a solution process, most preferably a continuous solution process.
The catalyst composition may be prepared as a homogeneous catalyst by addition of the requisite components to a solvent or diluent in which polymerization will be conducted. The catalyst composition may also be prepared and employed as a heterogeneous catalyst by adsorbing, depositing or chemically attaching the requisite components on an inorganic or organic particulated solid. Examples of such solids include, silica, silica gel, alumina, clays, expanded clays (aerogels), aluminosilicates, trialkylaluminum compounds, and organic or inorganic polymeric materials, especially polyolefins. In a preferred embodiment, a heterogeneous catalyst is prepared by reacting an inorganic compound, preferably a tri(C 1-4 alkyl)aluminum compound, with an activating cocatalyst, especially an ammonium salt of a hydroxyaryl(trispentafluorophenyl)borate, such as an ammonium salt of (4-hydroxy-3,5-ditertiarybutylphenyl)tris-(pentafluorophenyl)borate or (4-hydroxyphenyl)-tris(pentafluorophenyl)borate. This activating cocatalyst is deposited onto the support by coprecipitating, imbibing, spraying, or similar technique, and thereafter removing any solvent or diluent. The metal complex is added to the support, also by adsorbing, depositing or chemically attaching the same to the support, either subsequently, simultaneously or prior to addition of the activating cocatalyst.
When prepared in heterogeneous or supported form, the catalyst composition is employed in a slurry or gas phase polymerization. As a practical limitation, slurry polymerization takes place in liquid diluents in which the polymer product is substantially insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent. Likewise, the α-olefin monomer or a mixture of different α-olefin monomers may be used in whole or part as the diluent. Most preferably, at least a major part of the diluent comprises the α-olefin monomer or monomers to be polymerized. A dispersant, particularly an elastomer, may be dissolved in the diluent utilizing techniques known in the art, if desired.
At all times, the individual ingredients as well as the recovered catalyst components must be protected from oxygen and moisture. Therefore, the catalyst components and catalysts must be prepared and recovered in an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are performed in the presence of an dry, inert gas, such as, for example, nitrogen.
The polymerization may be carried out as a batchwise or a continuous polymerization process. A continuous process is preferred, in which event catalyst, ethylene, comonomer, and optionally solvent, are continuously supplied to the reaction zone, and polymer product continuously removed therefrom.
Without limiting in any way the scope of the invention, one means for carrying out such a polymerization process is as follows: In a stirred-tank reactor, the monomers to be polymerized are introduced continuously, together with solvent and an optional chain transfer agent. The reactor contains a liquid phase composed substantially of monomers, together with any solvent or additional diluent and dissolved polymer. If desired, a small amount of a “H”-branch inducing diene such as norbornadiene, 1,7-octadiene or 1,9-decadiene may also be added. Catalyst and cocatalyst are continuously introduced in the reactor liquid phase. The reactor temperature and pressure may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by cooling or heating coils, jackets or both. The polymerization rate is controlled by the rate of catalyst addition. The ethylene content of the polymer product is determined by the ratio of ethylene to comonomer in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. The polymer product molecular weight is controlled, optionally, by controlling other polymerization variables such as the temperature, monomer concentration, or by the previously mention chain transfer agent, such as a stream of hydrogen introduced to the reactor, as is well known in the art. The reactor effluent is contacted with a catalyst kill agent such as water. The polymer solution is optionally heated, and the polymer product is recovered by flashing off gaseous monomers as well as residual solvent or diluent at reduced pressure, and, if necessary, conducting further devolatilization in equipment such as a devolatilizing extruder. In a continuous process the mean residence time of the catalyst and polymer in the reactor generally is from about 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours.
Ethylene homopolymers and ethylene/α-olefin copolymers are particularly suited for preparation according to the invention. Generally such polymers have densities from 0.85 to 0.96 g/ml. Typically the molar ratio of α-olefin comonomer to ethylene used in the polymerization may be varied in order to adjust the density of the resulting polymer. When producing materials with a density range of from 0.91 to 0.93 the comonomer to monomer ratio is less than 0.2, preferably less than 0.05, even more preferably less than 0.02, and may even be less than 0.01. In the above polymerization process hydrogen has been found to effectively control the molecular weight of the resulting polymer. Typically, the molar ratio of hydrogen to monomer is less than about 0.5, preferably less than 0.2, more preferably less than 0.05, even more preferably less than 0.02 and may even be less than 0.01.
The polymerization of ethylene in combination with a diene, especially conjugated dienes and polycyclic bulky dienes such as ethylidene norbornene, optionally in the presence of a third monomer, especially a C 3-12 α-olefin, is particularly advantageously accomplished by the use of metal complexes according to the present invention according to formula (I) containing a 2-alkyl-4-arylinden-1-yl substituent of up to 30 total carbon atoms, especially a 2-methyl-4-phenylinden-1-yl or 2-methyl-4-naphthylinden-1-yl group. That is, preferred metal complexes are those of formula (I) wherein:
is a 2-alkyl-4-arylinden-1-yl group of up to 30 total carbon atoms.
Surprisingly, the activity of catalysts comprising the foregoing metal complexes is relatively unaffected by the diene in comparison with similar metal complexes lacking in the foregoing structure, and the resulting polymers contain relative large quantities of the polymerized diene. Especially preferred metal complexes for the foregoing polymerization are:
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(cyclohexyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl -1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl -1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl -1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl -1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl;
(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl -1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene;
dichloro(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium;
(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium dimethyl;
(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium bis(trimethylsilylmethyl);
(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (dimethylsilylene)bis(methylene);
(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (III) 2-(N,N-dimethylamino)benzyl; and
(N-(cyclohexyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-4-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,4-diphenyl-1,3-butadiene.
EXAMPLES
It is understood that the present invention is operable in the absence of any component which has not been specifically disclosed. The following examples are provided in order to further illustrate the invention and are not to be construed as limiting. Unless stated to the contrary, all parts and percentages are expressed on a weight basis. The term “overnight”, if used, refers to a time of approximately 16-18 hours, “room temperature”, if used, refers to a temperature of about 20-25° C., and “mixed alkanes” refers to a mixture of hydrogenated propylene oligomers, mostly C 6 -C 12 isoalkanes, available commercially under the trademark Isopar E™ from Exxon Chemicals Inc. HRMS refers to high resolution mass spectroscopy.
All solvents were purified using the technique disclosed by Pangborn et al, Organometallics, 15, 1518-1520, (1996). All compounds, solutions, and reactions were handled under an inert atmosphere (dry box). 1 H and 13 C NMR shifts were referenced to internal solvent resonances and are reported relative to TMS.
X-ray analysis was performed in the following manner:
Data Collection: A single crystal of suitable dimensions was immersed in oil, Paratone N™, available from Exxon Chemicals, Inc., and mounted on a thin glass fiber. The crystal was transferred to a Bruker SMART PLATFORM diffractometer equipped with a graphite monochromatic crystal, a MoKox radiation source (λ=0.71073 Å), and a CCD (charge coupled device) area detector. The crystal was bathed in a cold nitrogen stream for the duration of data collection (−100° C.).
Program SMART (available from Bruker AXS, Inc., Madison, Wis., USA) was used for diffractometer control, frame scans, indexing, orientation matrix calculations, least squares refinement of cell parameters, crystal faces measurements and the actual data collection. Program ASTRO (available from Bruker AXS, Inc., Madison, Wis., USA) was used to set up data collection strategy.
Raw data frames were read by. program SAINT (available from Bruker AXS, Inc., Madison, Wis., USA) and integrated using 3D profiling algorithms. The resulting data were reduced to produce hkl reflections and their intensities and estimated standard deviations. The data were corrected for Lorentz and polarization effects. Sufficient reflections were collected to represent a range of 1.51 to 2.16 redundancy level with an R sym value range of 2.5 percent, at the lowest 2θ shell of reflections, to 3.0 percent at the highest 2θ shell of reflections (550). Crystal decay correction was applied and was less than 1 percent. The unit cell parameters were refined by least squares of the setting angles of the reflections.
Absorption corrections were applied by integration based on indexed measured faces. Data preparation was carried out using program XPREP (available from Bruker AXS, Inc., Madison, Wis., USA). The structure was solved by direct methods in SHELXTL5.1 (available from Bruker AXS, Inc., Madison, Wis., USA) from which the positions of all of the non-H atoms were obtained. The structure was refined, also in SHELXTL5.1, using full-matrix least-squares refinement. The non-H atoms were refined with anisotropic thermal parameters and all of the H atoms were calculated in idealized positions and refined riding on their parent atoms, or were obtained from a Difference Fourier map and refined without any constraints. A correction for secondary extinction was not applied. The final refinement was carried out using F 2 rather than F values. R 1 is calculated to provide a reference to the conventional R value but its function is not minimized. Additionally, wR 2 is the function that is minimized, and not R 1 .
The linear absorption coefficient, atomic scattering factors and anomalous-dispersion corrections were calculated from values from the International Tables for X-ray Crystallography (1974). Vol. IV, p. 55. Birmingham: Kynoch Press (Present distributor, D. Reidel, Dordrecht.).
Relevant functions:
R 1 =Σ(∥ F o |−|F c ∥)/Σ| F o |
wR 2 =[Σ[w ( F o 2 −F c 2 ) 2 ]/Σ[wF o 22 ]] 1/2
R int. =Σ|F o 2 −F o 2 (mean)| 2 /Σ[F o 2 ]
S=[Σ[w ( F o 2 −F c 2 ) 2 ]/( n−p )] 1/2
where n is the number of reflections and p is the total number of parameters refined
w= 1/[σ 2 ( F o 2 )+(0.0370* p ) 2 +0.31* p], p =[max( F o 2 , 0)+2* F c 2 ]/3
Example 1
Preparation of dichloro(N-(1,1-dimethylethyl)-1,1-di(p-tolyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium
(A) Preparation of N-(tert-butyl)-N-(1,1-p-tolyl)-1-(3-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine
To a 1.70 g (5.35 mmol) of N-(tert-butyl)-N-(1-chloro-1,1-di(3-p-tolyl)silylamine dissolved in 20 mL of THF was added 1.279 g (5.35 mmol) of 1-(1H-3-indenyl)-1-(2,3-dihydro-1H-isoindolinyl) lithium salt dissolved in 20 mL of THF. After the reaction mixture was stirred for 9 h and then solvent was removed under reduced pressure. The residue was extracted with 40 mL of hexane and filtered. Solvent was removed under reduced pressure giving 2.806 of product as a gray solid. Yield 101.9 percent.
1 H(C 6 D 6 ) δ: 1.10 (s, 9H), 2.01 (s, 3H), 2.08 (s, 3H), 4.12 (d, 1H, 3 J H-H =1.5 Hz), 4.39 (d, 1H, 2 J H-H =11.1 Hz), 4.57 (d, 1H, 2 J H-H =11.7 Hz), 5.55 (d, 1H, 3 J H-H =2.1 Hz), 6.9-7.22 (m, 10H), 7.56 (d, 1H, 3 J H-H =7.8 Hz), 7.62 (d, 1H, 3 J H-H =6.9 Hz), 7.67 (d, 1H, 3 J H-H =7.8 Hz), 7.83 (d, 1H, 3 J H-H =7.8 Hz). 13 C{ 1 H} (C 6 D 6 ) δ: 21.37, 21.43, 33.78, 41.09, 50.05, 56.56, 104.28, 120.98, 122.46, 123.84, 124.71, 124.84, 126.98, 128.29, 128.52, 129.05, 132.99, 133.68, 135.08, 135.90, 136.01, 138.89, 139.05, 139.09, 141.27, 146.39, 148.48.
(B) Preparation of N-(tert-butyl)-N-(1,1-p-tolyl)-1-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amin dilithium salt
To a 50 mL hexane solution containing 2.726 g (5.61 mmol) of the N-(tert-butyl)-N-(1,1-p-tolyl)-1-(3-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine was added 7.4 mL of 1.6 M n-BuLi solution. During addition of the n-BuLi, a yellow precipitate appeared. After stirring for 6 h, the yellow precipitate was collected on a frit, washed with 2×25 mL of hexane, and dried under reduced pressure to give 2.262 g of the product as a yellow powder. Yield was 76.6 percent.
1 H(C 6 D 6 ) δ: 1.17 (s, 9H), 2.30 (s, 6H), 4.51 (s, 4H), 6.21 (s, 1H), 6.47 (m, 2H), 6.97 (d, 4H, 3 J H-H =8.1 Hz), 7.15 (m, 2H), 7.23 (m, 2H), 7.50 (m, 1H), 7.81 (d, 4H, 3 J H-H =7.8 Hz), 8.07 (d, 1H, 3 J H-H =7.2 Hz). 13 C{ 1 H} (C 6 D 6 ) δ: 21.65, 38.83, 52.46, 59.82, 95.33, 112.93, 114.15, 115.78, 118.29, 122.05, 122.60, 124.16, 124.78, 126.94, 127.30, 133.06, 134.75, 137.30, 141.98, 148.17.
(C) Preparation of dichloro(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium
In the drybox 1.552 g (4.19 mmol) of TiCl 3 (THF) 3 was suspended in 20 mL of THF. To this solution, 2.206 g (4.19 mmol) of N-(tert-butyl)-N-(1,1-p-tolyl)-1-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine, dilithium salt dissolved in 30 mL of THF was added within 1 min. The solution was then stirred for 60 min. After this time, 0.76 g of PbCl 2 (2.75 mmol) was added and the solution was stirred for 60 min. The THF was then removed under reduced pressure. The residue was first extracted with 60 mL of methylene chloride and filtered. Solvent was removed under reduced pressure leaving a black crystalline solid. Hexane was added (30 mL) and the black suspension was stirred for 10 hour. The solids were collected on a frit, washed with 30 mL of hexane and dried under reduced pressure to give 2.23 g of the desired product as a deep purple solid. Yield was 88.2 percent.
1 H (THF-d 8 ) δ: 1.40 (s, 9H), 2.46 (s, 3H), 2.48 (s, 3H), 5.07 (d, 2H, 2 J H-H =12.3 Hz), 5.45 (d, 2H, 2 J H-H =12.6 Hz), 5.93 (s, 1H), 6.95 (d, 1H, 3 J H-H =9.0 Hz), 7.08 (d, 1H, 3 J H-H =7.8 Hz), 7.15-7.4 (m, 9H), 7.76 (d, 1H, 3 J H-H =7.8 Hz), 7.82 (d, 1H, 3 J H-H =7.5 Hz), 8.05 (d, 1H, 3 J H-H =8.7 Hz). 13 C{ 1 H} (THF-d 8 ) δ: 21.71, 21.76, 33.38, 56.87, 61.41, 94.5, 107.95, 122.86, 125.77, 126.68, 127.84, 127.92, 128.40, 128.49, 129.36, 129.79, 131.23, 131.29, 135.79, 136.43, 136.73, 141.02, 141.22, 150.14.
Example 2
Preparation of(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium
In the drybox 0.50 g of dichloro(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium complex (0.79 mmol) was dissolved in 30 mL of diethyl ether. To this solution, 1.14 mL (1.6 mmol) of MeLi (1.6 M in ether) was added dropwise while stirring over a 1 minute period. After the addition of MeLi was completed, the solution was stirred for 1.5 hour. Diethyl ether was removed under reduced pressure and the residue extracted with 45 mL of hexane. Hexane was removed under reduced pressure giving a red crystalline material. This solid was dissolved in about 7 mL of toluene and 25 mL of hexane, filtered, and the solution was put into the freezer (−27° C.) for 2 days. The solvent was then decanted and the resulting crystals were washed with cold hexane and dried under reduced pressure to give 156 mg of product. Yield was 33.3 percent
1 H(C 6 D 6 ) δ: 0.25 (s, 3H), 0.99 (3H), 1.72 (s, 9H), 2.12 (s, 3H), 2.15 (s, 3H), 4.53 (d, 2H, 2 J H-H =11.7 Hz), 4.83 (d, 2H, 2 J H-H =11.7 Hz), 5.68 (s, 1H), 6.72 (dd, 1H, 3 J H-H =8.6 Hz, 3 J H-H =6.6 Hz), 6.9-7.2 (m, 11H), 7.30 (d, 1H, 3 J H-H =8.6 Hz).7.71 (d, 1H, 3 J H-H =8.5 Hz), 7.93 (d, 1H, 3 J H-H =7.8 Hz), 8.11 (d, 1H, 3 J H-H =7.8 Hz). 13 C{ 1 H} (C 6 D 6 ) δ: 21.45, 21.52, 35.30, 50.83, 56.03, 56.66, 57.65, 83.80, 105.64, 122.69, 124.51, 124.56, 125.06, 125.35, 127.33, 128.98, 129.06, 129.22, 133.51, 134.02, 134.62, 136.49, 136.84, 137.69, 139.72, 139.87, 143.84.
Example 3
Preparation of dichloro(N-1,1-dimethylethyl)-1,1-(4-butyl-phenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium
A) Tetramethylsilane[MgCl] 2 (THF) 6
To 40 mL diethyl ether solution of 2.5 g, 15.9 mmol of Me 2 Si(CH 2 Cl) 2 was added 0.851 g, 35.0 mmol of Mg turnings. After stirring overnight, a large amount of white solid was visible. Solvent was removed under reduced pressure and replaced with 40 mL of tetrahydrofuran (THF). Upon addition of THF, all of the white solid dissolved. After stirring an additional 24 h., about 20 mL of hexane was added and the solution was filtered. The filtrate was put into a freezer (−27° C.) overnight. Solvent was decanted and large colorless crystals were washed with cold hexane (2×20 mL). The solid was then dried under reduced pressure to give 2.753 g of product as the THF hexa-adduct. Yield was 27.1 percent
1 H NMR (THF-d 8 ): δ−1.81 (s, 4H), −0.21 (s, 6H), 1.77 (m, 28H, THF), 3.66 (m, 28H, THF). 13 C{ 1 H} NMR (THF-d 8 ): δ −2.50, 9.14, 26.37 (THF), 68.46 (THF).
B) dichloro(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium
i) Preparation of (p-Bu-Ph) 2 SiCl 2 .
To a three-necked 250 mL round-bottom flask under a nitrogen atmosphere equipped with a reflux condenser and a 250 mL dropping funnel 4.87 g of Mg turnings (0.200 moles) were introduced. 1-bromo-4-butyl benzene (42.6 g, 0.200 moles) and 80 mL of THF were then added to the dropping funnel. At this time 10 mL of the bromobenzene/THF solution was added to the Mg turnings with a small amount of ethyl bromide. The solution was then stirred until initiation occurred. The rest of the bromo benzene/THF solution was then added dropwise to allow refluxing to occur. After addition of the bromo benzene/THF solution, the mixture was heated at reflux until the magnesium was consumed.
The resulting Grignard solution was then transferred to a 250 mL dropping funnel which was attached to a three-necked 250 mL round-bottom flask under a nitrogen atmosphere equipped with a reflux condenser. To the round bottomed flask, 100 mL of heptane was introduced followed by SiCl 4 (15.3 g, 0.090 moles). To this solution, the Grignard solution was added dropwise. After addition was complete the resulting mixture was refluxed for 2 h and then allowed to cool to room temperature. Under an inert atmosphere the solution was filtered. The remaining salts were further washed with heptane (3×40 mL), filtered and combined with the original heptane solution.
The heptane was then removed via distillation at atmospheric pressure. The resulting viscous oil was then vacuum distilled with collection of the product at 1 mm Hg, (133 Pa) at 210° C. giving 19.3 g (58 percent) of the desired product.
ii) Preparation of bis(4-n-butylphenyl)(t-butylamido)chlorosilane
Dichloro-di(4-n-butylphenyl)silane (4.572 g, 12.51 mmol) was dissolved in 45 mL of methylene chloride. To this solution was added 1.83 g, 25.03 mmol of t-BuNH 2 . After stirring overnight, the solvent was removed under reduced pressure. The residue was extracted with 45 mL of hexane and filtered. Solvent was removed under reduced pressure leaving 4.852 g of the desired product.
iii) Preparation of (4-n-Bu-Ph) 2 Si(3-isoindolino-indenyl)(NH-t-Bu)
To a 4.612 g (11.47 mmol) of (4-n-Bu-Ph) 2 Si(Cl)(NH-t-Bu) dissolved in 20 mL of THF was added 2.744 g (8.37 mmol) of lithium 1-isoindolino-indenide dissolved in 30 mL of THF. After the reaction mixture was stirred overnight solvent was removed under reduced pressure. The residue was extracted with 50 mL of hexane and filtered. Solvent removal gave 6.870 g of product as a very viscous red-brown oil. Yield was 91.0 percent.
iv) Preparation of dilithium salt of (4-n-Bu-Ph) 2 Si(3-isoindolino-indenyl)(NH-t-Bu)
To a 50 mL of hexane solution containing 6.186 g (10.33 mmol) of (4-n-Bu-Ph) 2 Si(3-isoindolino-indenyl)(NH-t-Bu) was added 13.5 mL of 1.6 M n-BuLi solution. A few minutes after n-BuLi addition, a yellow precipitate appeared. After stirring overnight, the yellow precipitate was collected on the frit, washed with 4×20 mL of hexane and dried under reduced pressure to give 4.42 g of the desired product as a yellow powder. Yield was 70.0 percent.
v) Preparation of dichloro(N-1,1-dimethylethyl)-1,1-(4-butyl-phenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium
In the drybox, 2.62 g (7.10 mmol) of TiCl 3 (THF) 3 was suspended in 40 mL of THF. To this solution, 4.32 g (7.07 mmol) of dilithium salt of (4-n-Bu-Ph) 2 Si(3-isoindolino-indenyl)(NH-t-Bu) dissolved in 60 mL of THF was added within 2 minutes. The solution was then stirred for 60 minutes. After this time, 1.28 g of PbCl 2 (4.60 mmol) was added and the solution was stirred for 60 minutes. The THF was then removed under reduced pressure. The residue was extracted with 50 mL of toluene and filtered. Solvent was removed under reduced pressure leaving a black crystalline solid. Hexane was added (35 mL) and the black suspension was stirred for 0.5 hour. The solids were collected on the frit, washed with 2×30 mL of hexane and dried under reduced pressure to give 4.68 g of the desired product as a black-blue, crystalline solid. Yield was 92.4 percent.
Example 4
Preparation of (N-1,1-dimethylethyl)-1,1-(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-dimethyltitanium
Dichloro(N-1,1-dimethylethyl)-1,1-(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium (1.61 g, 2.25 mmol, Example 14) was suspended in 35 mL of toluene. To this suspension was added 3 mL (4.75 mmol) of 1.6 M MeLi ether solution. The reaction color changed at once from dark green-black to dark red. After stirring for 1 hour, the solvent was removed under reduced pressure. The residue was extracted with 55 mL of hexane and filtered. Solvent was removed leaving 1.46 g of the desired product as a red solid.
Example 5
Preparation of (N-1,1-dimethylethyl)-1,1-(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium (II) 1,3-pentadiene
Dichloro(N-1,1-dimethylethyl)-1,1-(4-butyl-phenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium (1.266 g, 1.77 mmol, Example 14) was suspended in 60 mL of hexane. The mixture was brought to gentle reflux and then 0.9 mL (0.89 mmol) of piperylene was added followed by 1.86 mL (3.72 mmol) of BrMgBu (2 M in THF). The reaction mixture was refluxed for 2.5 hour. After cooling to room temperature the solution was filtered and solvent was removed under reduced pressure leaving 1.30 g of the desired product as a black glassy solid.
Example 6
Preparation of (N-(1,1-dimethylethyl)-1,1-di(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-) -[(dimethylsilylene)bis(methylene)]titanium
To a 50 mL toluene solution containing 2.33 g, (3.26 mmol) of dichloro(N-(1,1-dimethylethyl)-1,1-di(4-n-butyl-phenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium (Example 14) was added 3.62 g, 4.23 mmol of Me 2 Si(CH 2 MgCl) 2 (THF) 9 as a solid. After stirring overnight at room temperature, the solution color changed from green-black to red. Solvent was removed under reduced pressure. The residue was extracted with 40 mL of hexane and filtered. The solvent was removed under reduced pressure to give a red glassy solid. This material was dissolved in 40 mL of hexane and filtered thought a fine frit. Solvent removal gave 2.16 g of product as a red glassy solid. Yield was 89.0 percent.
1 H NMR (C 6 D 6 ): δ 0.03 (s, 3H), 0.44 (s, 3H), 0.62 (d, 1H, 2 J H-H =7.9 Hz), 1.24 (m, 4H), 1.52 (m, 4H), 1.54 (s, 9H), 2.34 (s, 2H), 2.45 (d, 1H, 2 J H-H =13.4 Hz), 2.52 (t, 4H, 3 J H-H =7.8 Hz), 4.61 (m, 4H), 5.84 (s, 1H), 6.74 (t, 1H, 3 J H-H =7.7 Hz), 6.89 (d, 1H, 3 J H-H =8.7 Hz), 6.94 (m, 2H), 7.05 (m, 2H), 7.15 (d, 2H, 3 J H-H =7.5 Hz), 7.26 (d, 2H 13 J H-H =7.8 Hz), 7.31 (d, 1H, 3 J H-H =9.0 Hz), 7.57 (d, 1H, 3 J H-H =8.7 Hz), 8.13 (d, 2H, 3 J H-H =7.8 Hz), 8.17 (d, 2H, 3 J H-H =7.8 Hz). 13 C{ 1 H} NMR (C 6 D 6 ): δ −1.08, −0.28, 14.11, 14.15, 33.70, 33.78, 35.91, 36.06, 56.63, 56.88, 80.31, 84.35, 85.24, 103.81, 122.61, 122.81, 122.82, 124.27, 124.36, 127.34, 128.47, 128.51, 129.72, 131.03, 134.87, 135.00, 136.66, 137.16, 137.79, 143.36, 144.66, 144.85. HRMS (EI): calculated for C 39 H 46 N 2 Si 2 Ti (M) + 646.2679. found 646.2640.
Analysis: Calculated for C 39 H 46 N 2 Si 2 Ti: C, 72.42; H, 7.17; N, 4.33. Found: C, 72.78; H, 7.53; N, 4.13.
Example 7
Preparation of (N-1,1-dimethylethyl)-1,1-(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-,H-inden-1-yl)silanaminato-(2-)-N-)-bis[(trimethylsilyl)methyl]-titanium
In the drybox 3.42 g of dichloro(N-1,1-dimethylethyl)-1,1-(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium (5.42 mmol) (prepared substantially according to example 5) was partly dissolved in 70 mL of toluene. To this solution 11.6 mL (11.6 mmol) of LiCH 2 TMS (1 M in pentane) was added dropwise while stirring over a one minute period. After the addition of lithium reagent was completed, the solution was stirred for 15 hours at room temperature. The reaction mixture was filtered and solvent was removed under reduced pressure. The resulting solid was dissolved in 15 mL of toluene followed by addition of 45 mL of hexane. The solution was filtered and solvent removed under reduced pressure leaving a red-brown crystalline solid. Hexane was added (25 mL) and the mixture was stirred for 10 min. and then put into freezer for 24 hours. Red crystalline solid was collected by filtration, washed with 2×8 mL of cold hexane, and then dried under reduced pressure to give 2.722 g of the desired product.
1 H NMR (C 6 D 6 ): δ −0.67 (d, 2H, 2 J H-H =11.7 Hz, —CH 2 Si(CH 3 ) 3 ), 0.14 (s, 9H, —CH 2 Si(CH 3 ) 3 ), 0.20 (s, 9H, —CH 2 Si(CH 3 ) 3 ), 1.10 (d, 2H, 2 J H-H =12.0 Hz, —CH 2 Si(CH 3 ) 3 ), 1.31 (m, 2H, —CH 2 Si(CH 3 ) 3 ), 1.71 (s, 9H, C(CH 3 ) 3 ), 2.13 (s, 6H), 4.77 (d, 2H, 2 J H-H =12.0 Hz), 4.91 (d, 2H, 2 J H-H =12.0 Hz), 5.78 (s, 1H), 6.73 (t, 1H, 3 J H-H =7.7 Hz), 6.98 (m, 3H), 7.05 (m, 2H), 7.13 (d, 2H, 3 J H-H =7.8 Hz), 7.20 (d, 2H, 3 J H-H =7.8 Hz), 7.33 (d, 1H, 3 J H-H =8.4 Hz), 7.78 (d, 1H, 3 J H-H =90 Hz), 7.98 (d, 2H, 3 J H-H =7.5 Hz), 8.06 (d, 2H, 3 J H-H =7.8 Hz). 13 C{ 1 H} NMR (C 6 D 6 ): δ 2.74, 3.52, 21.47, 21.50, 35.33, 57.03, 58.74, 69.08, 80.50, 84.92, 102.34, 122.57, 124.42, 124.78, 124.92, 125.12, 127.55, 128.92, 129.09, 129.49, 133.99, 134.30, 134.60, 136.65, 137.09, 137.43, 139.72, 139.83, 146.11. HRMS (EI): calculated for C 43 H 58 N 2 Si 3 Ti (M) + 735.3465, found 735.3461. Analysis Calculated for C 43 H 58 N 2 Si 3 Ti: C, 70.26; H, 7.95; N, 3.81. Found: C, 65.96; H, 8.74; N, 2.11.
The X-ray structure (ORTEP) for the compound is provided in FIG. 1 .
Example 8
Preparation of (N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-[(dimethylsilylene)bis(methylene)]titanium
A) Tetramethylsilane[MgCl] 2 (THF) 6
To 40 mL diethyl ether solution of 2.5 g, 15.9 mmol of Me 2 Si(CH 2 Cl) 2 was added 0.851 g, 35.0 mmol of Mg turnings. After stirring overnight large amount of white solid was visible. Solvent was removed under reduced pressure and replaced with 40 mL of tetrahydrofuran (THF). Upon addition of THF all of the white solid dissolved. After stirring an additional 24 hr, about 20 mL of hexane was added and the solution was filtered. The filtrate was put into a freezer (−27° C.) overnight. Solvent was decanted and large colorless crystals were washed with cold hexane (2×20 mL). The solid was then dried under reduced pressure to give 2.753 g of product as the THF hexa-adduct. Yield was 27.1 percent.
1 H NMR (THF-d 8 ): δ −1.81 (s, 4H), −0.21 (s, 6H), 1.77 (m, 28H, THF), 3.66 (m, 28H, THF). 13 C{ 1 H} NMR (THF-d 8 ): δ −2.50, 9.14, 26.37 (THF), 68.46 (THF).
B) Preparation of (N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-[(dimethylsilylene)bis-(methylene)]titanium
To a 50 mL toluene solution containing 0.60 g, 0.95 mmol of dichloro(N-(1,1-dimethylethyl)-1,1-di(4-methyl-phenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium (prepared substantially according to the technique of Example 5) was added 0.667 g, 1.05 mmol of Me 2 Si(CH 2 MgCl) 2 (THF) 6 as a solid. After stirring for 2 hours at room temperature, proton NMR analysis showed about 70 percent conversion to the product. After stirring an additional 2 days, the 1 H NMR spectrum did not change. An additional 0.25 g of the diGrigniard was added. Within minutes the reaction mixture turned from green-yellow to red. After stirring an additional 6 hours, the solvent was removed under reduced pressure. The residue was extracted with 40 mL of hexane and filtered. Solvent was removed under reduced pressure to give a red glassy solid. This solid was dissolved back in 15 mL of hexane. After standing at room temperature overnight, the solvent was decanted and red crystals were washed with cold hexane (2×2 mL). These crystals were dried under reduced pressure to give 0.448 g of the desired product. Yield was 72.9 percent.
1 H NMR (C 6 D 6 ): δ −0.04 (s, 3H), 0.44 (s, 3H), 0.63 (d, 1H, 2 J H-H =12.9 Hz), 1.52 (s, 9H), 2.15 (s, 6H), 2.34 (m, 2H), 2.45 (d, 1H, 2 J H-H =12.9 Hz), 4.61 (m, 4H), 5.81 (s, 1H), 6.74 (t, 1H, 3 J H-H =7.8 Hz), 6.88 (d, 1H, 3 J H-H =6.6 Hz), 6.92 (m, 2H), 7.05 (m, 2H), 7.15 (d, 2H, 3 J H-H =8.1 Hz), 7.21 (d, 2H, 3 J H-H =8.1 Hz), 7.37 (d, 1H, 3 J H-H =8.4 Hz), 7.56 (d, 1H, 3 J H-H =8.4 Hz), 8.09 (d, 2H, 3 J H-H =6.9 Hz), 8.11 (d, 2H, 3 J H-H =7.2 Hz). 13 C{ 1 H} NMR (C 6 D 6 ): δ −1.10, −0.30, 21.50, 21.56, 35.87, 56.62, 56.88, 80.27, 84.40, 85.15, 103.75, 122.61, 122.81, 123.83, 124.29, 124.37, 127.35, 129.12, 129.68, 130.98, 134.58, 134.61, 136.65, 137.14, 137.78, 139.66, 139.86, 143.33. HRMS (EI): calculated for C 39 H 46 N 2 Si 2 Ti (M) + 646.2679, found 646.2640. Analysis: Calculated for C 39 H 46 N 2 Si 2 Ti: C, 72.42; H, 7.17; N, 4.33. Found: C, 72.78; H, 7.53; N, 4.13.
The X-ray structure (ORTEP) for the compound is provided in FIG. 2 .
Example 9
Preparation of dichloro(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium
(A) Preparation of N-(tert-butyl)-N-(1-chloro-1,1-di-p-tolylsilyl)amine. To a solution of of 10.0 g (35.6 mmol) of dichloro-p-ditolylsilane in 300 mL of hexane was added 5.20 g (71.1 mmol) of t-butyl amine. The reaction mixture was stirred overnight, then filtered. The hexane was removed under reduced pressure to give the product as a viscous, colorless oil. The yield was 10.83 g (96 percent).
1 H(C 6 D 6 ) δ: 1.12 (s, 9H), 2.04 (s, 6H), 7.01 (d, 4H), 7.82 (d, 2H). 13 C{ 1 H}(C 6 D 6 ) δ: 21.4, 33.2, 50.80, 129.06, 132.67, 135.09, 140.46.
(B) Preparation of N-(tert-butyl)-N-(1,1-di(4-methylphenyl)-1-(3-tetrahydro-1H-1-pyrrolyl-1H-1-indenyl)silyl)amine. A solution of 1-(1H-3-indenyl)pyrrolidine, lithium salt (1.00 g, 5.23 mmol) in 40 mL of THF was added dropwise to a 80 mL THF solution N-(tert-butyl)-N-(1-chloro-1,1-di-p-tolylsilyl)amine (1.66 g, 5.23 mmol). After the addition was complete the reaction mixture was stirred overnight. The solvent was then removed under reduced pressure. The residue was extracted with hexane and the solution filtered. The solvent was then removed under reduced pressure leaving 2.41 g of product. Yield was 99 percent.
1 H(C 6 D 6 ) δ 1.07 (s, 9H), 1.52 (bs, 4H), 2.04 (s, 3H), 2.09 (s, 3H), 3.00 (bs, 2H), 3.14 (bs, 2H), 4.07 (s, 1H), 5.52 (s, 1H), 7.00-7.84 (m, 12H).
(C) Preparation of N-(tert-butyl)-N-(1,1-di(4-methylphenyl)-1-(3-tetrahydro-1H-1-pyrrolyl-1H-1-indenyl)silyl)amine, dilithium salt. In the drybox, 2.41 g (5.16 mmol) of N-(tert-butyl)-N-(1,1-di(4-methylphenyl)-1-1-(3-tetrahydro-1H-1-pyrrolyl-1H-1-indenyl)silyl)amine was combined with 80 mL of hexane. To this solution, 6.45 mL (10.33 mmol) of n-BuLi (1.6 M in hexanes) was added dropwise. Upon complete addition of the n-BuLi, the solution was stirred overnight. The resulting precipitate was collected via filtration, washed with hexane and dried under reduced pressure to give 1.52 g of product. Yield was 61 percent.
(D) Preparation of dichloro(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium N-(tert-butyl)-N-(1,1-di(4-methylphenyl)-1-(3-tetrahydro-1H-1-pyrrolyl-1H-1-indenyl)silyl)amine, dilithium salt (1.52 g, 3.26 mmol) was added as a solid to a 80 mL solution of THF containing TiCl 3 (THF) 3 (1.21 g 3.26 mmol). After 45 min, PbCl 2 (0.45 g, 1.63 mmol) was added as a solid. The reaction mixture was then stirred an additional hour. The solvent was removed under reduced pressure. The residue was extracted with toluene and filtered. Toluene was removed under reduced pressure and the residue was triturated with hexane. The solid was collected by filtration, washed with hexane and then dried under reduced pressure. 1.40 g of product was obtained. Yield was 73 percent.
1 H (CDCl 3 ) δ 1.33 (s, 9H), 1.99 (br s, 4H), 2.36 (s, 3H), 2.39 (s 3H), 3.65 (br s, 2H), 3.87 (br s, 2H), 5.74 (s, 11H), 7.10 (m, 11H), 7.25 (bs, 5H), 7.60 (m, 2H), 7.77 (s, 2H) 7.82 (d, 1H). 13 C{ 1 H}(CDCl 3 ) δ: 21.01, 21.68, 25.73, 333.35, 50.70, 60.86, 83.69, 107.91, 125.58, 126.81, 127.23, 127.98, 128.95, 128.99, 129.37, 131.23, 135.48, 136.08, 136.36, 140.33, 140.53, 150.38.
Example 10
Preparation of (N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium
In the drybox 0.444 g dichloro(N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium complex (0.76 mmol) was dissolved in 30 mL of diethylether. To this solution 1.00 mL (1.6 mmol) of MeLi (1.6 M in ether) was added dropwise while stirring over a 2 minute period. After the addition of MeLi was completed, the solution was stirred for 1.5 hour. Et 2 O was removed under reduced pressure and the residue extracted with 45 mL of hexane. Hexane was removed under reduced pressure giving 0.348 mg of red, crystalline material. This red solid was dissolved in about 5 mL of hexane (heating was used) and then the vial was put into freezer overnight at −27° C., giving 75 mg of red crystals.
1 H(C 6 D 6 ) δ: 0.26 (s, 3H), 1.01 (s, 3H), 1.44 (m, 4H), 1.72 (s, 9H), 2.01 (s, 3H), 2.14 (s, 3H), 3.12 (m, 2H), 3.36 (m, 2H), 5.60 (s, 11H), 6.70 (ddd, 1H, 3 J H-H =8.7 Hz, 3 J H-H =6.6 Hz, 4 J H-H =0.9 Hz), 6.96 (ddd, 1H, 3 J H-H =8.6 Hz, 3 J H-H =6.6 Hz, 4 J H-H =0.9 Hz), 7.12 (m, 4H), 7.68 (d, 1H, 3 J H-H =8.7 Hz), 7.68 (d, 1H, 3 J H-H =9.0 Hz), 7.89 (d, 2H, 3 J H-H =7.8 Hz), 8.11 (d, 2H, 3 J H-H =7.8 Hz). 13 C{ 1 H} (C 6 D 6 ) δ: 21.43, 21.50, 25.82, 35.31, 49.87, 50.45, 55.53, 57.45, 83.28, 105.28, 124.31, 124.86, 125.00, 125.50, 128.86, 128.96, 129.20, 133.65, 134.08, 134.77, 136.46, 136.81, 139.57, 139.76, 144.86.
Example 11
Preparation of (N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-3-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)titanium dichloride
(A) 2-methyl-4-phenyl indenyl lithium In a 400 mL jar were placed 10.6 g (51.4 mmoles) of 2-methyl-4-phenyl indene and 200 mL of hexanes. Then, 33 mL of a 1.6 M hexane solution of butyl lithium (52.4 mmoles) were added at room temperature; the mixture was stirred overnight. The precipitate was filtered and washed with hexane and dried to give 10.60 (97 percent) of a pale yellow solid.
(B) di(tolyl)(t-butylamido)chlorosilane To a vigorously stirred solution of di(p-tolyl)dichlorosilane (7.5 g, 27 mmoles) in 180 mL of hexane, was added a solution of tert-butyl amine in 30 mL of hexane (3.9 g, 53.3 mmoles) over a period of five minutes followed by stirring of the mixture overnight. The mixture was filtered and the filtrate dried under reduced pressure to give 4.7 grams (55 percent yield) of the desired product.
1 H NMR (C 6 D 6 ): δ7.8 (d, 4H), 7.0 (d, 4H), 2.0 (s, 6H), 1.55 (s, 1H), 1.1 (s, 9H). 13 C { 1 H} NMR(C 6 D 6 ): δ 140.4, 135.1, 132.7, 129.0, 50.8, 33.2, 21.4.
(C) di(tolyl)(t-butylamido)(triflate)silane To a mixture of 6.4 g (25 mmoles) of silver triflate in 100 mL of acetonitrile was added over a period of five minutes a solution of the di(tolyl)t-butylamidochlorosilane dissolved in 80 mL of acetonitrile. A white precipitate formed immediately. The mixture was stirred for one hour and decanted, after which the volatiles were removed. The residue was treated with hexane, filtered and the volatiles were removed to leave 9.64 g (95 percent yield) of a pale yellow viscous oil.
1 H NMR (CDCl 3 ): δ 7.58 (d, 4H), 7.2 (d, 4H), 2.4 (s, 6H), 2.2 (s, 1H), 1.24 (s, 9H); 13 C { 1 H} NMR (C 6 D 6 ): δ 141.7, 134.7, 129.1, 127.0, 50.9, 33.0, 21.6; 19 F NMR (CDCl 3 ): −77.0 δ (CCl 3 F=0 δ).
(D) (2-Methyl-4-phenyl inden-1-yl)-N-(1,1-dimethylethyl) bis(tolyl)silanamine To a mixture of di(tolyl)(t-butylamido)(triflate)silane (9.64 g, 22.3 mmoles) in 60 mL of THF was added a solution of 2-methyl-4-phenylindenyl lithium (5.0 g, 23.5 mmoles; 5 percent molar excess) in 100 mL of THF. The mixture was stirred for one hour at room temperature, the volatiles were removed under reduced pressure, and the residue was extracted with hexanes and filtered. The filtrate was dried in vacuo to give 11.5 g (105 percent) of a very viscous, sticky pale orange oil. THF was still evident by NMR analysis.
(E) (2-Methyl-4-phenylinden-1-yl)-N-(1,1-dimethylethyl)di(tolyl)silanamidetitanium dichloride also referred to as (N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-3-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)titanium dichloride In a 500 mL glass jar were placed 10.76 g (22.0 mmoles) of (2-methyl-4-phenylinden-1-yl)-N-(1,1-dimethylethyl)di(tolyl)silanamine, 300 mL of hexane, and then 28.2 mL of a 1.6 M hexane solution of BuLi (2.04 equiv., 45 mmoles) were added. The mixture was stirred for two hours, about ⅔ of the solvent was removed and then 200 mL of THF were added to the mixture. Then 8.2 g (22.0 mmoles) of TiCl 3 .3THF was added; the mixture was stirred for thirty minutes, followed by addition of PbCl 2 (4.2 g, 1.3 electron equivalents), and 10 mL of CH 2 Cl 2 . After thirty minutes the volatiles were removed in vacuo, the residue repeatedly extracted with hexane, and the extracts filtered. The filtrate was dried to give 5.0 g (37 percent) of a dark orange-red solid.
1 H NMR (C 6 D 6 ): δ7.8 (d), 7.6 (d), 7.2 (m), 7.1 (br s), 7.05 (m), 6.8 (m), 2.1 (s, 6H), 1.95 (s, 3H), 1.65 (s, 9H).
Example 12
Preparation of (N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-3-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)titanium dimethyl
In a 50 mL jar were placed 0.54 g (0.9 mmoles) of (N-(1,1-dimethylethyl)-1,1-di(4-methylphenyl)-1-((1,2,3,3a,7a-η)-2-methyl-3-phenyl-1H-inden-1-yl)silanaminato-(2-)-N-)titanium dichloride and 20 mL of ether. Then, 0.6 mL of a 3 M diethylether solution of methyl magnesium iodide (1.8 mmoles) were added and the mixture was stirred for one hour. The volatiles were removed under reduced pressure and the residue (0.3 g) was redissolved in hexane, filtered and the filtrate dried again; this process (redissolve-filter-dry) was repeated three times to remove insoluble material. The semi-solid residue was treated with about 0.3 mL of ether, and the ether was quickly removed under reduced pressure to give a brownish-golden glassy solid (0.22 g, 43 precent yield).
1 H NMR (C 6 D 6 ): δ 7.9 (d), 7.75 (d), 7.6 (d), 7.2 (m), 7.1 (br s), 7.05 (m), 6.8 (m), 2.1 (s, 3H), 2.08 (s, 3H), 1.8 (s, 3H), 1.75 (s, 9H), 1.0 (s, 3H), 0.2 (s, 3H). 13 C { 1 H} NMR (C 6 D 6 ): δ 142.9, 141.0, 139.9, 139.5, 138.7, 137.0, 136.0, 135.2, 135.0, 134.5, 131.0, 129.0, 128.9, 128.6, 127.74, 127.67, 127.3, 125.6, 125.4, 116.0, 89.9, 66.5, 57.9, 57.7, 53.4, 35.0, 34.8, 31.8, 25.5, 22.9, 21.4, 20.7, 19.0, 14.2, 13.9.
Ethylene/1-Octene Polymerization Conditions I
All liquid and gas feeds were passed through columns of alumina and a decontaminant (Q5™ catalyst available from Englehardt Chemicals Inc.) prior to introduction into the reactor. Catalyst components are handled in a glovebox containing an atmosphere of argon or nitrogen. A stirred 2.0 liter reactor is charged with about 740 g of mixed alkanes solvent and 118 g of 1-octene comonomer. Hydrogen (25 psi, 170 kPa) is added as a molecular weight control agent by differential pressure expansion from a 75 mL addition tank. The reactor is heated to 140° C. and saturated with ethylene at 500 psig (3.4 MPa). Metal complex as dilute toluene solution and cocatalyst as dilute solutions in toluene or methylcyclohexane, were mixed in a 1:1 molar ratio and transferred to a catalyst addition tank and injected into the reactor. The cocatalyst was methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate, the ammonium cation of which is derived from a mixture of amines available commercially as methyl bis(tallow)amine. The polymerization conditions were maintained for 15 minutes with ethylene added on demand. The resulting solution was removed from the reactor, quenched with isopropyl alcohol, and stabilized by addition of a toluene solution containing about 67 mg/100 g polymer of a hindered phenol antioxidant (Irganox™ 1010 from Ciba Geigy Corporation) and about 133 mg/100 g polymer of a phosphorus stabilizer (Irgafos 168 from Ciba Geigy Corporation).
Between sequential polymerization runs, a wash cycle was conducted in which 850 g of mixed alkanes was added to the reactor and the reactor was heated to 150° C. The reactor was then emptied of the heated solvent immediately before beginning a new polymerization run.
Polymers were recovered by drying in a vacuum oven programmed to reach 140° C. over a period of about 20 hours. Density values are derived by determining the polymer's mass when in air and when immersed in methylethyl ketone. Micro melt index values (MMI) are obtained using a Custom Scientific Instrument Inc. Model CS-127MF-015 apparatus at 190° C., and are unit less values calculated as follows: MMI=1/(0.00343 t−0.00251), where t=time in seconds as measured by the instrument. Results are contained in Table 1.
TABLE 1
Catalyst
Yield
Density
Mw (×
Run
(μmol)
(g)
Eff. 1
(g/ml)
10 3 )
Mw/Mn
MMI 2
1
Ex. 2 (0.3)
18.8
1.31
0.897
<0.1
2
Ex. 4 (0.3)
40.9
2.85
0.892
<0.1
3
Ex. 10 (0.15)
19.5
2.7
0.901
331
1.96
—
4
Ex. 10 (0.25)
46.7
3.9
0.902
—
—
<0.1
5
Ex 12 (0.40)
21.1
1.1
0.874
125
2.28
0.7
A*
DSAT 3 (0.4)
76.1
4.0
0.897
67
2.23
8.9
1 efficiency, g polymer/μg titanium
2 micro melt index 190° C., (comparative technique of melt index determination)
3 dimethyl(N-(1,1-dimethylethyl)-1,1-dimethyl-1-(2,3,4,5-tetramethyl-cyclopentadienyl)-silanaminato titanium
*comparative, not an example of the invention
Ethylene/1-Octene/Ethylidenenorbornene Polymerization Conditions
All liquid except ethylidenenorbornene (ENB) and gas feeds were passed through columns of alumina and a decontaminant (Q5™ catalyst available from Englehardt Chemicals Inc.) prior to introduction into the reactor. ENB was passed through a short column (3×10 cm) of alumina prior to introduction to the reactor. Catalyst components are handled in a glovebox containing an atmosphere of argon or nitrogen. A stirred 2.0 liter reactor is charged with about 640 g of mixed alkanes solvent, 150 g of 1-octene and 16 g of ENB. Hydrogen (20 psi, 140 kPa) is added as a molecular weight control agent by differential pressure expansion from a 75 mL addition tank. The reactor is heated to 100° C. and saturated with ethylene at 500 psig (3.5 MPa). Metal complex as dilute toluene solution and cocatalyst as dilute solutions in toluene were mixed in a 1:1 molar ratio and transferred to a catalyst addition tank and injected into the reactor. The cocatalyst was methyldi(octadecyl)ammonium tetrakis(pentafluoro-phenyl)borate, the ammonium cation of which is derived from a mixture of amines available commercially as methyl bis(tallow)amine. The polymerization conditions were maintained for 15 minutes with ethylene added on demand. The resulting solution was removed from the reactor, quenched with isopropyl alcohol, and stabilized by addition of a toluene solution containing about 67 mg/100 g polymer of a hindered phenol antioxidant (Irganox™ 1010 from Ciba Geigy Corporation) and about 133 mg/100 g polymer of a phosphorus stabilizer (Irgafos 168 from Ciba Geigy Corporation).
Between sequential polymerization runs, a wash cycle was conducted in which 850 g of mixed alkanes was added to the reactor and the reactor was heated to 130° C. The reactor was then emptied of the heated solvent immediately before beginning a new polymerization run.
Polymers were recovered by drying in a vacuum oven set at 140° C. for about 20 hours. Density values are derived by determining the polymer's mass when in air and when immersed in methylethyl ketone. GPC results are determined by standard methods and are reported relative to a polystyrene/polyethylene universal calibration. The percent ethylene, octene and ENB for the polymer were determined by 13 C NMR analysis of the material. Results are contained in Table 2.
TABLE 2
Per-
cent
Per-
Catalyst
Yield
Density
Mw (×
oct-
cent
Run
(μmol)
(g)
Eff. 1
(g/ml)
10 3 )
Mw/Mn
ene
ENB
6
Ex. 12
33.2
0.73
0.860
407
2.3
41
2.5
(0.95)
B*
ID 2
59.1
1.23
0.874
317
2.0
33
2.8
(1.0)
1 efficiency, g polymer/μg titanium
2 dimethyl(N-(1,1-dimethylethyl)-1,1-dimethyl-1-(2,3,4,5-tetramethylcyclopentadienyl)-silanaminato titanium
*comparative, not an example of the invention
|
Group 4 metal complexes of the constrained geometry type, catalysts derived therefrom, and polymerization processes using the same, characterized by an alkaryl-substituted silane bridging group are disclosed.
| 2
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This is a divisional of application Ser. No. 10/446,009 filed May 26, 2003.
This invention is a Continuation-In-Part of U.S. patent application No. 09/680,495 filed Oct. 5, 2000 now U.S. Pat. No. 6,568,291, now allowed.
FIELD OF INVENTION
This invention relates to shaftless gyrostabilizers, and in particular to methods and apparatus for stabilizing aerial platforms and vehicles while in motion or hover mode, where the gyrostabilizers control pitching, rolling, yawing and other unsteadiness in aerial platforms and vehicles that have limited or no other inherent controls for self-stabilization, and this invention also is used to dampen tremors, vibrations, swaying in buildings.
BACKGROUND AND PRIOR ART
Counter-rotating or oppositely spinning discs, or wheels, mounted on centrally located shafts or axles are known to be used as stabilizers for guided missiles in U.S. Pat. No. 3,193,216; for rotation control of a space vehicle in U.S. Pat. No. 3,424,401; and to suppress oscillation about an axis of a loaded crane in U.S. Pat. No. 3,498,476. In U.S. Pat. No. 3,540,289 a device having flat annular or circular rotors of magnetic material in a rigid frame is used to anchor a body subject to attitude change. Typical types of gyroscopes known to the subject inventor include for examples U.S. Pat. Nos.: 2,872,707 to Kuiper; 3,158,340 to Sellers; 3,226,982 to Betts; 3,410,143 to Bowles; 3,509,778 to Bowles; and 4,150,579 to Vaughn. The devices identified above occupy valuable space and add considerable weight to the body that is being stabilized.
The disadvantages of the oppositely spinning discs arise from the requirement that they be physically mounted to a centrally located shaft or axle; thereby causing the entire disc to rotate and adding considerably more weight, volume, and surface area to the stabilizing device. Another disadvantage is that the centrally located axle or shaft restricts that space for other uses and finally the disc, axle or shaft arrangement limits the total revolutions per minute for discs due to wear and fatigue of the parts.
The disadvantages of the weight involved in spinning an entire disc have been addressed as follows. In U.S. Pat. No. 4,669,323, an attitude correction device is mounted above a gyro rotor and utilizes the flow of a viscous liquid and the rotation of one ball. U.S. Pat. No. 4,674,356 discloses a counter-balancing device having a discoid body with a circumferential ring of balls in a lubricating and damping fluid functioning to reduce vibrations and uneven bearing wear associated with unbalanced rotating members; the emphasis is on counter-balancing and not gyrostabilizing. According to U.S. Pat. No. 4,905,776 vibrational dampening for a drilling assembly is accomplished with races or tracks of tungsten-carbide balls in a fluid medium attached to the axial support rotating a drill bit. In a series of patents assigned to ETI Technologies, Inc. (U.S. Pat. Nos. 5,605,078; 5,768,951; 5,829,318; and 5,941,133) balancer and vibration removing devices are disclosed which employ balls, cylindrical weights, disc-like weights and viscous fluids moving freely inside a housing with an annular groove, called a “race.” All of the above spinning or rotating devices are arguably of less weight than a solid disc surface, but they all require mounting on a shaft or axle for rotation. Thus, the use restriction on the area in which the device is rotating remains a disadvantage. In addition, there are limits on the size of the stabilizing device based on space available within each application.
Attempts have been made over the years to rotate masses in closed type tracks. U.S. Pat. No. 2,871,707 to Kuiper patent describes a “gyroscopic stabilizer” that is limited rotor type devices in side-by-side arrangements that is used for binoculars, and has no description for use with stabilizing any type of vehicles such as aero platforms. This arrangement would also not be able to stabilize such vehicles for at least the reason of requiring extra side-by-side storage space for the side-by-side tracks.
U.S. Pat. No. 3,927,329 to Fawcett describes an energy converting system that clearly shows and requires rotatable wheels in FIGS. 8-9 being in a side-by-side configuration about shafts. Similar to the deficiencies to Kuiper, this reference has no description for being used as a gyrostabilizer.
Thus, the need exists for improved gyrostabilizers for use with vehicles such as aeroplatforms.
SUMMARY OF THE INVENTION
A first objective of the present invention is to provide a counter-revolving stabilizer for aerial platforms and vehicles such as vertical takeoff and land aircraft.
A second objective of the present invention is to provide a counter-revolving stabilizer with no physically mountable axle of shaft requirement.
A third objective of the present invention is to provide a gyrostabilizer having less mass than a disk of equal radius.
A fourth objective of the present invention is to provide a gyrostabilizer that requires less space than a disk.
A fifth objective of the present invention is to provide a stabilizer that produces more controllable revolutions per minute than a disk.
A sixth objective of the present invention is to provide a dual counter-revolving gyrostabilizer that permits independent control of each gyro.
A seventh objective of the present invention is to offset gyroscopic precession and double the effect of angular momentum available from a single gyro.
An eighth objective of the present invention is to provide a gyrostabilizer that can be retrofitted to function in many existing vehicles and structures.
A ninth objective of the invention is to provide a shaftless gyrostabilizer of simultaneously counter-revolving masses that are sandwiched together for use with aerial platforms and vehicles.
A first embodiment of the present invention is a design wherein a race or track contains balls propelled in a circular motion via fluid pressure or electromagnetic propulsion in an arrangement where there is no center shaft or axle. This arrangement shifts the weight of the gyrostabilizer to the perimeter where most of the momentum is created. Thus, greater momentum can be generated at a fraction of the weight of gyrostabilizers that spin on an axis. Also, the space between the center of revolution and the revolving weights is usable or void space for vehicles or structures that are weight sensitive. The absence of a physical shaft or axle also provides unlimited flexibility in sizing the stabilizing device, such that the device can be scaled to fit very large or very small vehicles and structures, including toys.
Additional embodiments of the rotatable rings can include rigid contiguous ring members, such as those formed from metal, plastic, composites, and the like, that rotate with or without tracks. The rings can include flexible, bendable contiguous materials, such as chains and ropes, that rotate with or without tracks. Additionally, the rings can include liquids, such as but not limited to oils, water and the like. Furthermore, the rings can include rotating gasses.
Further objects and advantages of this invention will be apparent from the following detailed description of the presently preferred embodiments that are illustrated schematically in the accompanying drawings.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a top view of a fluid driven gyrostabilizer.
FIG. 2 is a side view of the races or tracks of the gyrostabilizer.
FIG. 3 is a perspective view of the gyrostabilizer having the fluid pump centrally located.
FIG. 4 is a view of the gyrostabilizer with the top cover of the race removed.
FIG. 5 is an exploded view of the gyrostabilizer with upper and lower tracks separated.
FIG. 6 is an exploded side view of the gyrostabilizer showing steel balls, spacer vanes, upper and lower track assemblies.
FIG. 7 is a top view of the gyrostabilizer with the top cover of the race removed.
FIG. 8 is an enlarged view of balls and vanes in the lower race.
FIG. 9 is an enlarged cross-section of the upper and lower gyro assembly.
FIG. 10 is a top view of the electromagnet driven gyro.
FIG. 11 is a side view of the electromagnet driven gyro showing a series of magnets equally distributed along the upper and lower gyro assembly.
FIG. 12 is an exploded view of the upper and lower tracks of the electromagnet driven assembly.
FIG. 13 is an exploded side view of the electromagnet driven gyrostabilizer showing ferrous and nonferrous balls, spacer vanes, upper and lower track assemblies.
FIGS. 14A , 14 B, and 14 C show three views of ferrous and nonferrous ball progression propelled by electromagnets (spacer vanes are omitted).
FIGS. 15A , 15 B, and 15 C show three views of the gyrostabilizer used in a boat.
FIG. 16 shows three view of the gyrostabilizer used in a hovercraft.
FIGS. 17A , 17 B, and 17 C show three views of the gyrostabilizer used in a skyscraper.
FIG. 18 is a perspective view of another embodiment of the gyrostabilizer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Before explaining the disclosed embodiments 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 since the invention is capable of other embodiments, including, but not limited to, machines such a camera mount on boats and helicopters. Also, the terminology used herein is for the purpose of description and not of limitation.
The term “race” is used interchangeably with track or groove to mean a circular or annular cavity in which are placed movable weight, usually spherical and made of metal or metal alloys. The term “revolving” is used herein to mean to cause to go round in an orbit which is in contrast to the terms “rotate” meaning to turn about an axis or a physical shaft or axle.
In the preferred embodiment of the present invention, weights such as metal balls are rotatably inserted in a track and are separated by vanes which minimize hydraulic resistance to movement of the weights and provide a surface area against which a fluid is directed to propel the track of rotating balls in a circular motion, known herein as revolving. The vanes also hold each spacer in place and direct the balls in the direction of fluid flow. In order to create a stabilizing device, two circular tracks are used in a stacked arrangement, such that the counter-revolving effects of the balls in their respective tracks assist in stabilizing vehicles and structures moving in different directions.
The circular race or track is formed of a durable, lightweight composite material such as, carbon fiber or a lightweight metal alloy. In a preferred embodiment, the two circular tracks of the present gyrostabilizer are bolted together in a stacked arrangement with a gasket or other suitable packing material between the upper and lower track.
The rotating weights that are propelled by a fluid can be any spherical balls made of noncorrosive materials such as silicon-nitride, dense polymers or metallic alloys such as tungsten-carbide, and the like. The weights may be one-piece discs or rings having a spherical shape to reduce friction during rotation or spinning within the track. The vanes, also sometimes called “spacer vanes,” separate each ball in the track and can be made from the same durable, lightweight composite material as the track. Thus, carbon fiber or a lightweight metal alloy may be used in the fabrication of the vanes.
The fluid used to propel the track of balls can be any synthetic or petroleum-based, high pressure, hydraulic fluid. Likewise, any viscous, lubricating and noise dampening, non-flammable oil, water or air, may be used as a fluid propellant. The pump that is used to propel the fluid into the track can be any suitable pressure pump and can be located in any convenient location within the vehicle or structure that is being stabilized. Such a pump is manufactured by Hi-Speco Corporation and is identified as an engine driven hydraulic pressure pump.
When the materials described above are assembled as shown in the detailed description that follows, a method of stabilizing vehicles and structures is possible. A first set of balls is rotated in a first circular track in a first direction. A second set of balls is rotated in a second circular track in a second direction that is opposite to the first direction, simultaneous to the first set of balls wherein counter-revolving effects of the first and second set of balls assist in dampening pitch and rolls when the gyro is revolving perpendicularly to the pull of gravity and parallel to the direction of unsteady movement. In addition, the counter-revolving gyrostabilizer of this invention can be used to dampen yaw if it is positioned at right angles to the pull of gravity. In zero gravity, the gyrostabilizer maintains an object in a stationary position.
A second embodiment of the present invention consists of a first circular track having a first set of balls that are alternatingly made of ferrous and non-ferrous material. The first circular track is adjacently stacked on a second circular track having a second set of balls that are also alternatingly made of ferrous and non-ferrous material. In combination with the first and second circular tracks is a means for moving the first and second track in opposite, counter-revolving directions by electromagnetic propulsion. Electrified magnets are positioned in an efficient and symmetrical pattern on both the first and second circular tracks. When power is applied, the magnets attract the ferrous balls in the desired direction and with a controllable speed to accomplish stabilization of a vehicle or structure which may be subject to vibrations, pitching, yawing, rolling, swaying and the like.
The ferrous balls of the second embodiment are by definition largely comprised of iron or an iron alloy. Steel is a suitable material because of its strength and durability. The non-ferrous balls can be formed of ceramic material or a non-ferrous alloys such as silicon nitride. The non-ferrous balls are preferably of the same density as the ferrous balls.
The diameter of the gyrostabilizer of the present invention can range from a few inches for a flying toy, to over ten (10) feet in diameter for larger structures. The rate of revolution can be in the range from less than approximately 100 to approximately 20,000 revolutions per minute (rpm). In the preferred embodiment wherein a fluid pressure pump is used to propel the gyrostabilizer, an oil pressure pump manufactured by Hi-Speco Corporation can produce pressure in a range from approximately 1500 to approximately 3000 pounds per square inch (psi). Specifications for the pump are dependent on the size of the gyro.
In case of an emergency, the gyrostabilizer can be shut down by reversing the direction of fluid flow or by reversing the direction of electromagnetic propulsion. Also, when mounting the gyrostabilizer in a vehicle or structure, rubber bushings are used to attach the stabilizer in a manner similar to the mounting of an engine in an automobile. The stabilizer is positioned symmetrically and centrally to the center of gravity of the area in which stability is desired.
Referring to the drawings in more detail:
The reference numeral 1 when shown in each Figure designates a first circular track having a first set of balls. Reference numeral 2 when shown in each Figure designates a second circular track having a second set of balls. In addition, the track structures 1 and 2 include a top race 15 and a bottom race 16 which is joined to form an annular groove filled with circumferentially movable weights 8 . According to the present invention, at least a pair of the track structures 1 and 2 are installed in vehicles, machines and structures either perpendicular to or parallel to direction of the force that causes unsteady movement. Ideally, a gyrostabilizer is centered and placed symmetrically in the area of unsteady movement.
In FIG. 1 a top view of the gyrostabilizer shows a first track 1 positioned directly above a counter-revolving track (not shown). The fastening means 100 are shown around the inside and outside perimeter of the top race 15 and when attached to the bottom race (not shown) it forms a cavity that contains the rotating and revolving weights of the stabilizer. An oil pressure 3 is positioned inside the circular track 1 and forces oil simultaneously into the upper gyro drive line 4 and a lower gyro drive line 6 . The oil flow direction 13 is indicated by arrows along each pipeline. The oil pressure which can range between 1,500 and 3,000 psi, causes the balls inside the upper track to rotate and turn in a first direction before the oil enters an upper gyro return line 5 while the balls inside the lower track rotate and turn in a second direction before the oil enters return line 7 . In this manner the oil is re-circulated to the pump to provide continuous propulsion of balls in the two tracks in a counter-revolving direction. A power source 10 is connected to the pump 3 .
In FIG. 2 a side view of the upper gyro assembly 1 is shown in a stacked arrangement with the lower gyro assembly 2 . FIG. 3 is a perspective view of the gyrostabilizer showing the first track 1 and the second track 2 with the fluid pressure pump 3 centrally located among the gyro drive lines 4 and 6 and the return lines 5 and 7 . More detail is shown with the “Y” connector 11 which connects the upper and lower drive lines and the “Y” connector 12 which connects the upper and lower return lines to support simultaneous revolutions and recycling of fluid. The power connection 10 for the pump is shown. The counter revolving direction of the balls is indicated as 14 a and 14 b.
FIG. 4 provides a view of the gyrostabilizer with the top cover of the first track 1 removed. Each steel ball 8 is separated by a spacer vane 9 in a manner that efficiently and completely fills the track thereby placing the maximum weight on the perimeter of the gyrostabilizer. Counter revolving movement of balls in the first track 1 and second track 2 is shown by arrows 14 a and 14 b.
FIGS. 5 and 6 are exploded views of the gyrostabilizer assembly. In FIG. 5 the first track 1 and the second track 2 are separated to show how the “Y” connector for the drive lines 11 and the “Y” connector for the return lines 12 are connected to the pump 3 . FIG. 6 is a side view of the first track 1 with top cover 15 and bottom cover 16 with a concentric ring of balls 8 separated by space vanes 9 . The same arrangement is shown for the second track 2 having a top cover 150 separated from the bottom cover 160 that contains a concentric ring of balls 8 separately by spacer vanes 9 .
FIG. 7 is a top view of the gyrostabilizer with the top cover of the first track 1 removed. This view provides greater detail on the arrangement of each ball 8 and the spacer vanes 9 . The spacer vanes are constructed of a lightweight metal alloy and provide a confined space for each ball to rotate freely thus adding to the momentum of revolution in the direction shown by arrow 14 a.
FIGS. 8 and 9 are enlarged drawings of sections of FIGS. 7 and 1 , respectively. FIG. 8 is a top view of balls 8 and spacer vanes 9 in the bottom cover 16 of the upper track as shown in FIG. 7 . In FIG. 9 a cross sectional view of the first track 1 in a stacked arrangement above the second track 2 shows how the top cover 15 fits over the bottom cover 16 forming a leak-free, octagonal shaped track that permits free movement of the ball 8 and the secure positioning of the spacer vane 9 within the cavity formed by the top and bottom covers.
FIG. 10 is a top view of the first track 19 of an electromagnet driven gyro. A series of three electromagnets 17 are positioned strategically above the cavity filled with ferrous and non-ferrous balls (not shown). The electric power source 10 for each magnet is shown. It should be noted that the center of the gyrostabilizer is usable space or can be left void. FIG. 11 is a side view of the assembly propelled by electromagnets. Here a series of five magnets 17 are equally distributed along the first track 19 and the second track 20 of the electromagnet driven gyro.
FIGS. 12 and 13 are exploded views of electromagnet driven gyrostabilizers. FIG. 12 shows the first track 19 separated from the second track 20 with a strategically positioned series of three electromagnets 17 having power source connections 10 . The direction of revolution of balls in each track is as indicated by arrows 14 a and 14 b. FIG. 13 shows a first track 19 separated from a second track 20 with the top cover 15 apart from the bottom cover 16 showing the concentric ring of balls 8 separated by vanes 9 . The balls 8 are propelled in a counter revolving direction by a series of five magnets 17 positioned at equidistant points around the track. It is understood that the first track 19 and the second track 20 have the same arrangement of balls and magnets except that the balls in the first track 19 simultaneously revolve in the opposite direction from the balls in the second track 20 . The vanes 9 hold the spacers in place and in the assembled gyro are called, “spacer vanes.”
FIG. 14 has three views of nonferrous balls 21 and ferrous balls 22 being propelled by a series of three electromagnets 210 , 220 , 230 along the bottom cover 16 in the direction 14 . For clarity, spacer vanes are not shown in FIG. 14 . The non-ferrous balls are of the same density as the ferrous balls. The sequence for switching the magnets on and off is preferably first, middle and last. Thus, FIG. 14A shows movement within the race when the first magnet 210 is turned on to pull a ferrous ball in the desired direction. FIG. 14B shows middle magnet 220 switched on to propel another ferrous ball in the desired direction. Finally, FIG. 14C shows movement that occurs when the last magnet in the series 230 is switched on to support and sustain the movement of all ferrous balls in the desired direction. The ferrous balls 22 cause the nonferrous balls 21 to revolve in the same direction as the ferrous balls propelled by the electromagnets. Also the arrangement of magnets propels the balls in the desired direction.
FIGS. 15 through 17 contain illustrations as to how the gyrostabilizer can be used in a variety of vehicles and structures. On a smaller scale each vehicle shown could be designed as a toy. FIGS. 15A , 15 B and 15 C show a boat 25 with a dual counter revolving gyrostabilizer 24 positioned to revolve horizontally to prevent the boat from pitching upward on take off. FIGS. 16A , 16 B and 16 C show a hovercraft 26 , sometimes called a Vertical Takeoff & Land Craft (VTOL) with turbine intake 27 and a rotating thruster 28 wherein the dotted line configuration in each figure is a gyrostabilizer 24 . FIGS. 17A , 17 B, and 17 C show placement of a gyrostabilizer 24 in a skyscraper to dampen the sway experienced in the higher portion of the structure. The gyrostabilizer is centered horizontally about the central axis of the building in the area subject to the swaying phenomenon.
FIG. 18 is a perspective view of another embodiment of the gyrostabilizer 300 . This embodiment can include two rigid ring means 310 , 320 that can be formed rigid contiguous materials, such as but not limited to stainless steel, aluminum, plastics, composites, and the like. The ring masses 310 , 320 can be arranged to overlay one another and in a sandwich configuration to one another. The ring masses 310 , 320 can be kept parallel and sandwiched to one another by one or more similar rotating stations 330 , 340 , 350 , and 360 . Station 330 can include an outer rectangular housing 331 that wraps about the ring masses 310 , 320 , with upper freely moveable roller 332 above upper ring mass 310 , with another identical freely moveable roller (not visible) underneath the lower ring mass 320 . Two rotatable wheels 334 , 336 can be rotated in opposite directions from one another by a motor 339 , so that both ring masses 310 , 320 simultaneously counter revolve relative to another.
The contiguous rigid ring masses can be rotated relative to one another without the use of tracks. Alternatively, the rigid ring masses can be rotated relative to one another in tracks such as those described in the previous embodiments.
In additional embodiments, the ring masses 310 , 320 can be flexible contiguous materials, such as chains formed from metal, plastic, composites, and the like. Still furthermore, the flexible contiguous materials can be formed form other types of materials such as but not limited to rope, and the like. The flexible contiguous materials can also be use with or without tracks such as those embodiments previously described.
The embodiment of FIGS. 1-7 can be modified to be used without any ball type masses or any other solid type masses, so that the pressure pump 3 is positioned inside the circular track 1 and only forces different types of fluid simultaneously into the upper gyro drive line 4 and a lower gyro drive line 6 . The fluid embodiments can include liquids, gases, combinations thereof, that can operate similar to the first embodiment.
In a liquid application, the pressure pump can move liquids solely through the two tracks, such as only oil. Alternatively, the pressure pump can move other types of liquids such as water, and the like. The liquid density and mass can be selectively adjusted to achieve various stability effects in this embodiment by using different types and/or mixtures of liquid.
In a gas state application, the pressure pump can move gasses solely through the two tracks, such as only oxygen, argon, helium, and the like, and combinations thereof. The density and mass of the gases can be selectively adjusted to achieve various stability effects in this embodiment by using different types and/or mixtures of gases.
Still furthermore, the pressure pump can combine and move combinations of liquids and gasses. Additionally, the other types of masses, such as particles of various sizes such as up to approximately 1000 microns or more, can be mixed with either or both the liquids and/or gasses as the moveable masses in the simultaneously counter-revolving sandwiched gyroscope.
Still furthermore, the second electromagnetic embodiment can be used with fluid applications where for example the fluid contains conductive materials such as but not limited to metal particles, and the like.
While the invention has been described, disclosed, illustrated and shown in various terms of certain embodiments or modifications which it has presumed in practice, the scope of the invention is not intended to be, nor should it be deemed to be, limited thereby. Other modifications or embodiments, such as gyrostabilizers in machines, as may be suggested by the teachings herein are particularly reserved especially as they fall within the breadth and scope of the claims here appended.
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Gyrostabilizer methods and apparatus having simultaneously counter-revolving masses that do not require physical shafts or axles. The stabilizer can have dual counter-revolving concentric rings, or tracks filled with weights such as spherical balls, that are propelled in orbital fashion by fluid pressure or electromagnet propulsion. The rings can include rigid contiguous rings, such as metal, plastic, composites, and the like. Additionally, the rings can include liquids and/or gasses. Still furthermore, the rings can include flexible, bendable contiguous materials, such as chains and ropes. The concentric ring diameters can be a few inches to more than ten (10) feet. Without an axle or shaft the weight of the gyrostabilizer is shifted to the perimeter where most of the momentum is generated at a fraction of the weight of gyrostabilizers that spin on an axle. The gyrostabilizer can dampen unsteadiness such as tremors, vibrations, sway, pitch, roll, and yaw.
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This invention was made with government support under Contract No. F04704-86-C-0165 awarded by the Department of the Air Force. The government has certain rights in this invention.
BACKGROUND OF THE INVENTION
1. Technical Field
This invention relates to fiber optic systems and, more particularly, to a fiber optic connector.
2. Discussion
Fiber optic cables are used in a wide variety of systems. These applications range from low power systems in areas such as illumination and communications, to high power systems such as laser surgery and laser firing units While fiber optic cables are relatively efficient transmitters of electromagnetic energy, significant losses in transmission efficiency can occur at interface points. These interface points may occur where two separate cables are connected, or where a cable is terminated and light enters or exits a cable from adjacent devices.
There are many reasons for significant losses at the interfaces. Among these include the loss of light due to divergence or spreading of light rays exiting an optical fiber For example, where it is desired to couple the light from one optical fiber to another, the divergence of the light rays upon exiting one optical fiber will cause some light to miss the adjacent optical fiber. Diffraction of the exiting light rays will cause a similar effect.
Transmission losses may also be caused by misalignment of the coupled optical fibers or by lack of perpendicularity of the terminal face of the fibers. These situations may cause transmission losses by causing some light rays to miss the receiving fiber, or to be reflected by the receiving fiber. Another cause of transmission losses at optical fiber interfaces is contamination by dust or other particles which will absorb the transmitted light. Accordingly, it is important that a fiber optic connector maintain the fiber ends in close proximity, and in accurate alignment.
Besides transmission losses, a number of other problems are frequently encountered at fiber optic couplings. Because of the forces applied to optical fibers at the coupling during coupling and decoupling, damage to the optical fiber is frequently experienced at or near the coupling. To minimize damage to optical couplings by forces applied during handling, an effective means of strain relief is necessary. In addition, damage to the fiber can be caused during mating and demating by contact with the adjacent coupling if the couplings are misaligned during mating.
The above problems are even more acute in high power optical fiber applications. In such applications light losses become critical because any stray light may cause damage to the optical fiber connector itself. For example, such stray light may melt the adjacent connector material. Not only may such melting compromise the structural integrity of the connector, but the melted material can deposit itself on the optical fiber and cause further transmission losses. This is usually catastrophic in high power applications because any contamination on the face of the optical fiber will absorb the light energy, heat up, and seriously damage the optical fiber. In particular, when high power laser pulses in the range of 425 milliJoules (mJ) are transmitted through conventional optical fiber couplers (such as G and H, Part No. 211133), damage frequently occurs for the above described reasons. An additional problem with conventional fiber optic connectors is that while it is important to inspect and clean fiber optic faces at coupling points, the geometry of the coupler frequently makes cleaning and inspecting the fiber optic face difficult.
In view of the above problems, it would be desirable to provide an optical fiber coupling device which minimizes transmission losses even at high power. In addition, it would be desirable to provide an optical fiber coupler which aligns the two fibers to be coupled in very close proximity while keeping the optical fiber faces perpendicular. In addition, it would be desirable to provide an optical fiber connector having a geometry such that even where light does escape and melt surrounding connector material, this melted material will not reach the optical fiber faces.
Further, it would be desirable to provide such an optical fiber connector that can be mated and demated repeatedly without damage to the fibers. It would further be desirable to provide an optical fiber coupler which incorporates strain relief to prevent damage to he optical fiber during handling. Also it would be desirable to provide an optical fiber coupler which would permit cleaning and inspecting of the optical fiber faces with relative ease.
SUMMARY OF THE INVENTION
Pursuant to the present invention, an apparatus for coupling optical fibers is provided having a pair of connectors each with an axial opening extending therethrough for receiving the optical fibers. The connectors include a protruding portion having a substantially flat face at its distal end, the plane of the face being perpendicular to the axial opening. The face on the protruding portion is provided with a recessed portion surrounding the axial opening so that when the optical fiber is inserted into the opening, the optical fiber end extends into the recessed portion and into the plane of the face. The connectors, each containing an optical fiber, are then joined by an interconnect unit which removably secures the connector units so that the optical fiber faces are in close, parallel alignment with each other. In this way, the space formed by the recessed portions of the connectors surrounds the optical fiber interface to minimize the possibility of melted connector material reaching the fiber ends.
BRIEF DESCRIPTION OF THE DRAWINGS
The various advantages of the present invention will become apparent to one skilled in the art by reading the following specification and by reference to the drawings in which:
FIG. 1 is a cross-sectional view of the various components of the present invention before mating;
FIG. 2 is a perspective view of one type of convention optical cable used in the present invention;
FIG. 3 is a perspective view of a second type of conventional optical cable used in the present invention;
FIG. 4 is a cross-sectional view of the various components of the present invention shown in the mated configuration; and
FIG. 5 is an expanded cross-sectional view of the interface portion of the mated connectors.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now to the drawings, a fiber optic connector apparatus 10 is provided for coupling electromagnetic energy carried by two fiber optic cables 12 and 14, as shown in FIG. 1. Fiber optic cables 12 and 14 may be conventional fiber optic cables as shown in more detail in FIGS. 2 and 3. The first fiber optic cable 12 shown in FIG. 2 has an overall diameter of about 4.3 millimeters, and include an optical fiber having a diameter of 0.432 millimeters. The second optical fiber optic cable 14 shown in FIG. 3 is similar to the first, with the primary difference being that the overall diameter is only about 2.2 millimeters. The diameter of the optical fiber in the second fiber optic cable 14 is the same as the first, about 0.432 millimeters.
The 4.3 millimeter fiber optic cable 12 is composed of five discrete layers. At the center is a conventional optical fiber 16 having a diameter of 0.432 millimeters for carrying electromagnetic energy. Surrounding the optical fiber is a tube 18 forming a first inner layer 18 having a diameter of about 0.73 millimeters, which loosely encases the optical fiber 16. The first inner layer 18 may be made of a material such as Tefzel. The second inner layer 20 surrounds the first inner layer 18 and has a diameter of about 2 millimeters. The second inner layer 20 may be composed of a material such as Hytrel. Surrounding the second inner layer 20 is a layer of Kevlar fibers 22 which are used to provide strain relief as will be described in more detail below. An outer layer 24, which may be composed of polyurethane, has a diameter of 4.3 millimeters and surrounds the layer of Kevlar fibers 22.
It will be appreciated that the 4.3 millimeter fiber optic cable 12 is conventional in the art and may be obtained from Fnsign Bickford company of Avon, Conn. FIG. 3 shows the 2.2 millimeter optical cable 14, which, like the 4.3 millimeter fiber optic cable 12, includes a 0.432 millimeter optical fiber 26; a first inner layer 28 composed of 0.73 millimeter Tefzel tube; a second inner layer 30 composed of a 1.4 millimeter hytrel tube; a layer of Kevlar fibers 31; and an outer layer 34 composed of a 2.2 millimeter polyurethane tube. The 2.2 millimeter fiber optic cable 14, like 4.3 millimeter fiber optic cable 12, is conventional in the art and may be obtained from the same source as the 4.3 millimeter fiber optic cable.
As shown in FIGS. 2 and 3, the 4.3 and 2.2 millimeter fiber optic cables 12 and 14, are prepared for use with the fiber optic connector of the present invention by stripping successive layers so that each layer is exposed along a predetermined length. Referring again to FIG. 1, the 4.3 millimeter fiber optic cable 12, having been prepared as indicated in FIG. 2, is inserted into a crimping tip 36 which has, on one end, an annular portion 38 having an inside diameter of about 4.3 millimeters so that the outer casing 24 of the 4.3 millimeter fiber optic cable 12 may be inserted therein. Crimping tip 36 also has on its other end a reduced diameter portion 42 having an inside diameter which receives the first inner layer 18 of the 4.3 millimeter fiber optic cable 12. The crimping tip 36 also has two raised crimping surfaces 44 and 46 to facilitate the crimping procedure as will be explained in more detail below. Crimping tip 36 may preferably be constructed of a conventional material such as 304 stainless steel Kevlar fibers 22 are bent around reduced diameter portion 42 of the crimping tip 36 to provide strain relief. When the optical fiber cable 12 is pulled in tension, it is necessary that the Kevlar fibers 22 pull tight before the strain is taken up by the glass core 16. Thus it is desirable to pretension the Kevlar fibers 22 before the crimping process.
A first ferrule 48 has a central opening 50 for receiving the first inner tube 18 of the 4.3 millimeter fiber optic cable 12. Ferrule 48 is composed of a copper nickel zinc alloy in the preferred embodiment. However, it will be appreciated that o&her materials may also be used. On one end, the first ferrule 48 has an outer crimping portion 52 which fits over the crimping surfaces 44 and 46. By means of a conventional crimping tool, the ferrule 48 may be permanently attached to the crimping tip 36 by causing the crimping portion 52 to be deformed around the crimping surface 42 of the crimping tip 36. Ferrule 48 also includes a protruding cylindrical portion 54 having a flat face 56 perpendicular to the axis of the ferrule 48 central opening 50. The protruding portion 54 also includes a reduced diameter central opening portion 58 which has a diameter of appropriate size to permit the optical fiber 16 to snugly fit therein.
Adjacent the face 56 is a recessed portion 60 which is seen more clearly in FIG. 5. Recessed portion 60 forms an annular dish shaped opening which surrounds the optical fiber 16. It will also be seen that optical fiber 16 is inserted into the ferrule 48 so that the end face 62 of optical fiber 16 is in the same plane as the end face 56 of ferrule 48 It is important that ferrule face 56 and optical fiber face 62 be polished to relatively tight tolerances so that the surfaces are flat and in the same plane. For example, one model of polishing to achieve the desired tolerance would be to mount the fiber 16 so that it initially protrudes beyond face 56. Recessed portion 60 is then filled with a hard wax. Then the fiber and ferrule are polished in a carefully controlled manner. Afterwards, the hard wax may be dissolved. Such polishing is desirable because, in accordance with the present invention, these faces will be positioned adjacent to the corresponding faces in a coupled optical fiber, so that the interface between them is controlled to be extremely close. For example, a separation of 0.005 inches or less is desirable, as will be explained in more detail below.
Further, to maintain the ferrule face 56 and the fiber optic face 62 in the same plane, relative movement of the optical fiber 16 with the ferrule 48 must not occur. Prevention of such movement is accomplished by bonding the optical fiber 12 inside the ferrule 48 at reduced diameter portion 58. This bonding may be accomplished by filling opening 58 with an adhesive such as 3M Scotchbond 2216 prior to inserting the fiber.
Attached to ferrule 48 is a nut 64 which may be attached to the ferrule 48 by sliding over the crimp portion 52 until it reaches annular raised portion 66 of the ferrule 48. Annular raised portion 66 includes a first raised portion 68, and a second raised portion 70 having a larger diameter than portion 68. Raised portion 70 has a seat portion 72 which mates with a seat portion 74 of the nut 64. Also, the inner diameter of nut 64 is slightly larger than the outer diameter of raised portion 68. To retain nut 64 in transverse alignment with the ferrule 48, a washer 76 and a spring clip 78 engage with the nut 64. In this way, spring clip 78 retains the washer 76 and the nut 64 in a locked position by engaging with recessed portion 80 of ferrule 48. Consequently, nut 64 may not be moved axially along ferrule 48 but may rotate about ferrule 48 in alignment with raised diameter portion 70.
Nut 64 also contains threads 82 on its inside diameter for engagement with corresponding threads 84 on an interconnect member 86. In general, the fiber optic cable 12, having crimping tip 36, ferrule 48, and nut 64 attached thereto, may be mated with another optical fiber having identical crimping tip 36, ferrule 48, and nut 64 attached thereto, in accordance with the preferred embodiment of the present invention. To accomplish mating, interconnect 86 is first attached to one ferrule 48 as shown in FIG. 2. First, protruding portion 54 of ferrule 48 is inserted into a central opening 88 in connector 86. During insertion, nut 64 threads 82 contact interconnect threads 84, and nut 64 is rotated until ferrule protruding portion 54 is brought progressively deeper into central opening 88.
Interconnect 86 also contains a recessed portion 90 and a transverse face 92. Nut 64 is rotated until transverse face 92 makes contact with a transverse face 93 in ferrule 48. In accordance with the preferred embodiment, an O-ring 94 is placed over protruding portion 58 until it rests on ferrule transverse face 93 before the protruding portion 54 is inserted into the interconnect. Thus, when nut 64 is rotated into an engagement with threads 84, O-ring 94 will make contact with the recessed portion 90 and be compressed until face 92 contacts face 93. In this way, O-ring 94 creates an environmentally tight seal to protect the optical fiber 16.
To mate fiber optic cable 12 with an identical fiber optic cable 12, the mating optical fiber is fitted with identical components including the crimping tip 36, the ferrule 48, the nut 64, washer 76 and spring clip 78 as described above. This identical optical cable assembled unit is then inserted into the opposite end of the interconnect 86 in a manner similar to the first assembled unit. Tightening the nut 64 until face 92 contacts face 93 will thereby cause the ferrule face 56 and optical fiber face 62 to line up, close to, but not touching the adjacent ferrule face 56 and optical fiber 62 as shown in FIG. 4.
In accordance with an alternative embodiment, it may be desirable to mate 4.3 mm fiber optic cable 12 with a 2.2 mm fiber optic cable 14. This is accomplished as shown in FIG. 2 by first attaching a crimping tip 96 to the 2.2 mm optical cable 14. Crimping tip 96 is similar to crimping tip 36 with the exception that its diameter is configured to accept the 2.2 mm optical fiber 14. The ferrule 98 central opening 100 is adapted to receive first inner layer 28. The only major distinction between using the 4.3 fiber optic cable 12 and the 2.2 mm fiber optic cable 14 is that 2.2 mm fiber is designed to have strain relief taken up by a separate ruggedization which bundles several fibers together.
Besides this distinction, the 2.2 mm fiber optic cable 14 is coupled in a similar manner, by use of ferrule 98, having protruding portion 102, with recess 104, and flat face 106. Also ferrule 98 is coupled to connector 86 by means of nut 108, having threads 110, washer 112 and clip 114. Other corresponding details are the same as discussed above in connection with the 4.3 mm fiber optic cable 12.
As evident in FIG. 5, in the mated position recesses 60 and 104 in the adjacent mated ferrules 48 and 98 create an air space surrounding the interface between adjacent optical fibers 16 and 26. While the close proximity of the two optical fiber faces 62, for example 0.005 inches or less, will reduce the amount of light which escapes from the optical fibers 14 and 16, should some light escape it would have to travel through the air space in the recesses 60 and 104 before reaching ferrule 48. In the preferred embodiment this distance is at least 0.020 inches away from the fiber faces 62. At light energy of 425 milliJoules, the deposited energy could easily be sufficient to melt the copper-nickel-zinc material of the ferrules 48 and 98. However, because of the geometry and this relatively large distance, it is unlikely that the melted material could be deposited back onto the face of either optical fiber 16 or 26. Further, the greater distance will lessen the damage to the ferrules 48 and 98.
It can be seen that in the demated configuration optical fiber faces 62 can be readily inspected and cleaned if necessary. Also, because of the relative close proximity of the two optical fiber faces 62 in the mated condition, transmission losses at the fiber interface is low. For example, it has been found to range between 2% and 7% in some cases. In addition, it can be appreciated that the optical fiber connector 10 can be mated and demated numerous times without damage Also, the optical fiber connector 10 provides an effective means of strain relief to prevent damage to the optical fiber. Those skilled in the art can appreciate that other advantages can be obtained from the use of this invention without departing from the true spirit of the invention after studying the specification, drawings and following claims.
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A fiber optic connector apparatus (10) for coupling two fiber optic cables (12, 14) including a pair of connectors (48, 98) permanently attached to the fiber optic cables (12, 14). The connectors include a protruding portion (58, 102) with a central opening therethrough for receiving the fiber optic cables (12, 14). The protruding portions have a flat face (56) on their distal end and the optical fibers (16, 26) are inserted into the protruding portion (58, 102) so that end of the optical fiber (16, 26) lies in the plane of the flat face of the protruding portion (58, 102). A recessed portion (60, 104) in the flat face surrounds the optical fiber end to create an air space around the optical fiber ends. An interconnect member (86) removably adjoins a pair of the connectors (48, 98) so that the optical fiber ends are held in close proximity to each other. The close proximity reduces transmission losses and the recessed portion (60, 104) reduces the possibility of damage to the optical fiber ends should high power light energy escape at the interface and melt the parts of the connector. The connector apparatus (10) also permits the optical fiber ends to be easily inspected and cleaned when disconnected.
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BACKGROUND
Technical Field
[0001] The present disclosure relates to a phase-change memory cell and to a method for manufacturing the phase-change memory cell. In particular, the present disclosure relates to production of a heater of the phase-change memory cell.
Description of the Related Art
[0002] As is known, phase-change memories use a class of materials having the property of switching between two phases having distinct electrical characteristics, associated to two different crystallographic structures of the material, and precisely a non-orderly amorphous phase and an orderly crystalline or polycrystalline phase. The two phases are thus associated to values of resistivity that differ considerably from one another, even by two or more orders of magnitude.
[0003] Currently, the elements of Group XVI of the periodic table, such as for example Te or Se, also known as chalcogenide materials or chalcogenides, may be used in phase-change memory cells. As is known, for example, from P. Zuliani, et al., “Overcoming Temperature Limitations in Phase Change Memories With Optimized Ge x Sb y Te z ”, IEEE Transactions on Electron Devices, Volume 60, Issue 12, pages 4020-4026, Nov. 1, 2013, it is possible to use alloys of Ge, Sb, and Te (Ge x Sb y Te z , for example Ge 2 Sb 2 Te 5 ) optimized by appropriately choosing the percentages of the elements that form said alloys.
[0004] The temperature at which phase transition occurs depends upon the phase-change material used. In the case of Ge 2 Sb 2 Te 5 alloy, for example, below 150° C. both the amorphous phase and the crystalline phase are stable. If the temperature is increased beyond 200° C., there is noted a fast re-arrangement of the crystals, and the material becomes crystalline. To bring the chalcogenide into the amorphous state, one can increase further the temperature up to melting point (approximately 600° C.) and then cool it rapidly.
[0005] Numerous memories are known that exploit phase-change materials as elements for storage of the two stable states (amorphous and crystalline states), which may each be associated to a respective bit at “1” or at “0”. In these memories, a plurality of memory cells are arranged in rows and columns to form an array. Each memory cell is coupled to a respective selection element, which may be implemented by any switching device, such as PN diodes, bipolar junction transistors, or MOS transistors, and typically includes a chalcogenide region in contact with a resistive contact, also known as heater. A storage element is formed in a contact area between the chalcogenide region and the heater. The heater is connected to a conduction terminal of the selection element.
[0006] In fact, from an electrical standpoint, the crystallization temperature and the melting temperature are obtained by causing flow of an electric current through the resistive contact that extends in direct contact with or is functionally coupled to the chalcogenide material, thus heating it by the Joule effect.
[0007] According to the prior art, various processes of production of phase-change memory cells are known, which, however, present some disadvantages and limitations. In particular, processes of a known type normally require numerous manufacturing steps to form the selection elements, the chalcogenide regions, the heaters, and the contacts for connecting the selection elements and the storage elements to the bitlines and to the wordlines. An example of embodiment of a phase-change memory device of this type is described, for example, in U.S. Pat. No. 7,422,926.
[0008] These problems have been partially solved by techniques of self-alignment of the chalcogenide regions, of the heaters, and of the contacts. However, the manufacturing steps, and in particular the precision for producing the heaters, as well as solutions for minimizing the contact area between the heaters and the chalcogenide regions (formation of heaters having a thickness and/or diameter of sublithographic dimensions) render the process for manufacture of this type of memory cells problematical, long, and easily subject to errors.
[0009] Further, there are increasingly efforts aimed at integrating phase-change memories in CMOS platforms provided with logic devices having a wide range of functions (e.g., micro-controllers), thus providing devices or circuits of an embedded type.
BRIEF SUMMARY
[0010] At least some embodiments of the present disclosure provide a phase-change memory cell and a method for manufacturing the phase-change memory cell that overcome the drawbacks set forth above.
[0011] At least one embodiment is a phase-change memory cell that includes:
[0012] a substrate;
[0013] a selection transistor in the substrate and including a first conduction electrode;
[0014] a first electrical-insulation layer on the selection transistor;
[0015] a first conductive through via through the electrical-insulation layer and electrically coupled to the first conduction electrode;
[0016] a heater element including a first portion in electrical contact with the first conductive through via and a second portion that extends in electrical continuity with, and orthogonal to, the first portion;
[0017] a first protection element extending on the first and second portions of the heater element;
[0018] a second protection element extending in direct lateral contact with the first portion of the heater element and with the first protection element; and
[0019] a phase-change region extending over, and in electrical and thermal contact with, the heater element.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0020] For a better understanding of the present disclosure, preferred embodiments thereof are now described, purely by way of non-limiting example and with reference to the attached drawings, wherein:
[0021] FIG. 1 is a perspective view of a portion of a wafer that houses a phase-change memory and a logic device, in an initial step of a manufacturing process;
[0022] FIG. 2 is a top plan view of the portion of wafer of FIG. 1 ;
[0023] FIG. 3 is a lateral cross-sectional view of the portion of wafer of FIGS. 1 and 2 , taken along the line of section of FIG. 2 ;
[0024] FIG. 4 is a perspective view of the portion of wafer of FIG. 1 , in a subsequent manufacturing step;
[0025] FIGS. 5-13 show an enlarged detail of the portion of wafer of FIG. 4 , and regard manufacturing steps subsequent to that of FIG. 4 ;
[0026] FIG. 14 reproduces the same perspective view as that of FIGS. 1 and 4 , and illustrates a manufacturing step subsequent to that of FIG. 13 ;
[0027] FIG. 15 illustrates the portion of wafer of FIG. 14 in lateral cross-sectional view;
[0028] FIG. 16 shows, in perspective view, the portion of wafer of FIG. 14 in a manufacturing step subsequent to that of FIG. 14 ;
[0029] FIG. 17 illustrates the portion of wafer of FIG. 16 in lateral cross-sectional view;
[0030] FIG. 18 is a perspective view of the portion of wafer of FIG. 16 in a manufacturing step subsequent to that of FIG. 16 ;
[0031] FIG. 19 illustrates the portion of wafer of FIG. 18 in lateral cross-sectional view;
[0032] FIG. 20 is a lateral cross-sectional view of the portion of wafer of FIG. 19 in a manufacturing step subsequent to that of FIG. 19 ;
[0033] FIG. 21 is a lateral cross-sectional view of the portion of wafer of FIG. 20 in a manufacturing step subsequent to that of FIG. 20 ; and
[0034] FIG. 22 is a schematic representation of a system that uses the phase-change memory device according to the present disclosure.
DETAILED DESCRIPTION
[0035] Illustrated with joint reference to FIG. 1 (perspective view), FIG. 2 (top plan view), and FIG. 3 (cross-sectional view along the line of section of FIG. 2 ) is a wafer 1 (in particular a portion of a wafer 1 , for simplicity of representation). The wafer 1 is represented in a triaxial system X, Y, Z, in which the axes X, Y, and Z are mutually orthogonal.
[0036] The wafer 1 , comprising a substrate 2 , for example of a P type, is subjected to front-end processing steps of a standard type, in particular manufacturing steps of a CMOS process. In particular, formed in the substrate 2 are insulation regions (not illustrated), which delimit active areas 4 . Then formed (e.g., implanted) in the active areas 4 are drain regions 5 , source regions 8 , and gate regions 9 of respective MOS transistors.
[0037] Next, one or more dielectric layers 10 are deposited and planarized, for electrical insulation of the gate regions 9 , typically a pre-metal dielectric (PMD) layer. Openings are formed in the dielectric layer 10 over the drain regions 5 and the source regions 8 , and said openings are filled with tungsten to form a plurality of plugs, having the function of drain contacts 11 a and source contacts 11 b of the aforementioned MOS transistors. The drain contacts 11 a are, in particular, in electrical contact with the implanted drain regions 5 , and the source contacts 11 b are in electrical contact with the implanted source regions 8 .
[0038] In a per se known manner, the openings formed in the dielectric layer 10 may be covered by a first barrier layer, for example a Ti/TiN layer, before being filled with tungsten.
[0039] The left-hand side of the representation of the wafer 1 in FIG. 1 is dedicated to creation of a phase-change memory and will consequently be identified, in the sequel of the description, as memory side 1 ′; the right-hand side of the representation of the wafer 1 in FIG. 1 is dedicated to creation of a logic device 16 , which is to form an embedded circuit integrated in the same chip as the one that houses the phase-change memory and will consequently be identified, in the sequel of the description, as logic side 1 ″. It is evident that the use of the terms “right-hand” and “left-hand” has exclusively purposes of description with reference to the view of the figures and is in no way limiting for the purposes of the present disclosure.
[0040] The drain regions 5 , the source regions 8 , and the gate regions 9 formed on the memory side 1 ′ form selection transistors 15 of an nMOS type for cells of the phase-change memory, whereas the source regions 8 and the gate regions 9 formed on the logic side 1 ″ form transistors of the logic device 16 .
[0041] As may be noted, the source contact 11 b of each selection transistor 15 extends in a continuous way in the direction of the axis Y, parallel to the gate regions 9 . This embodiment presents the advantage of enabling electrical contact of the gate regions 9 and of the source contacts 11 b in a dedicated area of the wafer 1 , thus simplifying routing of the metal levels of the memory.
[0042] The drain contacts 11 a extend in the form of pillars and so that drain contacts 11 a belonging to one and the same selection transistor 15 are aligned with respect to one another in the direction Y. Drain contacts 11 a belonging to different selection transistors extend aligned with respect to one another in the direction X.
[0043] Once the steps for formation of the selection transistors 15 (memory side 1 ′) and of the transistors of the logic device 16 (logic side 1 ″) are completed, a protective layer 20 , for example of silicon nitride Si 3 N 4 , and a dielectric layer 21 , for example of silicon oxide SiO 2 , are deposited on the wafer 1 and then defined by lithographic and etching steps to form trenches 24 on the memory side 1 ′. The trenches 24 have a main (major) extension along Y and a secondary (minor) extension along X.
[0044] In each trench 24 there are exposed respective top faces of drain contacts 11 a , which are aligned with respect to one another along one and the same direction parallel to the direction Y.
[0045] More in particular, the steps of lithography and etching of the protective layer 20 and of the dielectric layer 21 are carried out so that a side wall 24 a of each trench 24 extends alongside, or partially over, the top faces of the drain contacts 11 a . The latter are thus completely or partially exposed through the respective trench 24 . The fact that the top faces of the drain contacts 11 a are exposed only partially guarantees a certain safety margin in the case of alignment errors. In this way, the problems regarding the fact that the wall 24 a could extend at an excessive distance, in the direction X, from the top faces of the drain contacts 11 a are solved. It is in fact convenient for the side wall 24 a of each trench 24 to extend (even in the case of misalignments) adjacent to, or in the proximity of, respective drain contacts 11 a . Acceptable distances between the wall 24 a and the center (or centroid) of the drain contacts 11 a , measured along X, are, for example, comprised between 0 nm (condition of contiguity or partial overlapping) and 30 nm.
[0046] It should be noted that the steps of deposition of the protective layer 20 and of the dielectric layer 21 are carried out over the entire wafer 1 , and thus also on the logic side 1 ″ of the wafer 1 . The portions of the protective layer 20 and dielectric layer 21 , which extend on the logic side 1 ″, will then be removed.
[0047] Illustrated with reference to FIGS. 5-9 is a method of production of a heater within the trenches 24 , according to one aspect of the present disclosure. For simplicity of representation, FIGS. 5-9 regard a portion of a trench 24 . It is evident that what has been described with reference thereto applies to all the trenches 24 provided in the wafer 1 on the memory side 1 ′.
[0048] First of all ( FIG. 5 ), a step of deposition of a resistive layer 26 , for example silicon and titanium nitride (TiSiN), is carried out to cover the wafer 1 and in particular the walls and the bottom of the trench 24 . The resistive layer 26 extends over the side wall 24 a and in direct contact with the top face of the drain contacts 11 a exposed through the trench 24 .
[0049] Since the material used for the resistive layer 26 tends to undergo fast oxidation in air and thus its own electrical characteristics tend to deteriorate, a step is carried out of deposition of a protective layer 28 , for example of dielectric material such as silicon nitride (Si 3 N 4 ), on the resistive layer 26 , in particular on the side wall 24 a of the trench 24 . The protective layer 28 has a thickness, measured along X on the side wall 24 a , of some tens of nanometers, for example between 20 and 100 nm, or in any case a thickness greater than the distance, along X, between the side wall 24 a and the drain contacts 11 a that extend in the trench 24 considered.
[0050] Then ( FIG. 6 ), a first step of dry etching of the protective layer 28 is carried out, for example anisotropic plasma etching, in the direction of the arrows 29 (i.e., in the direction Z). This first etch enables removal of portions of the protective layer 28 that extend parallel to the plane XY, maintaining the portions thereof that extend parallel to the plane YZ, i.e., on the side walls inside the trench 24 and in particular on the side wall 24 a , substantially unaltered. The protection walls 32 ′ and 32 ″ of FIG. 6 are thus formed.
[0051] Via an appropriate choice of the thickness of the protective layer 28 , after the etching step of FIG. 6 , the extension in the direction X of the protection wall 32 ′ on the side wall 24 a of the trench 24 is such as to overlie at least in part (in top plan view) the top faces of the drain contacts 11 a . In this way, during subsequent removal of selective portions of the resistive layer 26 , also the regions of the latter that extend underneath the protection walls 32 ′, 32 ″ will at least in part overlie (and, more in particular, will be in direct electrical contact with) the drain contacts 11 a . This step is illustrated with reference to FIG. 7 and may be carried out simultaneously with the step of etching of the protective layer 28 or else in a separate and subsequent etching step. Selective portions of the resistive layer 26 are thus removed from the wafer 1 except for the regions thereof protected (masked) by the protection walls 32 ′, 32 ″.
[0052] Resistive regions 34 ′ and 34 ″ are thus formed, which are, in lateral cross-sectional view in the plane XZ, substantially L-shaped and cover the side walls of the trench 24 (longer leg of the L) and, in part, the bottom of the trench 24 (shorter leg of the L). The resistive region 34 ′ extends over the side wall 24 a of the trench 24 and proceeds, with electrical continuity, until it electrically contacts, at least partially, the drain contacts 11 a . Preferably, the resistive region 34 ′ extends over the bottom wall of the trench 24 entirely covering the drain contacts 11 a . The resistive regions 34 ′, 34 ″ present, following upon the step of FIG. 7 , exposed regions at the bottom of the trench 24 , where coverage of the protection walls 32 ′, 32 ″ is not present.
[0053] Next ( FIG. 8 ), a step of deposition on the wafer 1 of a further protective layer 38 , for example silicon nitride (Si 3 N 4 ), is carried out. The protective layer 38 has a thickness, measured along X on the side wall 24 a , of some tens of nanometers, for example between 10 and 60 nm, and in any case a thickness such as not to occlude the trench 24 completely.
[0054] Then ( FIG. 9 ), a dry etching step is carried out to remove the protective layer 38 from the front of the wafer 1 and partially from the trench 24 except for portions of the protective layer 38 that extend coplanar to the protection walls 32 ′, 32 ″.
[0055] Further protection walls 40 ′, 40 ″ are thus formed, which extend in the trench 24 in contact with the protection walls 32 ′, 32 ″ and with the exposed portions of the resistive regions 34 ′, 34 ″ that derive from the previous etching step. In this way, the resistive regions 34 ′, 34 ″ are effectively and completely protected from oxidation phenomena.
[0056] Next ( FIG. 10 ), a step is carried out of deposition of dielectric material, in particular silicon oxide, SiO 2 , on the wafer 1 , to form a filling layer 42 that extends over the wafer 1 and fills the trench 24 completely. Portions of the filling layer 42 that extend outside the trench 24 are removed by a step of chemical mechanical polishing (CMP). CMP is carried out over the entire wafer 1 .
[0057] With reference to FIG. 11 , the CMP step completely removes the filling layer 42 that extends outside the trench 24 and thus completely removes, from the entire wafer 1 , also the dielectric layer 21 , stopping at the protective layer 20 . If the CMP step proceeds beyond the dielectric layer 21 , any possible removal of a minimal top portion of the protective layer 20 does not involve significant problems. During the step of removal of the dielectric layer 21 , the CMP technique is not, in practice, selective in regard to the Si 3 N 4 layers and to the material used for the resistive layer 26 that extend in the trench 24 , which are thus also removed partially until the maximum height, along Z, to which the protective layer 20 extends is reached. The thickness of the protective layer 20 and the duration of the CMP process thus define the maximum extension, along Z, of the resistive regions 34 ′, 34 ″ and of the protection walls 32 ′, 32 ″ and 40 ′, 40 ″.
[0058] This is followed by formation ( FIG. 12 ), in a per se known manner, of a layer of phase-change material (in what follows, “PCM layer”) 50 , for example by depositing a chalcogenide, such as a GST (Ge—Sb—Te) compound, e.g., Ge 2 Sb 2 Te 5 . Other phase-change materials may be used. Formation of the PCM layer 50 is carried out over the entire wafer 1 . A barrier layer 51 , of metal material, for example TiN, is formed on the PCM layer 50 to protect the PCM layer 50 from oxidation phenomena and likewise to form a low-resistivity layer for subsequent electrical-contact steps.
[0059] This is then followed ( FIG. 13 ) by deposition of an etch-protection layer, or “hard mask”, 52 (made, for example, of silicon nitride) and by lithographic and etching steps in order to remove selective portions of the barrier layer 51 and of the PCM layer 50 exposed through the hard mask 52 to create resistive bitlines 54 on the memory side 1 ′. Etching proceeds in the direction Z with removal of exposed portions of the protective layer 20 between adjacent resistive bitlines 54 . In this step, selective portions of the resistive regions 34 ′, 34 ″, of the protection walls 32 ′, 32 ″, of the protection walls 40 ′, 40 ″, and of the filling layer 42 that extend, in top plan view XY, between one resistive bitline 54 and an adjacent one are likewise removed.
[0060] FIG. 14 is a perspective view, which reproduces the view of FIGS. 1 and 4 , of the wafer 1 after the manufacturing steps described with reference to FIG. 13 , and FIG. 15 is a lateral cross-sectional view in the plane XZ, which reproduces the view of the portion of the wafer 1 illustrated in FIG. 14 .
[0061] According to an embodiment alternative to the one illustrated in FIG. 14 , the resistive bitlines 54 have locally widened regions, i.e., regions having an extension, along Y, that is locally increased. These regions are formed, for example, at the source contact 11 b on the memory side 1 ′ or in any case in the regions where, in subsequent manufacturing steps (see FIGS. 18 and 19 ), conductive vias will be formed to provide a top electrical contact in order to enable electrical access to the resistive bitlines 54 . The locally widened regions have the functions of compensating for possible undesired misalignments.
[0062] As illustrated in FIGS. 13-15 , the resistive bitlines 54 , of chalcogenide, extend electrically separate from one another in the direction X, each of them in thermal contact with a plurality of resistive regions 34 ′. Each of said resistive regions 34 ′ is, in turn, in electrical contact with a respective drain contact 11 a and forms, in use, a heater designed to generate, when traversed by electric current, heat by the Joule effect having a value such as to cause phase change in a respective portion of the resistive bitline to which it is thermally coupled.
[0063] It may be noted that, since the resistive regions 34 ″ are not electrically coupled to any drain contact 11 a , or to other electrical contacts, they do not play an active role during use of the memory array.
[0064] Following upon the steps of FIGS. 14 and 15 , the hard mask 52 may then be removed. However, since it does not generate problems during subsequent processing steps, the step of removal of the hard mask 52 is optional.
[0065] Then ( FIGS. 16 and 17 ), deposited on the wafer 1 is a sealing layer 58 of dielectric material, for example silicon nitride, having the function of protection of the chalcogenide material from exposure to air and of electrical insulation between the resistive bitlines 54 . The sealing layer 58 is deposited on the hard mask 52 and in the gaps between one resistive bitline 54 and the adjacent one. The sealing layer 58 is likewise deposited on the logic side 1 ″, on the dielectric layer 10 , and on the drain contacts 11 a and source contacts 11 b exposed through the dielectric layer 10 on the logic side 1 ″.
[0066] The resistive bitlines 54 are not suited to being used for conveying electrical signals for selection of the memory cells to be read/written in so far as their resistivity is too high. It is thus expedient to proceed with formation of conductive bitlines, of metal material, in electrical contact with the resistive bitlines 54 through conductive vias.
[0067] For this purpose, as illustrated in FIGS. 18 and 19 , a dielectric layer 60 , for example a silicon-oxide layer, is deposited on the wafer 1 , over the sealing layer 58 , and, by lithographic and etching steps, a plurality of openings 62 a , 62 b are formed in the dielectric layer 60 . The openings 62 a are formed on the memory side 1 ′, aligned, along Z, to respective resistive bitlines 54 , so that each opening 62 a forms a path towards a respective resistive bitline 54 . The openings 62 a are preferably formed at a distance from the heater, for example, at the source contacts 11 b.
[0068] By choosing the materials of the sealing layer 58 and of the dielectric layer 60 such that they may be etched selectively with respect to one another, the sealing layer 58 has the function of etch-stop layer during the step of formation of the openings 62 a , 62 b.
[0069] Formation of the openings 62 a thus includes selective removal of the dielectric layer 60 until surface portions of the sealing layer 58 are exposed, and removal of the portions of the sealing layer 58 thus exposed. In the case where the hard mask 52 has not been removed in previous manufacturing steps, it is expedient to remove the portions of hard mask 52 exposed through the openings thus formed, until surface regions of the barrier layer 51 are reached and exposed.
[0070] The openings 62 b are formed on the logic side 1 ″ so that each opening 62 b is aligned, along Z, with a respective drain contact 11 a and source contact 11 b (there may be used for this purpose alignment marks, in a per se known manner). The openings 62 b have in fact the function of forming, during subsequent manufacturing steps, conductive paths in electrical contact with the drain contacts 11 a and source contacts 11 b on the logic side 1 ″.
[0071] Formation of the openings 62 b thus includes selective removal of the dielectric layer 60 on the logic side 1 ″ until surface portions of the sealing layer 58 are exposed, and removal of the portions of the sealing layer 58 thus exposed, until the drain contacts 11 a and source contacts 11 b are reached and exposed.
[0072] Formation of the openings 62 a and 62 is advantageously carried out using a single etching mask.
[0073] This is followed by a step of filling with conductive material, for example metal material, of the openings 62 a , 62 b to form conductive vias in electrical contact with the resistive bitlines 54 (memory side 1 ′) and with the drain contacts 11 a and source contacts 11 b (logic side 1 ″).
[0074] After a step of cleaning of the front of the wafer 1 in order to remove the metal layer formed therein during filling of the openings 62 a , 62 b , it is possible to proceed with processing steps of a known type. In particular, FIG. 20 , there are formed conductive bitlines 64 on the front of the wafer 1 (memory side 1 ′) and paths 66 for routing of the signals (logic side 1 ″), according to a desired pattern that does not form the subject of the present disclosure. In particular, each conductive bitline 64 extends parallel and aligned, along Z, to a respective resistive bitline 54 .
[0075] This is followed, as illustrated in FIG. 21 , by a step of deposition of a further dielectric layer 68 on the wafer 1 , over the conductive bitlines 64 and the paths 66 , and a step of deposition and photolithographic definition of a metal layer, for formation of wordlines 70 on the memory side 1 ′. The wordlines 70 are electrically coupled to the gate regions 9 by conductive vias (not illustrated), which extend through the dielectric layer 68 and the dielectric layer 60 . Metal paths 72 may likewise be formed on the dielectric layer 68 on the logic side 1 ″.
[0076] The thickness of inter-metal layer 60 is not the same in the memory and logic regions. It is defined at the same quota, so a thickness approximately doubled is obtained in the logic. Opening 62 a and 62 b are consequently of very different height ( 62 b twice 62 a ). Furthermore metallization levels 64 and 66 are the same quota, and also levels 70 and 72 are basically the same metal layer.
[0077] FIG. 22 illustrates a portion of a system 200 according to an embodiment of the present disclosure. The system 200 may be implemented in various devices, such as for example PDAs, portable computers, phones, photographic cameras, video cameras, etc.
[0078] The system 200 may include a controller 210 (e.g., a microprocessor), an input/output device 220 , for example a keypad and a display, a chip housing in an integrated form the phase-change memory device 1 ′ and the control logic 1″ (designated as a whole by the reference number 1 ), a wireless interface 240 , and a random-access memory (RAM) 260 , connected together by a bus system 250 . According to one embodiment, the system 200 may be supplied by a battery 280 , or alternatively by a mains supply source. It is clear that the scope of the present disclosure is not limited to embodiments comprising all the components of FIG. 22 . For example, one or more from among the random-access memory (RAM) 260 , the wireless interface 240 , the battery 280 , and the input/output device 220 may be omitted.
[0079] The advantages of the present disclosure emerge clearly from the foregoing description.
[0080] In particular, formation of the heater with dual protection effectively prevents oxidation thereof during the manufacturing steps.
[0081] Further, by providing the memory in the same wafer as the one that houses the logic circuitry, it is possible to obtain the conductive vias 62 a for the bitline contacts of the memory simultaneously (i.e., with one and the same mask) with formation of the conductive vias 62 b for the contacts of the logic circuitry.
[0082] Finally, it is clear that modifications and variations may be made to what has been described and illustrated herein, without thereby departing from the scope of the present disclosure.
[0083] The various embodiments described above can be combined to provide further embodiments. These and other changes can be made to the embodiments in light of the above-detailed description. In general, in the following claims, the terms used should not be construed to limit the claims to the specific embodiments disclosed in the specification and the claims, but should be construed to include all possible embodiments along with the full scope of equivalents to which such claims are entitled. Accordingly, the claims are not limited by the disclosure.
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A phase-change memory cell, comprising: a substrate housing a transistor, for selection of the memory cell, that includes a first conduction electrode; a first electrical-insulation layer on the selection transistor; a first conductive through via through the electrical-insulation layer electrically coupled to the first conduction electrode; a heater element including a first portion in electrical contact with the first conductive through via and a second portion that extends in electrical continuity with, and orthogonal to, the first portion; a first protection element extending on the first and second portions of the heater element; a second protection element extending in direct lateral contact with the first portion of the heater element and with the first protection element; and a phase-change region extending over the heater element in electrical and thermal contact therewith.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] The present application claims priority to Malaysian Patent Application No. ______, filed May 29, 2006, entitled “COLOR MATCHING UTILIZING COLOR SAMPLE CLUSTERING,” the entire contents of which are hereby incorporated by reference.
BACKGROUND
[0002] With Internet access broadly available, individuals and businesses are embracing it as a new media of exchange. In color-critical industries, the process of color specification, color matching and color approval is increasingly being automated by digital means. In a non-digital world, the manual way of visually assessing, matching, and approving color involves humans. For example, a user would need to compare samples in a light box, or leaf through a color palette book to lookup similar or complementary colors. The manual process is subject to human interpretations and is inconsistent. The same person may approve a sample one day and fail it another. In contrast, a digital color matching and approval system eliminates human subjectivity. The system can quickly compare thousands of samples against a target and reduce the need to send physical samples, saving lead time and courier charges. Color matching and approval thus become a manageable and controllable process.
[0003] Many digital color matching and approval systems use the conventionally denoted dE (delta E) tolerance values to either pass or fail samples matched against a target in a color space. A color space is a model describing the way colors can be represented as tuples of numbers, typically as three or four values or color components. One can also think of a color space as a model for representing color in terms of intensity values. Different types of color spaces include: RGB-based color spaces (used mainly for displays and scanners), CMYK-based color spaces (used mainly for color printing) and device-independent color spaces used mainly for color models (L*a*b*, LCH, LUV, etc.). Visually, these spaces often correspond to various solid shapes, such as spheres, cubes, cones, or polyhedrons. For example, the RGB space is a three-dimensional color space whose components are the red, green, and blue intensities that make up a given color.
[0004] Conventional methods employed for digitally searching and matching colors are usually based on compacting a multidimensional color space using arrays, with each array holding color information for a specific combination of external factors affecting color perception. When these arrays are used, searching and matching a target with a large amount of samples with external factors accounted for is slow and inefficient, as numerous passes through these arrays are essential every time a search and compare is carried out.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 illustrates a color space diagram to be used in embodiments of this invention;
[0006] FIG. 2 illustrates sample clusters and a target color represented with a color space in accordance with an embodiment of this invention;
[0007] FIG. 3 illustrates a data storage structure including cluster attributes to facilitate searching and/or matching operations in accordance with an embodiment of this invention;
[0008] FIG. 4 illustrates another data storage structure including other color information to facilitate searching and/or matching operations in accordance with an embodiment of this invention;
[0009] FIG. 5 illustrates sample clusters and a complement of a target color represented within a color space in accordance with an embodiment of this invention;
[0010] FIG. 6 illustrates a color matching system in accordance with an embodiment of this invention;
[0011] FIG. 7 illustrates an indexing operation in accordance with an embodiment of this invention;
[0012] FIG. 8 illustrates a search and match operation in accordance with an embodiment of this invention; and
[0013] FIG. 9 illustrates a color matching device in accordance with an embodiment of this invention.
DETAILED DESCRIPTION
[0014] In the following detailed description, reference is made to the accompanying drawings which form a part hereof wherein like numerals designate like parts throughout, and in which is shown by way of illustration embodiments in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural or logical changes may be made without departing from the scope of the present invention. Therefore, the following detailed description is not to be taken in a limiting sense, and the scope of embodiments in accordance with the present invention is defined by the appended claims and their equivalents.
[0015] Various operations may be described as multiple discrete operations in turn, in a manner that may be helpful in understanding embodiments of the present invention; however, the order of description should not be construed to imply that these operations are order dependent.
[0016] For the purposes of the present invention, the phrase “A/B” means A or B; the phrase “A and/or B” means “(A), (B), or (A and B)”; the phrase “A, B, and/or C” means “(A), (B), (C), (A and B), (A and C), (B and C), or (A, B and C)”; and the phrase “(A)B” means “(B) or (AB),” that is, A is an optional element.
[0017] The description may use the phrases “in an embodiment,” or “in embodiments,” which may each refer to one or more of the same or different embodiments.
[0018] Furthermore, the terms “comprising,” “including,” “having,” and the like, as used with respect to embodiments of the present invention, are synonymous.
[0019] In a color-critical industry employing digital color process (for example, textile and apparels), there may be thousands of color samples sitting in the organization's data storage. The amount of color samples may increase exponentially when considering and accounting for external factors that may affect the visual appearance of these samples. For example, different illuminations (e.g., D65, D55, F11 and others) on a surface can yield different visual appearance of colors. Other external factors such as, but not limited to, the observer (where the color perception of two people are different), field size (different observation angles), and geometry (different viewing geometries) may also influence the visual appearance of colors.
[0020] In various embodiments, the color samples may relate to colored goods such as, but limited to, substances (e.g., dyes, paints, and other substances used for coloring) and/or products (e.g., textiles, apparels, manufactured products, auto parts, toys, jewelry, accessories, etc.).
[0021] Embodiments of this invention may provide for an efficient arrangement of color information in a multi-dimensional color space to facilitate high-speed searching and comparison of color information, including complementary color matching, with external conditions factored in. Utilizing embodiments of the present invention, users may quickly search through a number of color samples and compare them against a target color. The target color may be a color inspiration for an upcoming season of apparels, for instance. The search and compare may allow the user to quickly determine if a matching and/or complementary color already exists in an organization's database of sample colors.
[0022] Referring now to FIG. 1 , there is illustrated an example of a color space 100 for describing color in accordance with embodiments of this invention. This color space is known as the CIE L*a*b* and is one of the most widely used color spaces established by the Commission Internationale de l'Eclairage (CIE) (a.k.a. International Commission on Illumination), an organization devoted to international cooperation and exchange of information among its member countries on matters relating to the science and art of lighting and illumination. The CIE L*a*b* color space is a mathematical model describing color sensations (caused by light from a particular illuminant reflecting from an object with particular reflectance properties as measured by a reflectance curve, for example) and is based on the color describing theory of opponent colors. The concept follows that colors can be considered as combinations of red and green, yellow and blue, and dark and light.
[0023] Like most color spaces, the difference between colors in the CIE L*a*b* agree consistently well with human visual perceptions of the differences. A given color may be associated with a series of parametric measurements measuring red/green factor, blue/yellow factor, and dark/light factor. These measurements uniquely describe the color and can be represented as a point in a three-dimensional color space 100 , where the red/green parametric measurement may be plotted as point on a red/green axis 110 a , where the blue/yellow parametric measurement may be plotted as point on a blue/yellow axis 110 b , and where the dark/light parametric measurement may be plotted as point on dark/light axis 110 c.
[0024] Information in a color space may be indexed and stored as records in a data storage structure. The foregoing data storage structure may allow such records to be searched by the visual appearance of the colors. While embodiments of the present invention may be discussed with reference to the CIE L*a*b* color space, other embodiments may employ any n-dimensional color space where each point represents a color value.
[0025] Referring now to FIG. 2 , there is illustrated a diagram organizing color information for searching and matching in a color space 200 , which may be a stripped-down diagram of color space 100 , in accordance with an embodiment of this invention. The target T may be depicted as one instance of the many combinations of external factors influencing visual color perception. For example, the target T may depict a color measured with a D65 illuminant and 2 degree observer angle. The tolerance value for target T may be dE, which may be set by the user. The boundary outlined by dE may be spherical. This means any color samples found within the dE tolerance may be considered a match. On the other hand, color samples which fall outside the dE tolerance may not be considered a match.
[0026] Embodiments of this invention may cluster together a plurality of values in the color space 200 representing a particular color sample influenced by varying sets of external factors. For example, one color space value of a cluster may be determined by analyzing a color sample's spectral data under a first set of external factors, e.g., a first illuminant and a first angle. Another color space value of the cluster may be determined by analyzing the color sample's spectral data under a second set of external factors, e.g., a second illuminant and a second angle. As used herein, varying sets of external factors may be defined as at least two sets of external factors having at least one element which is different from the other set. These color sample clusters may be used to facilitate rapid searching and comparing of sample colors under different external factors.
[0027] A spherical boundary for each sample color cluster (e.g., SC 1 to SC 4 ) may be calculated and created such that it encompasses the plurality of values of the cluster. If a sample color cluster's spherical boundary happens to intersect the target T spherical boundary, there may be one or more colors in the cluster that fall within the target T's dE tolerance level. In the case of sample clusters in color space 200 , SC 1 and SC 2 meet these criteria, and will be identified as potential matches for further processing. SC 3 and SC 4 do not meet these criteria, and will not be processed further.
[0028] Note that the dE boundary for target T as well as the sample color clusters (SC 1 to SC 4 ) in color space 200 need not be spherical in nature. The boundary shape may be determined by the type of color space. For simplicity in illustration and calculation, however, a sphere may be used. The same assertion may be said of other n-dimensional color spaces.
[0029] FIG. 3 illustrates a data storage structure 310 including cluster attributes to facilitate searching and/or matching operations in accordance with an embodiment of this invention. The data storage structure 310 , which may also be referred to as the master array 310 , may include cluster attributes representative of the sample clusters SC 1 -SC 4 as they exist in the 3-D color space 200 . The color attributes may be information about the sample clusters SC 1 -SC 4 , arranged by indices 330 , including, e.g., the midpoints of each cluster 315 and its corresponding radius 320 . This information may allow each cluster to define its spherical boundary, and to facilitate a high-speed computation of whether the clusters intersect with the boundary of the target T. In various embodiments, other cluster attributes may additionally/alternatively be stored in the master array 310 to allow for preliminary matching operations as will be described later.
[0030] FIG. 4 illustrates another data storage structure 410 , which may also be referred to as a secondary array 410 , including further data for each color sample in accordance with an embodiment of this invention. Each index 330 in the master array 310 may be linked with one or more corresponding color keys in the secondary array 410 . Index information from intersecting color sample clusters (e.g., SC 1 and SC 2 ) may be used with secondary array 410 to extract further data, e.g., detailed color information, about the corresponding color sample, while the rest of the nonintersecting cluster colors may be ignored. The further data of the corresponding color samples may be used to compute for color matches.
[0031] In various embodiments, the further data may include information on attributes of the color sample such as, but not limited to, color key attributes (for indexing), cluster attributes (e.g., sample cluster key information from the master array 310 ), color space values defined by, e.g., L*, a*, and b* values, for given external factors, e.g., field size and illumination. In various embodiments the secondary array 410 may be additional/alternative color spaces and/or attributes.
[0032] The master array 310 and secondary array 410 may be flexible enough to accommodate adding, updating or deleting additional color attributes. Adding additional external factors, for example, a new illuminant or field size to an existing color is as easy as adding the attribute to the secondary array 410 under an existing cluster. Adding a new cluster of sample colors entails adding an additional row to the master array 310 and creating one or more color information for the new cluster in secondary array 410 .
[0033] Clustering colors under different external factors and storing them into master array 310 and secondary array 410 may facilitate searching and comparing sample colors against a target under different external conditions. In a single pass through the master array 310 intersecting sample color clusters may be identified and singled out for detailed color information drill-down using the secondary array 410 .
[0034] FIG. 5 illustrates sample clusters and a complement of a target color represented within a color space in accordance with an embodiment of this invention. Color space 500 may be similar to color space 200 ; however, color space 500 shows the original target T in color space 200 being projected to its complementary color, T C . The tolerance value set by the user for target T C may be dE. Again, note that the boundary outlined by dE is spherical. This means any sample colors found within the dE tolerance may be considered a match. On the other hand, samples which fall outside the dE tolerance may not be considered a match.
[0035] Similar to the above discussion with respect to FIG. 2 , to enable rapid searching and comparing of sample colors under different external factors, different color measurements of external factors influencing the sample may be clustered together (e.g., SC 1 to SC 4 ) in color space 500 . A spherical boundary for each sample color cluster (e.g., SC 1 to SC 4 ) may be calculated and created. If a sample color cluster's spherical boundary happens to intersect the target T C spherical boundary, this means there may be one or more colors in the cluster that falls within the target T C 's dE tolerance level. In the case of sample clusters in color space 500 , SC 3 meets these criteria, and may be singled out for further processing. SC 1 , SC 2 , and SC 4 do not meet these criteria and may not need to be processed further.
[0036] It should be pointed out that in color space 500 , T C may include any color correlated to the target color, e.g., a complementary color, a contrast color, a triad color, a tetradic color, an analogic color, etc. Note that the dE boundary for target T C as well as the sample color clusters (e.g., SC 1 to SC 4 ) in color space 500 need not be spherical in nature. The boundary shape is usually determined by the type of color space. For simplicity in illustration and calculation, however, a sphere is commonly used and accepted. The same assertion can be said of other n-dimensional color spaces.
[0037] FIG. 6 illustrates a color matching system 600 in accordance with an embodiment of this invention. In this embodiment, an index module 604 may be coupled to a communication interface 608 to receive data on color samples to be indexed from a color input device 612 . The color input device 612 may, for example, allow a seller of colored goods to upload color information relating to the colored goods to the color matching system 600 . The index module 604 may organize the data to facilitate matching operations of embodiments of this invention. The organized data may be stored in a data storage device, e.g., database 616 .
[0038] In an embodiment, the color matching system 600 may also include a search module 620 coupled to a communication interface 624 to receive search criteria from a search source 628 , e.g., a search engine. The search source 628 may, for example, allow a potential buyer to input search criteria related to a sought colored goods. In various embodiments, the search criteria may include, e.g., target color data, tolerance levels, one or more illuminants (e.g., a primary illuminant and a secondary illuminant), etc. In some embodiments, the search criteria may also include non-color information, e.g., type of good, quantity, etc.
[0039] The search module 620 may be coupled to the database 616 and configured to identify the color samples matching the provided search criteria. Further operation of the components introduced in FIG. 6 may be discussed below in accordance with various embodiments.
[0040] In some embodiments, all of the components of the color matching system 600 may be co-disposed at the same site. In other embodiments, one or more components may be disposed remotely from other components and coupled to the other components via a private and/or public network, e.g., the Internet.
[0041] FIG. 7 illustrates an indexing operation 700 in accordance with an embodiment of this invention. In this embodiment, the index module 604 may receive color sample spectral data from the color input device 612 for a plurality of color samples, block 704 . The index module 604 may then develop color sample clusters (e.g., SC 1 -SC 4 ), block 708 . As discussed above, each color sample cluster may include a plurality of values in a color space representing the particular color sample influenced by varying sets of external factors. The index module 604 may determine cluster attributes, block 712 , and store said attributes in a first data storage structure, e.g., master array 310 , block 716 . The index module 604 may store further data on the color samples, e.g., more detailed information about the plurality of values in the color space, in another data storage structure, e.g., the secondary array 410 , block 720 .
[0042] FIG. 8 illustrates a matching operation 800 in accordance with an embodiment of this invention. In this embodiment, the search module 620 may receive search criteria, including target data, from the search source 628 , block 804 . The search module 620 may compare target data to cluster attributes stored in the master array 310 , block 808 . This comparison may determine if any of the color samples are potential matches (e.g., they have the potential of satisfying the search criteria), block 812 . If no potential matches are found, the search module 620 may return an indication of no matches to the search source 628 , block 816 .
[0043] If potential matches are found, the search module may compare the search criteria to further data of the potential matches found in the secondary array 410 , block 820 . This comparison may determine if any of the color samples are matches (e.g., they satisfy the search criteria), block 824 . If matches are found, the matches may be returned to the search source 628 , block 828 . If no matches are found, an indication of such is returned, block 816 .
[0044] In some embodiments, accompanying information may be returned to the search source 628 along with match information based at least in part on the match information and/or search criteria. For example, if search criteria includes a blouse of a target color, matching results may be accompanied by other information that may be of interest to the potential buyer, e.g., complementary bottoms for the blouse, other goods of that target color, etc.
[0045] FIG. 9 illustrates a computing device 900 capable of implementing various color match operations in accordance with various embodiments. As used herein “color match operations” may include indexing, organizing, arranging, matching, searching, and/or other operations as described herein. As illustrated, for the embodiments, computing device 900 includes processor 904 , memory 908 , and bus 912 , coupled to each other as shown. Additionally, computing device 900 includes storage 916 , and communication interface 920 coupled to each other, and the earlier described elements as shown.
[0046] Memory 908 and storage 916 may include temporal and persistent copies of color match logic 924 , respectively. The color match logic 924 may include instructions that when accessed by the processor 904 result in the computing device 900 performing operations or executions described in accordance with embodiments of this invention. In particular, the accessing of the color match logic 924 by the processor 904 may facilitate indexing and/or searching operations as described above in connection with various embodiments.
[0047] In various embodiments, the memory 908 may include RAM, dynamic RAM (DRAM), static RAM (SRAM), synchronous DRAM (SDRAM), dual-data rate RAM (DDRRAM), etc.
[0048] In various embodiments, the processor 904 may include one or more single-core processors, multiple-core processors, controllers, application-specific integrated circuits (ASICs), etc.
[0049] In various embodiments, storage 916 may include integrated and/or peripheral storage devices, such as, but not limited to, disks and associated drives (e.g., magnetic, optical), universal serial bus (USB) storage devices and associated ports, flash memory, read-only memory (ROM), nonvolatile semiconductor devices, etc.
[0050] In various embodiments, storage 916 may be a storage resource physically part of the computing device 900 or it may be accessible by, but not necessarily a part of, the computing device 900 . For example, the storage 916 may be accessed by the computing device 900 over a network.
[0051] In various embodiments, computing device 900 may have more or less elements, and/or different architectures.
[0052] Various embodiments have been described to efficiently organize, search, and compare color information based on multidimensional color space information. Sample colors under different illuminations, observers and other external factors that affect the visual appearance of colors may be clustered. This color information may then be compacted into a primary array permitting efficient search and a second array for further processing of color samples identified as potential matches.
[0053] Although embodiments of the present inventions have been illustrated in the accompanying Drawings and described in the foregoing Detailed Description, it will be understood that the inventions are not limited to the embodiments disclosed, but are capable of numerous rearrangements, modifications, and substitutions without departing from the spirit of the invention as set forth and defined by the claims and equivalents thereof.
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A method, an apparatus, and a computer program product for color matching and/or indexing utilizing color sample clustering is generally disclosed. Other embodiments may be described and claimed.
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BACKGROUND OF THE INVENTION
This invention relates to a method and to an apparatus for controlling fuel of a gas turbine and, more particularly, relates to a method and to an apparatus for controlling fuel at the time of load rejection or FCB (first cut back).
In machinery combining power and load or in a combination plant of a generator and a prime mover serving as power source, for example, load rejection is when the load of the generator is reduced abruptly down to zero or a certain fixed load while keeping a ordinary or normal number of revolutions. In the event of such load rejection, it becomes necessary to control the prime mover to supply thereto less energy.
For example, in rotary machine such as a steam turbine, with load rejection, generated energy is converted to rotational energy to bring about an increase in the number of revolutions if the steam supply is not decreased. However, the rotary machine has an upper limit with the number of revolutions which is decided by the allowable stress of its material so that it is necessary to control the steam supply valve to be closed or opened at a proper opening for the purpose of preventing the number of revolutions from exceeding the upper limit. On the other hand, as the load rejection takes place in the gas turbine, it becomes necessary to reduce the fuel supplied to the gas turbine for the same reason as described above. It is noted here that the gas turbine is constructed in general by a compressor, a combustor and a turbine. Fuel is injected into the combustor to be burned with air compressed to high pressure by the compressor. The combustion gas is then expanded in the turbine to generate or perform work. Accordingly, since it is necessary to produce compressed air by the compressor at all times in order to maintain a constant number of revolutions of the gas turbine, work must be performed by the turbine by an amount corresponding to compression work even in the state of no load. Thus, it becomes necessary to inject a prescribed quantity of fuel even if the turbine is operated with no load. Further, in the combustor of the gas turbine, combustion cannot take place as the flow rate of fuel to be supplied to the combustor falls below a certain limit, resulting in a phenomenon known as flameout. Such flameout results in the air containing combustible matter and flowing downstream to be in an extremely dangerous state. For this reason, it is one of the necessary functions of the fuel flow rate control valve controlling apparatus to rapidly reduce the time required from the opening of the fuel flow rate control valve during normal operation to the opening of the fuel flow rate control value at which the fuel flow rate corresponds to no load operation without causing the flameout phenomenon and incurring a excessive number of revolutions at the time of load rejection.
FIG. 3 shows an example by a block diagram of a conventional fuel flow control system. In this system, an output W detected by an output detector 6 attached and belonging to a load 9 is compared with a set output W* as a desired or target value by a comparator 1 and is then converted into a desired number of revolutions N* by an arithmetic unit 2 in accordance with an output deviation ΔW thus obtained. In the gas turbine, this conversion function is usually set at 104% when a rated output is the desired value and at 100% for no load. The desired number of revolutions N* is increased at a predetermined fixed rate when the output deviation ΔW is positive, and N* is decreased at a predetermined fixed rate when ΔW is negative.
However, when no power is required for the load 9, it is set at 100%.
A number of revolutions N detected by a revolution detector 7 belonging to a gas turbine 8 is compared with the desired number of revolutions N* by a comparator 3, and an output ΔN thus obtained is converted into the desired opening θ 0 of fuel flow rate control valve by an arithmetic unit 4.
An arithmetic unit 5 calculates the minimum value of the desired opening of a fuel flow rate control valve 12 to set the opening of the fuel flow rate control valve within a range that can prevent a combustor 14 from causing a flameout. The flameout of the combustor 14 happens depending on the characteristics of the combustor; it takes place when the fuel air ratio becomes equal to or less than a certain predetermined value Since the flow rate of the air discharged from a compressor 13 to be supplied to the combustor 14 varies in accordance with the atmospheric temperature and the number of revolutions, the arithmetic unit 5 corrects for the minimum value of the desired opening of the fuel control valve 12 in response to the atmospheric temperature T detected by an atmospheric temperature detector 11 and number of revolutions N.
A pressure control valve 17 keeps constant an inlet pressure P 2 of the fuel flow rate control valve 12 detected by a pressure detector 18. Therefore, the fuel flow rate which decides the output (power) of the gas turbine is determined uniquely by the opening of the fuel flow rate control valve 12.
In accordance with the change of θ 1 which is the output of the arithmetic unit 5, the opening of the fuel flow rate control valve 12 is varied to change of the fuel flow rate and, thereby makes the output W approach the set output W*. In this way, a prescribed feedback control is performed.
Here, FIG. 4 shows the behavior of the above conventional control system in the case that load is rejected or the set output W* for the load 9 becomes zero from the rated value in substantially an instant.
Description will be given below of FIG. 4. It is assumed that the load rejection takes place at a point of time T 1 . The set output W* changes from point A 1 to point A 3 via point A 2 . Assuming that A and B are constants, the calculation is done in the arithmetic unit 4 based on the following formula;
θ.sub.0 =A×(N*-N)+B
Values for B correspond to lines g and h, for example, conditions without load.
A value for the desired minimum valve opening corresponding to line e is set in the arithmetic unit 5. Therefore, the desired fuel flow rate control valve opening θ 1 changes from point B 1 to point B 3 via point B 2 , thereafter, passes through point B 4 and asymptotically approaches line g. The opening of the fuel flow rate control valve 12 changes from point C 1 to point C 3 via point P, and thereafter, gets to line h in accordance with the change of the desired opening. The output (power) W of the gas turbine changes along a line equivalent to line c. During the period t 1 in which the output of the gas turbine is not less than zero after the load is rejected at point T 1 , the number of revolutions N rises temporarily form point D 1 to point D 2 , and however, it tends to drop as the opening of the fuel flow rate control valve 12 settles down to line d and, thereafter, settled down to line h.
In this way, the output W responds to the change of the set output W*.
According to this controlling method, however, the minimum opening of the valve becomes less than the minimum set value for the desired or target opening value, resulting in that fuel is supplied to the combustor only at the rate below the desired fuel flow rate. To cope with this, the limit can be fixed beforehand, which must be fixed to line f in actuality, to line e obtained by upwardly correcting by an amount of difference ΔB corresponding to a difference ΔC between lines d and b. However, this measure gives rise to a problem that the rise of the number of revolutions is further promoted at the time of load rejection so that it cannot be regarded as a solution.
OBJECT AND SUMMARY OF THE INVENTION
The present invention has been made in view of the above problem, and an object thereof is to provide a method and an apparatus for controlling fuel of a gas turbine which are capable of preventing the flameout of a combustor without permitting the opening of a fuel flow rate control valve to be less than a preset limit at the time of load rejection, while minimizing the rise of the number of revolutions.
To this end, there is provided according to the present invention a method for controlling fuel of a gas turbine in which a fuel supply control valve is controlled to control the amount of fuel supply to a combustor in proportion to the magnitude of load. The method comprises the steps of, when shifting the fuel supply amount that is to a fuel supply amount agreeable with changed load when load of the gas turbine has been changed, operating the fuel supply control valve at a high speed at the time of starting the control, and operating the fuel supply control valve at a lower speed than the high speed at a time near to when the fuel supply amount necessary for the changed load is reached.
In accordance with the controlling method of the present invention, when the fuel supply amount required for the changed load is approached, the desired opening command, and the opening and closing speed of the control valve are lowered. In consequence, its undershooting of the control valve is reduced and, hence, the flameout in the combustor is prevented without causing a rise of the number of revolution of the gas turbine over a certain limit.
According to this invention, the above-mentioned object is accomplished, as well, by an apparatus for controlling fuel of a gas turbine comprising:
a fuel control valve for controlling an amount of fuel supply to a combustor; and a valve opening command means for issuing an opening command to said fuel control valve according to a magnitude of load of the turbine, wherein combustion is performed in accordance with the load of the gas turbine, and said valve opening command means has a correction command means for operating said fuel control valve at high speed during an initial stage of opening and closing operation thereof and at lower speed than said high speed near the desired opening value.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a gas turbine control system for explanation of a fuel controlling method according to a preferred embodiment of the present invention;
FIG. 2 is a graph showing characteristic curves obtained when a gas turbine is started;
FIG. 3 is a block diagram of a gas turbine control system for explanation of a conventional fuel controlling method;
FIG. 4 is a graph showing characteristic curves obtained when a conventional gas turbine is started; and
FIGS. 5 and 6 are diagrammatic views showing correction values for the desired opening of a fuel flow rate control valve according to the preferred embodiment of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
A description is given below of an embodiment of the present invention with reference to FIG. 1. An output W detected by an output detector belonging to a load 9 is compared with a set output W* as a desired or target value by comparator 1 and is then converted into a desired number of revolutions N* by an arithmetic unit 2 in accordance with an output deviation ΔW thus obtained. In the gas turbine, this conversion function is designed to be usually set at 104% for the case where the rated output thereof is the desired value and at 100% for the case of no load; N* is increased at a predetermined fixed rate when the output deviation ΔW is positive and is decreased at a predetermined fixed rate when ΔW is negative. However, when no power is required for the load 9, it is set at 100%. A number of revolutions N detected by a revolution detector 7 belonging to a gas turbine 8 is compared with the desired number of revolutions N* by a comparator 3, and an output ΔN thus obtained is converted into a desired opening θ 0 of fuel flow rate control valve by an arithmetic unit 4.
An arithmetic unit 5 calculates the minimum value of the desired opening of a fuel flow rate control valve 12, where the opening of the fuel flow rate control valve corresponding to the blowout or flameout fuel flow rate of a combustor 14 is set. The blowout or flameout of the combustor 14 will take place depending on the characteristic of the combustor; it takes place when the fuel air ratio becomes equal to or less than a certain given level. On the other hand, the flow rate of air discharged from a compressor 13 and supplied to the combustor 14 varies in accordance with the atmospheric temperature and the number of revolutions. Therefore, the minimum value of the desired opening of the fuel control valve 12 calculated by the arithmetic unit 5 is corrected in accordance with the atmospheric temperature T detected by an atmospheric temperature detector 11 and the number of revolutions N. In an arithmetic unit 10, a series of feedback controls is performed such that a time-dependent correction factor Δθ 1 determined by a method to be explained later from parameters including a valve opening θ detected by a fuel flow rate control valve opening detector 15, are added to a desired opening θ 1 of the fuel flow rate control valve 12 by an adder 16; and, finally, θ 2 is a desired opening of the fuel flow rate control valve, thereby enabling the output to approach the set output W* in accordance with θ 2 . Here, FIG. 2 shows the behavior in which the load is rejected; for example, the set output W* necessary for the load 9 becomes zero from the rated value in substantially an instant. In this drawing, the behavior due to the controlling method of a preferred embodiment of the present invention is compared with the behavior due to the conventional control system. Further, FIG. 5 shows an example of the correction value Δθ 1 . In this drawing, the correction value Δθ 1 is expressed as Δθ 1 =f(θ(T 1 ), time) assuming that θ(T 1 ) represents the fuel flow rate control valve opening θ at time T 1 . Namely, this correction value Δθ 1 makes the correction to decrease the valve opening speed. In case the correction value Δθ 1 is used, it is possible to make the opening of the fuel flow rate control valve asymptotically and smoothly approach the line b which corresponds to the minimum desired opening of the fuel flow rate control valve without undershooting as indicated by point P in the conventional controlling method. It is also possible to express the correction value Δθ 1 using the gas turbine output W at time T 1 as a parameter. In this case, the correction value Δθ 1 is expressed by the formula below:
Δθ.sub.1 =f(W(T.sub.1), time).
Further, the correction value can be determined without difficulty by computer simulation with a model of the gas turbine 8, other devices and the controlling apparatus. When the correction value Δθ 1 is expressed as Δθ 1 =f(W(T 1 ), time), assuming that, for example,
Δθ.sub.1 =b×W(T.sub.1)-a×(T-T.sub.1)
where "a" and "b" are constants. The computer simulation can be performed while determining the values of "a" and "b" so that the maximum value of the first term of the above formula does not exceed the valve opening of the fuel control valve at time T 1 , and the correction amount becomes zero before time T 2 at the latest; the number of revolutions is maximized after the load rejection, decreasing the fuel supply as much as possible. This is equally applicable to other cases using other polynominal expressions or other functions for Δθ 1 , and, in these cases, the accuracy of the results is judged by the prevention of undershooting of the opening of the fuel control valve; or the prevention of the undershooting of fuel air ratio.
The above-mentioned embodiments of the present invention is realized by either analog electronic circuits or a digital computer. FIG. 6 shows an example of the correction value Δθ 1 while using the digital computer. In this case, outputs are produced at every sampling time ΔT so that the correction value is expressed as Δθ=f(θ(T 1 ), time) being like the correction value shown in FIG. 5 but having staircase-like values.
As has been described above, according to the present invention by making the fuel supply amount immediately respond to the value of the required low-load fuel supply amount when the load is reduced abruptly, the fuel control valve is closed at high speed until the required low-load fuel supply amount is reached halfway, and, thereafter, closed at lower speed than initially according to correction. Therefore, when approaching the fuel supply amount required for the changed load, that is, the desired or target opening value, the opening and closing speed of the control valve can be lowered. In consequence, it is possible to reduce the undershooting of the control valve and, hence, it is possible to sufficiently prevent occurrence of a flameout in the combustor without causing a rise of the number of revolution of the gas turbine over a certain limit.
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A fuel supply amount is controlled while the load of a gas turbine is changed so that the fuel supply amount is shifted to a fuel supply amount in accordance with the changed load. A fuel supply control valve is operated at high speed during an initial stage and operated at a lower speed as the fuel supply amount necessary for the changed load is reached. Therefore flameout of a combustor is prevented without increasing the number of revolutions of the gas turbine over a certain upper limit.
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BACKGROUND OF THE INVENTION
The present invention concerns a process for tufting, and a device for implementing said process.
The technique of tufting, which is used in particular in the production of floor carpeting, consists of stitching needles linearly through a woven cloth, where said needles carry the thread, which is held by pivoting hooks during each stitch, and where said hooks and needles are situated on either side of the woven cloth. The cloth let-off operates continuously and regularly.
In the known devices, the needles and the hooks are placed in series in modules which together make up the needle frame and the hook frame respectively. In order to be able to form designs, the needle frame can move along its longitudinal axis with respect to the (transverse) direction of advance of the cloth, but the hook frame remains fixed.
The movement of the needle frame is limited, given that for each stitch every needle has to have a hook opposite it. The movement of the needle frame depends on the distance between two successive needles (known in the tufting technique as the gauge), and must correspond to one gauge or a multiple thereof.
This means that the only stitches possible with a needle frame are:
linear stitching, without movement of the needles;
zigzag stitching, with the needles being moved in steps of one gauge;
double zigzag stitching, provided that the machine is equipped with a second needle frame parallel to the first;
linear stitching with a to-and-fro movement of the cloth.
Another possibility is to change the pitch of the gauge, but changing from one gauge to another requires changing and adjusting the needle frames and hook frames. Furthermore, changing the gauge requires adjusting the controls, cams, hydraulics, etc. These adjustments are long and dull, so much so that tufting looms are generally left idle when the mill is not producing the gauge and height of tuft for which they are set.
The present invention has as its aim to offer a tufting process and a device for implementing said process which avoids the disadvantages mentioned.
Another aim of the invention is to offer a process and a device for implementing said process which enables a large number of designs to be made.
Yet another aim of the invention is to offer a tufting process which makes possible movements of the needles independently of the gauge.
SUMMARY OF THE INVENTION
According to a first characteristic of the process according to the invention, the hooks are moved in synchronization with the needles such that each needle forms a pair with its hook. The synchronous movement of a needle with its hook makes possible variable movements with a value independent of the gauge. Furthermore, each pair (needle-hook) can be permanently adjusted and set before the device is put into operation.
According to another characteristic of the invention, the woven cloth is let off at a variable speed, thus making possible variations in the designs. The cloth let-off is preferably stopped during the action of stitching. The cloth let-off can also be advantageously stopped during certain movements of the pairs (needles-hooks) in such a way that all the stitches in the same longitudinal plane (with reference to the transverse direction of advance of the cloth) can be carried out by the same pair.
The fact that each needle is always located opposite the same hook, whatever their position, makes possible long longitudinal displacements without limitations on the needles, which combined with the cloth stop or let-off control, gives greater possibility for transfer of colour or design. This technique makes it possible to "break" the effect of repetitive alignment of the carpet loops in the direction of the weft.
Numerous stitching possibilities become possible, including those which involve the needles and their respective hooks moving to the right or left in variable steps.
This advantage also enables the number of needles and hooks to be varied; many more designs with fewer pairs (needles-hooks) become possible. The distance between the needles can be chosen according to the size of the design, the required production and the rotation of the different qualities to be tufted.
For the same type of needle chosen, different designs can be programmed with different gauges and densities. Colour changes can be done using creels.
According to another characteristic of the invention, it is possible to use needles with a flat part, known as the blade, bearing the needle eye, with the needles mounted in modules where the longitudinal axis (of each needle) is turned so that the blade forms an angle with the plane vertical to the direction of the cloth let-off.
This angle is preferably between 15° and 45°. Further, the hooks are also mounted in modules so that the oscillating movement of each hook forms the same angle as that of the needle with which it is paired.
This characteristic enables the thread to be kept away from the point of the needle, so as to prevent stitching over it.
According to another characteristic of the invention, during stitching the cloth is let off in a vertical plane, and the needle frame and hook frame are placed in a horizontal plane on either side of the cloth.
As a result of the longitudinal positioning of the needles not being limited by the gauge, it is no longer possible to use a cloth support comb; however, its use is not necessary, since according to another characteristic of the invention, a smooth support and a continuous tensioner are used, enabling the stitching to be controlled without having to use a device similar to a predetermined gauge comb.
DESCRIPTION OF THE DRAWINGS
The invention is described below in detail with reference to drawings which represent the examples of embodiment, where
FIG. 1 is a schematic diagram of a tufting process
g to the state of the art;
FIG. 2 is a schematic diagram of a tufting process according to the invention;
FIG. 3 is a perspective view of the tufting zone in an example of embodiment of the invention;
FIG. 4 is a schematic vertical cross-section of the example in FIG. 3;
FIG. 5 is a plan view of an example of a device for synchronous positioning of the needle and hook frames;
FIG. 6 is a profile view of part of the device according to FIG. 5, showing the movement of the hooks.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows schematically the stitching system according to the state of the art, with a wovencloth (a) which is let off from a roll (b) and which is located in a horizontal plane (arrow c) below a frame (d) whose axis is perpendicular to the direction of let-off of the cloth (a). The frame (d) carries needles (e) according to a fixed gauge (f). Said frame (d) can move with a to-and-fro motion (arrow g) permitting a zig-zag pattern (h). The thread (i) is supplied from a battery of bobbins (not shown). The hooks, which are fixed-mounted on a hook frame, are located below the cloth and are not visible in the diagram. Since the tissue is let off in a regular fashion and the needles (a) can only move in steps of the gauge (f), because the hooks are fixed, and since the needles (e) must always be opposite a hook, the design cannot be in a line if th frame (d) does not move or in a zig-zag (h) if the needle frame (d) moves in gauge steps (f) with a to-and-fro motion (g).
FIG. 2 is a schematic diagram of the same type as FIG. 1, but according to the technique of the invention. A woven cloth 1 is let off in a vertical plane (arrow 13) between a frame 3 bearing needles 4 and a frame 10 bearing hooks 6 (FIG. 3). The needles 4 carrying the thread 11 are arranged in modules 8 on the frame 3, and similarly the hooks 6 are arranged in modules 9 on the frame 10.
According to a characteristic of the invention, the cloth 1 moves in a variable way so that the distance 15 between two neighboring stitches in a distinct horizontal plane is also variable, depending on the variation in movement of the cloth.
According to the invention, the hooks 6 move in synchronism with the needles 4, and there is no longer any reason to have uniform gauges; the distance 14 between two neighboring stitches in the same horizontal plane can therefore also be variable. The arrows 5 and 7 represent respectively the direction of stitching and the direction of horizontal positioning of the needles 4. From FIG. 2, it can clearly be seen that the design 2 obtained can be complex and have almost unlimited variation.
In the example shown in FIG. 3, the same elements as in FIG. 2 have the same reference numbers. This Figure shows the particular positioning of the needles 4 and the hooks 6. The needles 4 have a flattened part 21, called the blade, bearing the eye 22 through which passes the thread 11. The longitudinal axis of each needle is turned so that the blade 21 forms an angle 24 with the vertical plane 23 (in the direction of advance 13 of the cloth), where said angle is 30° in the example under consideration. The part of the hooks 6 which holds the thread 11 forms with the vertical plane 23 and an identical angle 24 of 30°, the represented in FIG. 3 by the plane 25. This plane 25 also illustrates the crossing angle of the needle with its hook. The arrow 26 represents the movement of the hooks 6. The spacing 12 between two neighboring hooks (and two neighboring needles) is not fixed and can have multiple gauges. The element 27 constitutes the structure for supporting the tissue. Together with the tension roller 28 and the cloth pressing element 29 (FIG. 4) it forms the device for keeping the woven cloth 1 under continuous tension.
FIG. 4 shows an example of let-off of the woven cloth 1. The cloth comes from a storage roller, passes a delivering cylinder 31 driven by a stepper motor 32 which drives the cloth let-off and which is equipped with an electromechanical locking system 33 for stopping the cloth. This system 32-33 enables the woven cloth to be stopped during stitches, and enables the let-off to be controlled with variable steps. The cloth 1 is tension in the stitching zone by means of the tension cylinder 28 driven by a continuous tensioning motor 34 equipped with an electromagnetic clutch 35 for regulating the tension. In the stitching zone the cloth passes the support structure 27 and the cloth pressing element 29.
A conventional, digital electronic apparatus for controlling the machine is used for general control of the loom. Said apparatus must enable the frames to be positioned longitudinally, and must enable the cloth let-off to be controlled at a speed such that stitching can be carried out at, for example, 600-700 stitches per minute. It also controls the automatic settings of the different tufting parameters: needle travel, loop height, thread delivery, thread tension and cloth tension. This conventional electronic apparatus is known to persons versed in the art, and its embodiment does not come within the scope of the invention.
An example of longitudinal guiding of the needle frame and the hook frame is shown in FIG. 4 by references 38 and 39, respectively, and is described in greater detail below.
The arrangement of the different elements and in particular the vertical let-off of the cloth makes it possible for the bobbins of thread (11) to be accommodated in the base of the machine, which is not possible with a horizontal cloth let-off. The important elements, such as needles and hooks, are thereby made more accessible, and ht machine is easier to control.
FIGS. 5 and 6, which describe an example of positioning of the needle and hook frames and of their movement, shows a stepper drive motor 51 which turns a worn 52 bearing a nut 53, linked by a pivot-pin rod 54 to the yoke 55 which is linked to the frame 3 bearing the needles 4 by means of a guide connector 56 and which is linked to the frame 10 bearing the hooks 6 by means of a guide connector 57. The guiding of the movement of the needles 4 is shown schematically by the broken line 58, while reference 59 indicates the plane of the woven cloth 1.
FIG. 6 shows schematically the movement 69 of the hooks 6. This movement is controlled by a twin cam 61 which turns (arrow 62) and rocks (arrow 63) a rocker 63 by means of rollers 64 pressing against its smooth outline. This movement 70 is transmitted by the connecting rod 66 to intermediate rockers 67 (two of which are shown) whose movement 71 determines the guiding 68 of the movement 69 of the hooks 6. The longitudinal guiding of the hook frame 10 is shown by reference 39, and the longitudinal guiding of the needle frame 3 is shown in FIG. 4 by reference 38. The device enables the frames 3 and 10 to be positioned with an accuracy of less than 0.1 mm.
It is clear that the invention is in no way limited to the embodiment described in the example and in the Figures. It is up to persons versed in the art to use the known mechanism to, for example, achieve the synchronism of movement between the needle modules and hook modules, sinc this movement can be obtained in many ways. Similarly, there are many possibilities for regulating and controlling the irregular cloth let-off. The combination of variable cloth let-off with the movement of needle and hook frames also falls within the field of conventional mechanics and electronics.
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The process consists of a cloth being let off at a variable speed between each stitch or to maintain the cloth in a fixed position, the hooks being moved in synchronism with the needles. The device consists of a frame bearing needles, a frame bearing hooks, a variable speed motor for letting off a woven cloth, a motor and linkage for stitching the needles bearing the thread through the cloth, and a cam and connected rockers for holding the thread which passes through the cloth, a stepper motor for letting off the cloth at a variable speed, and a motor and gear for moving the hook frame in synchronism with the needle frame.
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CROSS REFERENCE TO OTHER RELATED APPLICATIONS
[0001] This application claims priority from U.S. Provisional Application No. 60/271,413 filed on Feb. 27, 2001.
FIELD OF THE INVENTION
[0002] The invention relates in general to a polarization-maintaining optical fiber amplifier that is fabricated from non-polarization-maintaining gain optical fiber. More specifically, the invention employs coiling under tension to create a stress-induced axis of linear birefringence within the fiber.
BACKGROUND OF THE INVENTION
[0003] A wide variety of applications in fiber optic photonics require the use of polarization-maintaining optical fibers. In such a fiber the polarization planes of linearly polarized light waves launched into the optical fiber are maintained during propagation with little or no cross coupling of optical power between the orthogonal polarization modes. In many of these systems there is also a need for polarization-maintaining optical fiber amplifiers. An optical fiber amplifier is a device that amplifies an optical signal directly, i.e., without the need to convert it to an electrical signal, amplify it electrically, and reconvert it to an optical signal.
[0004] An optical fiber amplifier uses an optical fiber having a rare-earth-doped core, which will be referred to hereinafter as a gain optical fiber. Although Er 3+ is most commonly used as a rare-earth element in gain optical fibers, different rare earth elements such as Nd 3+ , Yb 3+ , Pr 3+ , Ho 3+ , Sm 3+ , and Tm 3+ may be used. The rare-earth ion is optically excited, typically but not exclusively using the output of a diode laser; a signal beam propagating in the core experiences gain if a population inversion has been established by absorption of the pump beam by the rare-earth ions (and if the signal beam has a wavelength within the gain spectrum of the rare-earth dopant).
[0005] Optical fiber amplifiers generally out-perform conventional solid-state amplifiers in the following key areas: small-signal gain, tunability, beam quality (for single-mode optical fibers), immunity to mechanical and thermal disturbances, size, weight, cost, and electrical efficiency. One notable disadvantage of optical fiber amplifiers is their tendency to scramble the input polarization of the seed signal. This polarization-scrambling effect is a consequence of azimuthal asymmetry in the refractive-index distribution of the optical fiber, commonly referred to as optical fiber birefringence. A linearly polarized seed signal injected into the fiber will generally be converted to an unspecified, time-dependent elliptical polarization state, i.e., the fiber is not polarization maintaining.
[0006] In an ideal optical fiber having an azimuthally symmetric refractive-index profile, a signal injected into one end of the fiber will propagate through the optical fiber with its polarization state unchanged. Each of the transverse modes supported by the optical fiber waveguide can exist in two orthogonal polarizations (e.g., vertical and horizontal), and in a perfectly symmetric optical fiber these two polarization modes propagate at the same speed, independent of one another (i.e., the fiber is not birefringent). In practice, it is impossible to manufacture an optical fiber that has perfect azimuthal symmetry, and all real optical fibers thus exhibit non-zero birefringence. Core or cladding ellipticity and mechanical strain, which causes random refractive-index perturbations, are the main contributors to random birefringence in an optical fiber and thus to non-polarization-maintaining behavior.
[0007] There are several solutions for the problem of polarization scrambling due to random birefringence in an optical fiber. As described below, random birefringence may be corrected by utilizing a polarization controller, a Faraday mirror, or a polarization-maintaining optical fiber.
[0008] The simplest solution to the problem of polarization scrambling due to optical fiber birefringence is the use of a polarization controller. There are a number of different designs for polarization controllers, but in all cases the principle of operation is the same. The birefringent optical fiber is sandwiched between two waveplates whose orientation and retardation are independently adjustable; alternatively the fiber input or output beam may be directed through three waveplates whose orientations but not retardations are adjustable. It can be shown that for any fiber birefringence, it is always possible to set the adjustable waveplates such that there is no change in the polarization state for a signal passing through the entire system (fiber plus polarization controller). Unfortunately, the birefringence properties of the optical fiber are sensitive to environmental factors, such as changes in temperature or mechanical disturbances. Changes in the birefringence properties of the optical fiber over time necessitate readjustment of the polarization controller, making it unsuitable for most real-world applications.
[0009] In some optical fiber circuits, a device known as a Faraday mirror can be used to compensate for optical fiber birefringence. In a Faraday mirror, a signal passing through the birefringent optical fiber must retrace it's path through the optical fiber, traveling in the opposite direction on the return trip, thereby creating a folded optical path. The Faraday mirror never needs adjustment and is able to compensate for rapid changes in birefringence, limited only by the round-trip propagation in the fiber. The main disadvantage of the Faraday mirror is that it is applicable to only a small subset of optical fiber circuits and is therefore lacking in generality. In addition, commercially available Faraday mirrors suffer from one or more the following drawbacks: high cost, large size and weight, limited power-handling capability, and limited wavelength range (i.e., a wavelength range smaller than the range over which the fiber exhibits gain).
[0010] The best all-around solution to the problem of optical fiber birefringence is the use of a polarization-maintaining (PM) optical fiber. In a PM optical fiber, a very large azimuthal asymmetry is introduced intentionally during the manufacturing process. The goal is to create a controlled linear birefringence that is very large (compared with the random birefringence) and oriented along a well-defined axis. This birefringence can be generated by fabricating an optical fiber core with an elliptical cross-section, by subjecting an optical fiber to mechanical stress, or by a combination of both techniques. When this linear birefringence is much greater than the random birefringence due to optical fiber imperfections, good PM behavior is obtained.
[0011] FIGS. 1 - 4 show cross-sections of various conventional PM optical fibers 10 , looking down the optical fiber axes. The components of the PM optical fibers may include a core 20 , a cladding 22 , and stress elements 24 .
[0012] The stress elements 24 shown in FIGS. 1 - 3 for the bow-tie 12 , Panda 14 , and oval-inner-clad 16 PM optical fibers are fabricated from a glass whose thermal expansion coefficient is different (usually greater) than that of the cladding 22 glass, which is usually silica. During manufacture, the optical fiber 10 is drawn from molten glass and therefore starts out stress-free. Solidification occurs several hundred degrees above room temperature, at which point the optical fiber 10 is capable of accumulating mechanical stress. As the optical fiber 10 cools further, the stress elements 24 contract differently (usually more) than the surrounding cladding, generating a stress field that is azimuthally asymmetric. Specifically, the stress distribution has two-fold bilateral symmetry, in which the mirror planes of minimum and maximum stress are perpendicular to each other. The stress-induced change in the refractive index has these same symmetry properties. Within each PM optical fiber 10 there is thus a fast axis 26 and a slow axis 28 that are mutually perpendicular (analogous to a waveplate). Because of the difference in index of refraction, a ray of light whose polarization direction is aligned along the fast axis propagates at a slightly faster speed than a ray of light whose polarization direction is aligned along the slow axis.
[0013] If linearly polarized light is injected into a PM optical fiber with its polarization direction aligned parallel to either the fast or slow axis of linear birefringence, no polarization scrambling is observed. There are three factors that determine how well such an optical fiber will preserve polarization in practice: the amount of stress-induced linear birefringence, the amount of random birefringence due to fiber imperfections, and the length of fiber. As mentioned earlier, good PM behavior is obtained if the induced linear birefringence is made much greater than the random birefringence due to optical fiber imperfections. In a well-designed PM fiber, random birefringence is thus kept to a minimum while the linear birefringence is made as large possible. A typical value for commercially available PM optical fiber is Δn=2×10 −4 , where Δn is the difference between the refractive indices of the fast and slow axes.
[0014] There has been very little progress in the area of optical fiber amplifiers based on PM rare-earth-doped gain optical fiber. The existing methods for gain optical fiber fabrication include modified chemical vapor deposition and solution doping, and these methods are generally incapable of producing optical fiber preforms with anything other than an azimuthally symmetric distribution of constituents. The incorporation of stress rods, for example, is not straightforward. At present there is only one rare-earth-doped PM gain optical fiber that is commercially available, an Er-doped gain optical fiber manufactured by Fibercore Ltd. (UK).
[0015] The Fibercore Er-doped gain optical fiber is not appropriate for the construction of high-power optical fiber amplifiers because it is single-clad and can thus be efficiently pumped only with single-mode pump sources. Single-mode pump sources for single-clad gain optical fiber are costly and provide relatively low pump powers (about $3000 for a 0.1 W pump source). It is therefore preferable to use a cladding-pumped amplifier with a double-clad gain optical fiber. The advantage of using double-clad gain optical fiber is that low-brightness, broad-area (multimode), laser diode pump sources can be efficiently coupled into the inner cladding. These multimode sources offer much higher power at much lower cost (less than $300 per Watt of pump power) than single-mode pump sources. In addition, the optics used to couple pump light into the double-clad gain optical fiber is much less sensitive to misalignment by mechanical disturbances or fluctuations in ambient temperature. This combination of properties makes double-clad gain optical fibers well suited to a wide variety of optical fiber amplifier applications. Unfortunately, PM gain optical fibers incorporating rare-earth dopants other than Er 3+ and double-clad PM gain optical fibers are not commercially available. A PM, Yb-doped, double-clad optical fiber was recently demonstrated, but this fiber is not yet available commercially.
[0016] It would therefore be desirable to provide a PM optical fiber amplifier that uses non-polarization-maintaining gain optical fiber, which is widely available.
SUMMARY OF THE INVENTION
[0017] These and other objects of the invention are achieved in a preferred method of the invention.
[0018] An aspect of the present invention is a method of forming a linear polarization-maintaining optical fiber for use in an amplifier, the method comprising the steps of: providing a rare-earth-doped non-polarization-maintaining optical fiber having one or more cladding layers and having a random birefringence; providing a mandrel having a selected diameter; coiling the non-polarization-maintaining optical fiber under a selected tension around the mandrel to induce a linear birefringence greater than the random birefringence in the non-polarization-maintaining optical fiber thereby forming a polarization-maintaining optical fiber; wherein the mandrel diameter is chosen to avoid significant bend loss; wherein the rare-earth dopant is selected from the group consisting Nd 3+ , Yb 3+ , Pr 3+ , Ho 3+ , Er 3+ , Sm 3+ and Tm 3+ ; wherein the mandrel diameter is selected to be from about 0.1 cm to about 10 cm; and wherein the tension is chosen to avoid undesirable weakening of the non-polarization-maintaining fiber.
[0019] Another aspect of the present invention is an optical amplifier with a rare-earth-doped polarization-maintaining optical fiber, the amplifier comprising: a mandrel having a selected diameter; a rare-earth-doped polarization-maintaining optical fiber having one or more cladding layers and having linear birefringence greater than a random birefringence; and a pump source which is coupled to the optical fiber; wherein the rare-earth-doped polarization-maintaining optical fiber is coiled around the mandrel under tension; wherein the mandrel diameter is chosen to avoid significant bend loss; wherein the rare-earth dopant is selected from the group consisting Nd 3+ , Yb 3+ , Pr 3+ , Ho 3+ , Er 3+ , Sm 3+ and Tm 3+ ; wherein the mandrel diameter is selected to be from about 0.1 cm to about 10 cm; and wherein the tension is chosen to avoid undesirable weakening of the polarization-maintaining fiber.
[0020] A further aspect of the present is a method of forming a linear polarization-maintaining optical fiber amplifier, the method comprising the steps of: providing a rare-earth-doped non-polarization-maintaining optical fiber having one or more cladding layers and having a random birefringence; providing a mandrel having a selected diameter; coiling the non-polarization-maintaining optical fiber under a selected tension around the mandrel to induce a linear birefringence greater than the random birefringence in the non-polarization-maintaining optical fiber thereby forming a polarization-maintaining optical fiber; and coupling a pump source to polarization-maintaining optical fiber; wherein the mandrel diameter is chosen to avoid significant bend loss; wherein the rare-earth dopant is selected from the group consisting Nd 3+ , Yb 3+ , Pr 3+ , Er 3+ , Sm 3+ , Ho 3+ and Tm 3+ ; wherein the mandrel diameter is selected to be from about 0.1 cm to about 10 cm; and wherein the tension is chosen to avoid undesirable weakening of the non-polarization maintaining fiber.
[0021] A further aspect of the present invention is an optical amplifier with a rare-earth-doped polarization-maintaining optical fiber, the amplifier comprising: a mandrel having a selected diameter; a rare-earth-doped polarization-maintaining optical fiber having one or more cladding layers and having linear birefringence greater than a random birefringence; and a pump signal source which is coupled to the optical fiber; wherein the rare-earth-doped polarization-maintaining optical fiber is coiled around the mandrel; wherein the mandrel diameter is chosen to avoid significant bend loss; wherein the rare-earth dopant is selected from the group consisting Nd 3+ , Yb 3+ , Pr 3+ , Ho 3+ , Er 3+ , Sm 3+ and Tm 3+ ; wherein the mandrel diameter is selected to be from about 0.1 cm to about 10 cm; and wherein the diameter of said polarization-maintaining optical fiber is from about 50 μm to about 1000 μm.
[0022] Another aspect of the present invention is a method of forming a linear polarization-maintaining optical fiber for use in an amplifier, the method comprising the steps of: providing a rare-earth-doped non-polarization-maintaining optical fiber having one or more cladding layers, a diameter and a random birefringence; providing a mandrel having a selected diameter; coiling the non-polarization-maintaining optical fiber around the mandrel to induce a linear birefringence greater than the random birefringence in the non-polarization-maintaining optical fiber thereby forming a polarization-maintaining optical fiber; wherein the mandrel diameter is chosen to avoid significant bend loss; wherein the rare-earth dopant is selected from the group consisting Nd 3+ , Yb 3+ , Pr 3+ , Ho 3+ , Er 3+ , Sm 3+ and Tm 3+ ; wherein the mandrel diameter is selected to be from about 0.1 cm to about 10 cm; and wherein the diameter of the non-polarization-maintaining optical fiber is from about 50 μm to about 1000 μm.
[0023] A further aspect of the present invention is a method of forming a linear polarization-maintaining optical amplifier for use in an amplifier, the method comprising the steps of: providing a rare-earth-doped non-polarization-maintaining optical fiber having one or more cladding layers, a diameter and a random birefringence; providing a mandrel having a selected diameter; coiling the non-polarization-maintaining optical fiber under a selected tension around the mandrel to induce a linear birefringence greater than the random birefringence in the non-polarization-maintaining optical fiber thereby forming a polarization-maintaining optical fiber; coupling a pump source to polarization-maintaining optical fiber; wherein the mandrel diameter is chosen to avoid significant bend loss; wherein the rare-earth dopant is selected from the group consisting Nd 3+ , Yb 3+ , Pr 3+ , Er 3+ , Sm 3+ , Ho 3+ and Tm 3+ ; wherein the mandrel diameter is selected to be from about 0.1 cm to about 10 cm; and wherein the non-polarization-maintaining optical fiber diameter is from about 50 μm to about 1000 μm.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] These and other objects, features and advantages of the invention, as well as the invention itself, will become better understood by reference to the following detailed description when considered in connection with the accompanying drawings wherein like reference numbers designated identical or corresponding parts throughout the several views, and wherein:
[0025] [0025]FIG. 1 illustrates a cross section of PM optical fiber with bow-tie stress elements;
[0026] [0026]FIG. 2 illustrates a cross section of PM optical fiber with round stress elements (a Panda fiber);
[0027] [0027]FIG. 3 illustrates a cross section of PM optical fiber with an oval-inner-cladding stress element;
[0028] [0028]FIG. 4 illustrates a cross section of PM optical fiber with an oval core;
[0029] [0029]FIG. 5 illustrates a PM optical fiber amplifier in accordance with the present invention;
[0030] [0030]FIG. 6 is a graph of applied tensile stress (GPa) vs. optical fiber time to failure (sec);
[0031] [0031]FIG. 7 is a graph of relative transmitted power (dB) vs. polarizer angle (degrees), which demonstrates the polarization extinction ratio measurement for the amplifier;
[0032] [0032]FIG. 8 is a graph of output power (mW) and extinction ratio (dB) vs. pump power (W); and
[0033] [0033]FIG. 9 is a graph of output power (dBm/nm) vs. wavelength (nm).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0034] [0034]FIG. 5 illustrates a polarization-maintaining (PM) optical fiber amplifier 30 in accordance with a preferred embodiment of the invention. The PM optical fiber amplifier 30 is constructed with a non-polarization-maintaining gain optical fiber 32 that is preferably coiled under tension around a spool 34 and thereby becomes PM optical fiber 50 . The spool 34 is any solid or hollow cylindrical object that is composed of a suitable material and that may be used to support the tension-coiled gain optical fiber 32 . The PM gain optical fiber 50 has an input end 36 and an output end 38 , which are spliced 40 to PM non-gain (passive) optical fiber pigtails 42 . To splice PM optical fibers 50 to 42 , it is important that the axes of birefringence for the two optical fibers be aligned to within plus or minus a few degrees. For this reason, a gain optical fiber with a square or rectangular cross section is ideal for fabrication of PM amplifiers based on stress-induced birefringence, because the axes of birefringence are constrained to run parallel to the edges of the square or rectangle and are therefore easily identified on an optical fiber splicing machine. However, other commercially available optical fiber cross-sections may also be used, including round, hexagonal, etc.
[0035] The seed signal that is to be amplified is introduced into the amplifier with a seed signal source 44 , which is optically directed through an optical isolator and a polarizer 46 to generate a polarized seed signal. The output of an optical pump source 48 is also introduced into the optical fiber.
[0036] The non-PM gain optical fiber 32 is coiled under tension around the spool 34 , resulting in stress-induced linear birefringence. The spool diameter, d spool , and tension induced axial strain, ε, are chosen to provide sufficient birefringence for PM operation without introducing significant bend loss. Bend loss occurs in an optical fiber when the optical fiber is curved to a diameter that is so small that light is no longer well guided within the fiber core.
[0037] Equations for the stress-induced birefringence of a tension-coiled single-mode optical fiber are presented in an article by S. C. Rashleigh and R. Ulrich, High birefringence in tension-coiled single-mode fibres, Opt. Lett., Vol. 5, No. 8, pg. 354 (1980). Stress-induced birefringence for a tension-coiled optical fiber may be much larger than that resulting when the optical fiber is bent without tension, and the resulting birefringence is given by:
β tc , slab = π n 3 ɛ d fiber λ d spool ( p 11 - p 12 ) ( 1 + v )
[0038] for a slab geometry, while the corresponding expression for a fiber of circular cross section is given by:
β tc , circ = π n 3 ɛ d fiber λ d spool ( p 11 - p 12 ) ( 1 + v ) ( 2 - 3 v 1 - v ) .
[0039] In these equations, n is the refractive index for fused silica (dimensionless), p 11 and p 12 represents strain-optic tensor components for fused silica (dimensionless), ν is Poisson's ratio for fused silica (dimensionless), d fiber is the diameter of the optical fiber 32 in the plane of curvature of the optical fiber coil (m), d spool is the diameter of the spool 34 around which the optical fiber is coiled (m), ε is the axial strain applied to the optical fiber (dimensionless), and λ is the free-space wavelength of a signal propagating in the gain optical fiber (m). The birefringence (β tc ) has units of radians/m.
[0040] The equation for β tc, circ , the birefringence induced by coiling under tension, may be compared with the birefringence induced by bending an optical fiber having a circular cross section without any tension, β bend, circ , which is also disclosed in the above referenced article by S. C. Rashleigh and R. Ulrich:
β bend , circ = π n 3 d fiber 2 2 λ d spool 2 ( p 11 - p 12 ) ( 1 + v ) .
[0041] Note that β tc, circ and β bend, circ are additive, with the fast axis of linear birefringence of the optical fiber lying in the plane of curvature of the optical fiber core.
[0042] Referring back to the above equation for the birefringence of the tension-coiled optical fiber, to maximize the stress-induced birefringence, the diameter of the gain optical fiber 32 and the tension should be made as large as possible, and the diameter of the spool 34 should be made as small as possible.
[0043] For a standard single-clad optical fiber d fiber =125 μm. For a typical double-clad optical fiber d fiber is usually between 100 μm and 500 μm. In the case of a single-clad optical fiber, the diameter of the silica cladding can be increased arbitrarily without affecting the properties of the waveguide region and is limited only by optical fiber stiffness above ˜500 μm. For the double-clad optical fiber the choice of d fiber is somewhat constrained by the need for efficient pump absorption.
[0044] The maximum tension induced axial strain, ε, that can be applied to the gain optical fiber 32 requires careful consideration. FIG. 6 is a graph of optical fiber lifetime as a function of tensile stress. As shown in FIG. 6, with increasing tension the mean time to fiber failure decreases dramatically. To be conservative, ε*0.010 (1.0% strain) may be used as an upper limit, corresponding to an applied stress of about 0.72 GPa in FIG. 6. This upper limit may be applied to all types of high-quality optical fiber. Fiber failure can also be caused by bending-induced stress for small spool diameters, but this limitation is not significant relative to the above considerations.
[0045] If the spool 34 diameter, d spool , is too small the gain optical fiber 32 will no longer function as a waveguide due to bend loss. The numerical aperture (NA) of the optical fiber determines its sensitivity to bend loss, and fibers with high NA are preferable for attaining maximum birefringence. (NA=sin α, where α is the acceptance half-angle of the optical fiber, and an incoming ray of light that lies outside of the acceptance cone of the optical fiber is not guided by the core.)
EXAMPLE
[0046] In this example, a PM optical fiber amplifier 30 was constructed in accordance with the invention using 5 m of an Er/Yb-doped double-clad non-PM gain optical fiber 32 (manufactured by Lucent Technologies). The fiber was side-pumped using a laser diode 48 . The gain optical fiber 32 had a hexagonal-shaped inner cladding with a diameter of 126 μm, measured from flat surface to flat surface. The NA of the gain optical fiber 32 was 0.16, which is typical for a telecommunications optical fiber, and this permitted a spool 34 diameter of 15 mm to be used.
[0047] The gain optical fiber 32 was wound around the spool 34 under 66 kg/m 2 of tension using a free-hanging weight, which corresponds to ε=0.91% strain along the length of the gain optical fiber 32 . Because the cross-section of the gain optical fiber 32 was hexagonal, it laid flat on the spool in one of six identical angular orientations. The hanging weight was free to rotate, so the gain optical fiber 32 wound onto the spool 34 without twisting. After winding, the gain optical fiber 32 was secured with a removable adhesive and spliced on both ends to 1 meter long PM non-gain (passive) optical fiber pigtails 42 . The length of non-PM gain optical fiber running from the spool 34 to the PM pigtail 42 was made as short as possible (about 10 cm) to minimize polarization scrambling.
[0048] To accomplish splicing 40 between the gain optical fiber 32 and the PM pigtails 42 , the hexagonal gain optical fiber 32 was secured in the chuck of an optical fiber splicing machine without introducing any twists, so that the orientation of the axes of linear birefringence could be referenced to that of the spool 34 .
[0049] A V-groove side pumping technique was used to couple light from a single-stripe laser diode into the inner cladding of the double-clad optical fiber, as disclosed in an article by L. Goldberg et al., V-groove side-pumped 1.5 μm fiber amplifier, Electron. Lett., Vol. 33, No. 25, pg. 2127 (1997); however any alternative pumping scheme may be used. As shown in FIG. 5, the pump signal source 48 , including the V-groove and its associated hardware, were located near one of gain optical fiber 40 .
[0050] The calculated birefringence for this system was β=β tc, slab +β bend, circ =95 rad/m+40 rad/m=135 rad/m. The actual birefringence was measured in the laboratory to be 110 rad/m using the broadband measurement technique described in an article by S. C. Rashleigh et al., Polarization holding in birefringent single-mode fibers, Opt. Lett., Vol. 7, No. 1, pg. 40 (1982). The discrepancy between the calculated and experimental values for β may be attributed to one or more of the following factors. The slab geometry used to calculate β γ applies only approximately to the hexagonal gain optical fiber, because each hexagonal face is concave rather than flat. Similarly, the cylindrical geometry used to calculate β bend applies only approximately to the hexagonal optical fiber. The distribution of tensile force between the optical fiber and the mandrel is altered somewhat by the presence of the optical fiber jacket. The optical fiber jacket material may be subject to creepage under strain, in which case the initial value for β would be expected to decrease somewhat after winding under tension. In light of these considerations, the agreement between the measured and calculated values of the birefringence is good.
[0051] The optical fiber amplifier was seeded by a linearly polarized amplified spontaneous emission source whose broadband output covered the 1530-1570 nm range. The PM optical fiber amplifier 30 had an output power in excess of 500 mW. FIGS. 7 - 9 summarize the results obtained with the above PM optical fiber amplifier. FIG. 7 is a graph of relative transmitted power (dB) vs. polarizer angle (θ), which demonstrates the polarization extinction ratio measurement for the amplifier. The data in FIG. 7 were recorded by passing the output of the optical fiber amplifier through a high-extinction-ratio polarizer. The angular orientation (θ) of the polarizer was varied from 0 to 270 degrees, showing the expected Sin 2 θ dependence for transmitted intensity. A polarization extinction ratio of 50:1 (17 dB) was obtained. It is likely that the actual extinction ratio was somewhat greater than indicated by the data in FIG. 7 because, in addition to amplified signal, spontaneous emissions and amplified spontaneous emission were present at the output of the amplifier.
[0052] [0052]FIG. 8 is a graph of output power (mW) and extinction ratio (dB) vs. pump power (W). FIG. 8 demonstrates that the polarization extinction ratio was independent of pump power. The wavelength distribution of the seed signal and the amplified output are shown in FIG. 9; winding the gain optical fiber 32 under tension in accordance with the present invention did not impair the performance of the amplifier from the standpoint of spectral coverage, gain, efficiency, etc.
[0053] In summary, the present invention provides a straightforward and flexible approach to the fabrication of PM optical fiber amplifiers and offers the following important advantages: (1) System complexity is not increased, as no additional components are inserted in the optical path. (2) The optical fiber ends are left unobstructed. (3) PM capability can be added without disturbing the design or performance characteristics of an existing optical fiber amplifier system (because addition of additional optics or reconfiguration of existing optics is not required). (4) The method can be applied to many non-PM gain optical fibers, both single- and double-clad. The exceptions are likely to be optical fibers with very low NA's or optical fibers of poor quality (intrinsically high random birefringence). (5) The technique is achromatic (6) It is compatible with single- or multiple-pass operation of the amplifier. (7) The required capital investment is negligible. The optical fiber winding apparatus is simple to construct and costs approximately $300 (in comparison, the cost of one optical fiber fabrication run is at least $20,000).
[0054] The invention has been described with reference to certain preferred embodiments thereof. It will be understood, however, that modification and variations are possible within the scope of the appended claims. For example, this technique may also be implemented using multimode gain optical fibers, which are of interest for applications that require very high average and/or peak powers. In addition, for certain high-NA optical fibers, typically a NA greater than 0.15 and depends on the d fiber , it may be possible to achieve adequate birefringence without winding the optical fiber under tension; if the spool diameter is small enough, bending stress alone may introduce sufficient linear birefringence for PM operation (see equation for β bend ).
[0055] Therefore, what has been described above is a method, which utilizes a mandrel having a selected diameter and tension or utilizes a mandrel having a selected diameter without tension for optical fiber having a high NA for fabricating a polarization-maintaining optical fiber for use in an amplifier.
[0056] It should therefore readily be understood that many modifications and variations of the present invention are possible within the purview of the claimed invention.
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A method of forming a linear polarization-maintaining optical fiber for use in an amplifier, the method comprising the steps of:
providing a rare-earth-doped non-polarization-maintaining optical fiber having one or more cladding layers and having a random birefringence;
providing a mandrel having a selected diameter;
coiling said non-polarization-maintaining optical fiber under a selected tension around said mandrel to induce a linear birefringence greater than said random birefringence in said non-polarization-maintaining optical fiber thereby forming a polarization-maintaining optical fiber;
wherein said mandrel diameter is chosen to avoid significant bend loss;
wherein said rare-earth dopant is selected from the group consisting Nd 3+ , Yb 3+ , Pr 3+ , Ho 3+ , Er 3+ , Sm 3+ and Tm 3+ ;
wherein said mandrel diameter is selected to be from about 0.1 cm to about 10 cm; and
wherein said tension is chosen to avoid undesirable weakening of said non-polarization-maintaining fiber.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a telecommunication system, comprising a bus conductor and a plurality of telecommunication stations each connected via a transformer to the bus conductor, in which system communication takes place by means of a pulse signal containing successive voltage pulses of opposite polarity to be transferred via the bus conductor.
The invention likewise relates to a telecommunication station suitable for use in such a telecommunication system.
2. Description of the Related Art
Such a telecommunication system is known from the journal "Electronic Design" of July 26, 1984, pp. 171-178, more specifically the FIGS. 1 and 3.
In such a system the telecommunication stations comprise an information transmitter and an information receiver. When transmitting a binary signal the transmitter does so by sending in a time slot of a time frame a voltage pulse onto the bus conductor, representing a first bit type, or by not transmitting a pulse, representing a second bit type. The receivers of the telecommunication stations detect in each time slot the voltage condition of the bus conductor. A receiver detects a bit of the first type if the absolute value of the detected voltage exceeds the predetermined threshold value; the receiver detects a bit of the second bit type if the absolute value of the detected voltage is lower than the threshold value.
When using a telecommunication system of the aforementioned type faulty detection will occasionally take place. More specifically, voltage pulses can be detected in time slots in which no voltage pulses have been transmitted.
SUMMARY OF THE INVENTION
The invention has for its object to provide such a telecommunication system in which the number of erroneously detected pulses can be reduced.
To realize the aforementioned object the telecommunication system in accordance with the invention is characterized in that the system comprises compensating means for producing compensating current in at least one winding of at least one bus-connected transformer for keeping the algebraic sum of the magnetizations of the transformer cores substantially unchanged at the instants of pulse termination.
The invention is based on the inventive understanding that faulty detection of voltage pulses in time slots wherein no pulse has actually been transmitted is caused by the non-ideal behaviour of the transformers which are connected to the bus conductor. Since a non-ideal transformer has a non-infinite self-inductance which will henceforth be designated as spurious self-inductance, energy is stored during the voltage pulse as a consequence of the magnetizing current. After the voltage pulse has finished, this magnetizing current causes to arise across the bus impedance a faulty voltage whose polarity is opposite to that of the preceding voltage pulse. In succeeding time slots the bus-connected receivers detect this faulty voltage, which if of sufficient pulse height will erroneously be interpreted as a voltage pulse.
The compensating current can be produced in one or more arbitrary windings of the connected transformers. It is possible to connect for that purpose a separate transformer comprising compensating means, or to bring about this compensating current change in a winding of the transformer of the transmitting station.
An advantageous embodiment of the telecommunication system in accordance with the invention in which the total magnetization can be kept unchanged whilst neglecting the delays on the bus conductor, is characterized in that each telecommunication station of the system comprises an individual compensating current-source supplying a compensating current to a winding of the transformer of the relevant station, which compensating current changes at the pulse terminating instants keep the magnetization of the relevant transformer core substantially unchanged at these instants.
In this embodiment the faulty voltage is compensated for in each telecommunication station the moment when the voltage pulse is terminated at the relevant station.
A further embodiment of the telecommunication system in accordance with the invention, which allows for the change of the amplitude of the voltage pulse as a result of line attenuation and other influences during the change of compensating current, is characterized in that the compensating means comprise an integrating sample-and-hold circuit for establishing the pulse voltage on the bus conductor at the relevant station. The individual compensating current-source can be controlled via a control input connected to the integrating sample-and-hold circuit for bringing about a current change directly proportional to the pulse voltage.
The value of the magnetizing current as a result of the spurious self-inductance is equal to the product of the pulse height and the pulse duration divided by the value of the spurious self-inductance. The pulse duration and the spurious self-inductance being accurately known and constant, the value of the magnetizing current can be accurately determined by measuring the pulse height. If necessary, this value can be converted to that transformer winding in which the compensating current change is introduced. The latter quantity should then be equal to the converted magnetizing current.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention and its advantages are described with reference to the following figures, with the same reference numerals indicating the same elements, in which:
FIG. 1 shows a known telecommunication system comprising a bus to which a plurality of stations is connected;
FIG. 2 shows a graphical representation of the pulse voltage on the bus conductor, the magnetizing current in a transformer and a compensating current;
FIG. 3 shows two embodiments of the compensating arrangement in a station;
FIG. 4 shows an embodiment of an integrating sample-and-hold circuit, to be used as a voltage source for compensating current;
FIG. 5 shows a graphical representation of the course of the pulse voltage on the bus conductor, the associated course of the magnetizing current and the course of the associated compensating current as generated in one of the circuits in accordance with FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a telecommunication system known per se in which the invention can be implemented. This system comprises a two-wire bus, terminated on either end, by characteristic impedances 2-1 and 2-2. A plurality N of telecommunication stations (terminals) 4-1 to 4-N is connected to bus 2. Of these terminals only 4-1 is shown in a detailed diagram, the remaining terminals are shown symbolically by their spurious self-inductances 6-2 to 6-N. Also transformer 8 of terminal 4-1 shows a spurious self-inductance 6-1. Terminal 4-1 further comprises a pulse transmitter for transmitting pulse signals onto the bus. This transmitter is shown schematically as a source of constant voltage 10 having an internal resistor 12 connected to the circuitsided winding 16 of the transformer 8 via a pulse switch 14. Terminal 4-1 further comprises a receiver 20 for receiving pulse signals transmitted onto the bus. Despite the fact that in principle all terminals are capable of both transmitting and receiving, it will be assumed that terminal 4-1 is the transmitting terminal and the remaining terminals 4-2 to 4-N are the receiving terminals.
FIG. 2 shows in the two upper graphs the course of the pulse voltage and the magnetizing current, the broken lines representing the course of these quantities which would occur if a compensating current were absent.
The top graph of FIG. 2 shows the course of the voltage on the bus if switch 14 is conductive for a pulse duration T. During the pulse in all spurious self-inductances 6-1 to 6-N a magnetizing current is generated whose final value per terminal is equal to the product of the pulse voltage V and the pulse duration T divided by the spurious selfinductance L. Thus the total magnetizing current in the system is N times as high.
At the final instant of a pulse on the bus this magnetizing current will cause a faulty voltage V f across the characteristic line impedance R of a value: ##EQU1## The minus sign in this formula indicates that the polarity of the faulty voltage is opposite to that of the pulse voltage. The faulty voltage curve then exponentially returns to zero having a time constant equal to R divided by L.
The middle graph of FIG. 2 shows the course of the magnetizing current in a spurious self-inductance resulting from a voltage pulse on the bus. The magnetizing current increases linearly during the pulse to the afore-mentioned terminal value; if there were no varying compensating current the magnetizing current after the pulse would exponentially decrease to zero having the afore-mentioned time constant.
The bottom graph of FIG. 2 shows the course of a possible compensating current. This current has zero value till the end of the pulse, after which this current is increased by an amount proportional to the decrease of the magnetizing current. If the magnetizing current has been calculated with the value of the spurious self-inductance as measured on the circuit-sided winding of the transformer and if the compensating current is conducted through this same winding, the change of compensating current will be equal to the maximum value of the magnetizing current. If the compensating current is conducted through another winding, the currents are in proportion to the ratio of the numbers of turns of these windings. If the change of compensating current had been brought about in the winding in which the magnetizing current occurs, there would not have been any faulty voltage in the course of the pulse voltage (top graph of FIG. 2).
FIG. 3 shows an embodiment of a terminal comprising a compensating arrangement in accordance with the invention. The transmitting terminal together with the line load 24 has been represented by reference numeral 22. The transmitter has been represented symbolically as the composition of two d.c. voltage sources 10-1 and 10-2 and a pulse switch 36. Voltage sources 10-1 and 10-2 are identical and of opposite polarity, so that this terminal is designed for alternately transmitting a positive and a negative voltage pulse. Thereto switch 36 switches alternately one of the voltage sources 10-1 and 10-2 into operation dependent on the polarity of the preceding pulse. If no pulse needs to be transmitted switch 36 has assumed the neutral position. The voltage course of the pulses generated by the terminal 22 has for example a form as shown in the top graph of FIG. 5.
The voltage pulses generated by the transmitting terminal 22 are transferred to the receiving terminal 26 via the associated transformer 8. In this receiving terminal 26 a compensating current is supplied to the circuit-sided winding of transformer 8. This compensating current is to change to such an extent that the change of magnetizing current is consequently compensated for.
For this purpose terminal 26 comprises a controllable voltage source 34 providing an output voltage whose change (at the pulse-terminating instant) is directly proportional to the pulse voltage. Together with resistor 30, this voltage source serves as a source of a current to the receiving circuit winding of the transformer 8. At a right choice of resistor 30 the change of compensating current then equals the (dropping) magnetizing current, as a consequence of which the magnetization of the core of the transformer remains unchanged.
The controllable voltage source 34 is preferably designed as an integrating sample-and-hold circuit, whose inputs 40 and 42 are connected to the circuit-sided winding of the transformer 8. By this integrating sample-and-hold circuit 34 the pulse height of the pulses on the bus is measured. This circuit produces an output voltage whose change is proportional to the measured pulse height. As the magnetizing current to be compensated for is likewise proportional to the pulse height, by the choice of resistor 30 the change of compensating current can be chosen such that it equals the change of magnetizing current.
FIG. 4 shows an embodiment of the integrating sample-and-hold circuit 34. This circuit comprises two synchronously operated change-over switches 44 and 46 whose movable contacts are connected via a capacitor 54. The movable contact of change-over switch 44 moves between the two inputs 40 and 42, the contact of change-over switch 46 moving between a contact point connected to input 42 and a second contact point. The latter two contact points are connected to the inputs of an operational amplifier 48 whose output is fed back via a capacitor 50 to a non-inverting input, to which the second contact point has also been connected. Capacitor 50 has the same capacitance value as capacitor 54. To the output of amplifier 48 also an inverting amplifier 52 having an amplification factor equal to one has been connected. The output of amplifier 52 forms the ouput 38 of the entire circuit.
At the sampling instant the contacts of switches 44 and 46 are reversed from their sketched position, equally changing the load of the capacitors 54 and 50 As a fed back operational amplifier controls its two inputs to equal potential, the non-inverting input of amplifier 48 will assume zero potential so that the output of this amplifier assumes the negative sample voltage. Output 38 thus remains via amplifier 52 at the sampled voltage until the next samping instant. If amplifier 52 is designed to have a low output impedance, circuit 34 may serve as a voltage source for supplying the compensating current.
FIG. 5 shows a graphical representation of the pulse voltage V b on the bus, the associated magnetizing current i m in the spurious self-inductance, and the relevant course of the compensating current i c . The course of the pulse current V b may have been caused by the terminal in which also the relevant magnetizing current is generated or by some other terminal. It is assumed that V b is the pulse voltage occurring on the circuit-sided winding of transformer 8, that i m is the magnetizing current in that same winding and that the compensating current is also led through this winding.
As hereinbefore described the rectangular voltage pulses cause a linearly increasing magnetizing current whose direction corresponds to the polarity of the (pulse) voltage. Both the size and the direction in which the magnetizing current will change at the pulse-terminating instant are therefore known. Since it is a known fact that the change of compensating current should be opposite to the magnetizing current at that same instant, the direction of the compensating current is also known. The size of this current is preferably chosen to be equal to half the magnetizing current so that at the end of the pulse only the direction of the compensating current is reversed. This process is repeated at each pulse-end so that the course as represented in figure 5 is thus developed.
It should be observed that it is not necessary for a proper functioning of the arrangement in accordance with the invention that the compensating current should be symmetrical with respect to zero current. The entire curve representing the current course i c may be shifted over an arbitrary vertical distance. This will only result in the maximum magnetic flux through the transformer core assuming a higher value. However, for the compensation of the faulty voltage only the change in the compensating current is of importance.
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A telecommunication system comprising a bus conductor to which respective stations are connected by respective transformers, communication taking place via voltage pulses V p on the bus. Each voltage pulse V p causes a magnetizing current i m to be developed in the spurious self-inductance of each connected transformer, which if not compensated will cause a faulty voltage to arise after termination of the pulse and so result in faulty information transfer. The invention provides a controllable voltage source which generates a compensating current i c in the winding of each connected transformer to compensate this faulty voltage, so that at the instants of pulse termination the total magnetization of all transformers remains unchanged.
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FIELD OF THE INVENTION
[0001] The invention relates to a disk carrier mechanism adopted for use in retracting optical disk drives, and particularly a disk carrier mechanism that operates with simplified element movements.
BACKGROUND OF THE INVENTION
[0002] Among the peripheral devices of personal computers, the optical disk drive has become an indispensable piece of equipment. With the growing popularity of multimedia information in recent years, a great amount of data and products are stored on optical disks. Optical disks also have many advantages over other data media, thus the demand and popularity of optical disk drives such as CD and DVD is constantly increasing.
[0003] In order to facilitate disk insertion and retrieval in the small space of the optical disk drive, a retracting optical disk drive has been development, such as the one disclosed in U.S. Pat. No. 2,193,24. Conventional retracting optical disk drives mostly employ a guiding board to direct and position the disk. The guiding board has a plurality of slots to couple with elements such as cams and latch hooks. The cited patent has many elements. Thus production cost is higher, the fabrication process is complicated, and accurate positioning and assembly are difficult.
[0004] In view of the aforesaid disadvantages, to design a disk carrier mechanism with fewer elements and simplified movements to make assembly simpler, positioning easier, fabrication procedures simpler, and production cost lower has become a key focus in the development of the retracting optical disk drive.
SUMMARY OF THE INVENTION
[0005] The primary object of the invention is to provide a disk carrier mechanism that can carrying a disk with fewer elements and simplified element movements, and make assembly easier and cost lower.
[0006] The disk carrier mechanism for optical disk drives of the invention is used to carry the disk between an inserted position and a reading position. The inserted position is the position on the disk carrier mechanism of the optical disk drive where the disk is placed. The reading position is the position of the chuck of the optical disk drive where the opening of the disk is located.
[0007] The invention consists of a wedged member set, a fixing board, a sliding board and a driver set. The wedged member set couples with guiding slots of the fixing board and fixing holes of the sliding board to enable the sliding board and wedged member set to slidably mount onto the fixing board. The wedged member set includes a plurality of wedged members, each with a wedged part to wedge the disk. The driver set is mounted onto the fixing board to drive the sliding board to slide relative to the fixing board.
[0008] When the disk is placed on the disk carrier mechanism, the disk is wedged in the wedged part to push the wedged member set to move along the guiding slots of the fixing board, and move the sliding board relative to the fixing board to the corresponding driver set. The driver set drives the sliding board and the wedged member set moves the disk to the reading position. In contrast, when retracting the disk, the driver set drives the sliding board, and the wedged member set moves along the guiding slots to move the disk on the wedged part of the wedged member set. When the sliding board separates from the driver set, the disk is moved to the inserted position by the wedged member set.
[0009] The foregoing, as well as additional objects, features and advantages of the invention will be more readily apparent from the following detailed description, which proceeds with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] [0010]FIG. 1 is a sectional view of the wedged member of the invention.
[0011] [0011]FIG. 2 is a perspective view of the fixing board of the invention.
[0012] [0012]FIG. 3 is a perspective view of the guiding board of the invention.
[0013] [0013]FIG. 4 is a perspective view of the sliding board of the invention.
[0014] [0014]FIG. 5 is a front perspective view of the invention.
[0015] [0015]FIG. 6 is a back perspective view of the invention.
[0016] [0016]FIGS. 7A through 7E are schematic views of the invention, showing the disk in various moving conditions.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0017] Referring to FIGS. 1 through 6, the disk carrier mechanism of the invention aims at carrying a disk A between an inserted position and a reading position. The inserted position is the location where the disk A is placed on the disk carrier mechanism of the optical disk drive. The reading position is the location of the chuck of the optical disk drive where the opening of the disk is mounted (also referring to FIGS. 7A and 7E).
[0018] The disk carrier mechanism of the invention includes a wedged member set 10 , a fixing board 20 , a sliding board 30 , a driver set 40 , a sliding member 50 and an elastic element 60 . The wedged member set 10 enables the sliding board 30 to movably couple on one side of the fixing board 20 and moves the disk A. The driver set 40 drives the sliding board 30 to move relative to the fixing board 20 . The sliding member 50 is connected to the sliding board 30 by the elastic element 60 .
[0019] The wedged member set 10 includes a plurality of wedged members 11 . Each wedged member 11 has a wedged part 111 and a washer 112 . The wedged part 111 may wedge the disk A. It includes a plane 111 a, a side wall 111 b and a sloped surface 111 c. The plane 111 a may hold the disk A horizontally. The side wall 111 b connects to the plane 111 a to allow the wedged member 11 to be pushed by the disk A and drives the disk A when the wedged member 11 is moved. The plane 111 a and the side wall 111 b may wedge the disk A. The sloped surface 111 c connects to the plane 111 a to guide the disk A to wedge in the wedged member 11 and escape from the wedged member 11 . The washer 112 is movably mounted onto the wedged member 11 to keep the sliding board 30 movably located on one side of the fixing board 20 .
[0020] The fixing board 20 has a plurality of guiding slots 21 , a retaining section 22 , a clamp set 23 , a front switch 24 , a rear switch 25 , a guiding board 26 and a lever 27 . Each guiding slot 21 couples with one wedged member 11 and guides the movement of the wedged member 11 . The retaining section 22 is located on one side of the fixing board 20 (opposite to the side of the fixing board 20 where the sliding board 30 is located) to enable the disk A to separate from the wedged member 11 . The clamp set 23 , front switch 24 and rear switch 25 are located on another side of the fixing board 20 (the side of the fixing board 20 where the sliding board 30 is located). The clamp set 23 includes a clamping rod 231 , a clamping spring (not shown in the drawings), a clamping plate 233 and a clamping member 234 . The clamping rod 231 is pivotally mounted on the fixing board 20 . The clamping spring (not shown in the drawings) is coupled with the clamping rod 231 . The clamping plate 233 is coupled with the clamping rod 231 in a turnable manner. The clamping member 234 is fixedly mounted onto the clamping plate 233 and is located in a position corresponding to the reading position of the disk A so that when the disk A is moved with its opening corresponding to the chuck of the optical disk drive, the clamp set 23 presses the disk A to the chuck on the reading position. The front switch 24 and the rear switch 25 connect electrically with the driver set 40 , and correspond respectively to the starting point and the finishing point of the movement displacement of the sliding board 30 relative to the fixing board 20 to actuate the driver set 40 . The guiding board 26 is located on one side of the fixing board 20 (opposite to the side of the fixing board 20 where the sliding board 30 is located) and has a guiding surface 261 to direct the disk A to the inserted position and make the disk A wedge in the wedged part 111 . The lever 27 is pivotally located on one side of the fixing board 20 (opposite to the side of the fixing board 20 where the sliding board 30 is located).
[0021] The sliding board 30 has a plurality of fixing holes 31 corresponding to the guiding slots 21 and an opening 32 corresponding to the clamp set 23 . It also has a first gear rack 33 . The dimensions of the fixing hole 31 correspond to the wedged member 11 so that the wedged member 11 may couple with the corresponding fixing hole 31 and the guiding slot 21 . When the wedge part 111 is located on one side of the fixing board 20 , the sliding board 30 is slidably located on another side of the fixing board 20 . When the sliding board 30 is moved, the clamp set 23 is located in the opening 32 without affecting the movement of the sliding board 30 . The first gear rack 33 is located on one side of the sliding board 30 adjacent to the driver set 40 to be driven by the driver set 40 .
[0022] The driver set 40 is mounted onto the fixing board 20 . It includes a motor 41 , a worm 42 , a first gear 43 and a second gear 44 . The motor 41 is located on one side of the fixing board 20 where the wedged part 111 is located. The worm 42 is coupled with the motor 41 and is located on one side of the fixing board 20 where the wedged part 111 is located. The first gear 43 engages with the worm 42 and is located on one side of the fixing board 20 where the wedged part 111 is located. The second gear 44 engages with the first gear 43 and is located on another side of the fixing board 20 opposite to where the wedged part 111 is located (but on the side of the fixing board 20 where the sliding board 30 is located). When the motor 41 rotates it drives the worm 42 , which in turn drives the first gear 43 and the second gear 44 to rotate.
[0023] The sliding member 50 is located on one side of the sliding board 30 adjacent to the driver set 40 , and is movable relative to the sliding board 30 . It has a second gear rack 51 formed on one side adjacent to and driven by the driver set 40 . The elastic element 60 couples with the sliding member 50 and the sliding board 30 such that when the wedged member set 10 moves along the guiding slots 21 , the sliding board 30 is driven and moved relative to the fixing board 20 , and the driver set 40 drives the sliding member 50 (through the second gear rack 51 ) to move. The elastic element 60 drives the sliding board 30 to move, the driver set 40 drives the sliding board 30 (through the first gear rack 33 ), and the disk A is moved to the reading position. On the other hand, when the sliding board 30 separates from the driver set 40 , the sliding member 50 and the elastic element 60 push the sliding board 30 outwards, and the disk A is moved to the inserted position.
[0024] Referring to FIGS. 7A through 7E, when the invention is in use and the disk A is inserted, the guiding surface 261 of the guiding plate 26 guides the disk A to the inserted position and pushes the lever 27 . The disk A is then wedged in the wedged part 111 of the wedged member 11 of the wedged member set 10 . The wedged member 11 is pushed by the external force applied to the disk A and is moved along the guiding slot 21 . It moves the sliding board 30 at the same time relative to the fixing board 20 . When the sliding member 50 is moved to the second gear rack 44 of the driver set 40 , the sliding board 30 is moved away from the front switch 24 , and the motor 41 is actuated to rotate. The worm 42 is then driven, and the first gear 43 and second gear 44 are driven to rotate. Through the second gear rack 51 , the sliding member 50 is driven by the second gear 44 , and the elastic element 60 drives the sliding board 30 to move. The second gear 44 drives the sliding board 30 through the first gear rack 33 . When the wedged member set 10 moves the disk A to couple its opening with the chuck of the optical disk drive, the sliding board 30 is driven continuously by the second gear 44 , so the sliding board 30 is moved continuously until reaching the rear switch 25 . Meanwhile, the lever 27 turns continuously because of the movement of the wedged member 11 . The disk A is stopped by the retaining section 22 , drops downwards from the plane 111 a and side wall 111 b of the wedged part 111 along the sloped surface 111 c, and escapes from the wedging of the wedged member 11 . Meanwhile, the clamping plate 233 of the clamp set 23 turns about the clamping rod 231 to press the disk A to the chuck through the clamping member 234 to keep the disk A in the reading position.
[0025] In contrast, when retracting the disk A, the motor 41 of the driver set 40 drives the sliding board 30 to move, the disk A is moved upwards along the sloped surface 111 c to the plane 111 a and the side wall 111 b, and is wedged in the wedged part 111 . Meanwhile, the clamp plate 233 raises the clamping member 234 to facilitate wedging of the disk A in the wedged part 111 of the wedged member 11 . As previously discussed, when the sliding board 30 is moved, the disk A is also moved with the wedged member set 11 until the first gear rack 33 of the sliding board 30 is separated from the second gear 44 of the driver set 40 . The elastic element 60 pushes the sliding board 30 , which presses the front switch 24 , and the driver set 40 stops operating. Meanwhile, the lever 27 moves the disk A outwards to complete the retracting movements for the disk A.
[0026] In summary, the disk carrier mechanism of the invention has fewer elements, and is thus easier to assemble. Element movements for loading the disk also are simplified. Thus cost may be reduced and positioning of the elements is more accurate.
[0027] While the preferred embodiment of the invention has been set forth for the purpose of disclosure, modifications of the disclosed embodiment of the invention as well as other embodiments thereof may occur to those skilled in the art. Accordingly, the appended claims are intended to cover all embodiments which do not depart from the spirit and scope of the invention.
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A disk carrier mechanism is used for moving a disk between an insertion position and a reading position. The disk carrier mechanism includes a wedged member set, a fixing board, a sliding board, and a driver set. The wedged member set includes multiple wedged members, each with a wedged part for wedging a disk. The driver set is formed on the fixing board for driving the sliding board to move relative to the fixing board. After being inserted, a disk is wedged in the wedged part and the force of inserting the disk pushes the sliding board to move to the position where the sliding board makes contact with the driver set. Thus the driver set drives the sliding board to place the disk in the reading position. Thus fewer members are used to accomplish the goal of moving the disk, which simplifies the actions of members, the fabrication of the mechanism, and reduces cost.
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FIELD OF THE INVENTION
[0001] The invention describes an LED lighting system, and a method of controlling an LED lighting system.
BACKGROUND OF THE INVENTION
[0002] Known types of indoor lighting arrangements can comprise various different types of light source such as halogen lamps, incandescent lamps, etc. Such lamps may be used in conjunction with various kinds of dimmers, for example phase-cut dimmers that cut a portion of the mains input power in order to reduce the average power provided to the conventional light source. LED lighting—using light-emitting diodes as light sources—is also becoming more widespread and popular owing to the reduced power consumption and longer lamp lifetimes. LED lamps are available with standard connectors such as E14, E27, GU10 etc., so that these lamps may be used to retrofit existing lighting fixtures. WO2013177167A1 discloses method and apparatus for controlling a lighting device wherein a dimming characteristic in an energy source is detected and a switch is controlled based on the dimming characteristic to transfer energy to the load.
[0003] However, such retrofit LED lamps should not be connected to the output of a legacy phase-cut dimmer such as a wall-mounted dimmer, since damage to the LED lamp is likely to occur. The range of a phase-cut dimmer can extend from a minimum (undimmed, corresponding to 100% or maximum light output) up to a maximum (fully dimmed, corresponding to minimum light output), and the “phase-cut angle” defines how much of the 180° half-wave is cut by a leading-edge or trailing-edge dimmer. At a minimum dimming setting, the phase-cut angle can be close to 0°, and at a maximum dimming setting, the phase-cut angle can approach 180°. The average voltage at the input to the lamp is decreased as the phase-cut angle increases. In the case of an LED lamp, this phase-cut voltage is applied to the inputs of the driver, and the reduced voltage can be a problem for the LED driver, particularly at large phase-cut angles. To warn the user, the manufacturer generally provides a printed warning with the lamp. However, this cannot reliably prevent the incorrect installation of the LED lamp.
[0004] For some types of LED lamp, it will not be immediately obvious to the user that the lamp has been connected to a legacy dimmer, since the lamp driver will manage to deliver a constant current to the LEDs until a certain maximum phase-cut angle is reached. Until this maximum phase-cut angle is reached, the light output remains essentially constant. Beyond this maximum phase-cut angle, the driver will not be able to match the input power to the required output, and the lamp will exhibit unstable behaviour, for example by noticeably flickering or by ceasing to emit light.
[0005] However, even below the maximum phase-cut angle, when the driver can ensure that the light output is constant, the behaviour of the lamp can still be compromised. For example, the sharp voltage increase on a leading-edge phase-cut input can result in a current spike in the lamp circuitry. Furthermore, ripple current can increase significantly in various parts of the lamp circuitry. The current spikes and/or ripple current can ultimately lead to lamp damage, but the effects are not noticeable to the user until the LED lamp starts to behave poorly or fails well before its expected lifetime.
[0006] Newer generations of LED lamps, in which the lamp driver has a high power factor, can exhibit a reaction to the dimmer setting of a legacy dimmer, i.e. the light output of LED lamp will be affected by the phase-cut angle. However, these LED lamps are also not intended to be used with a phase-cut dimmer. The user may misinterpret the apparent “response” of the lamp to mean that the lamp is dimmer-compatible, and may even interpret the “response” to actively use the dimmer to adjust the light output. As a result, the LED lamp may show erratic behaviour and may fail well before its expected lifetime.
[0007] Since the user may be unaware that an older or newer generation LED lamp has been incorrectly installed in an existing lighting setup, in spite of the manufacturer's printed warning, customer dissatisfaction in the event of premature lamp failure or unsatisfactory behaviour may be directed instead at the lamp and the lamp manufacturer.
[0008] Therefore, it is an object of the invention to provide an improved way of incorporating LED lamps into existing lighting arrangements, avoiding the problems described above.
SUMMARY OF THE INVENTION
[0009] The object of the invention is achieved by the LED lighting system of claim 1 ; by the LED lamp of claim 5 ; and by the method of claim 10 of controlling an LED lighting system.
[0010] According to the invention, the LED lighting system comprises a wireless communication arrangement for wireless transfer of signals between devices of the lighting system; at least one LED lamp connectable to a mains power supply, which LED lamp comprises a driver arrangement with a control unit for controlling the lamp according to a received signal received over the wireless communication arrangement; a phase-cut detector realized to detect a phase-cut input to the LED lamp; and a protection circuit realized to prevent operation of the LED lamp with the phase-cut input if the phase-cut angle of the phase-cut input exceeds a critical threshold, wherein said protection circuit is adapted to prevent an exposure of the LED lamp to the phase-cut input.
[0011] In the context of the invention, the expression “LED lamp” is to be understood as an LED lighting device comprising one or more light-emitting diodes as light sources, and a driver arrangement comprising one or more drivers for driving the LED light sources, and a control unit for controlling the driver(s). The LED light sources may be enclosed in a transparent or semi-transparent cover such as a glass bulb. The driver arrangement with its driver(s) and control unit may be understood to be incorporated in a housing of the lighting device. To allow the LED lamp to be used to retrofit existing conventional light sources, it may be understood to comprise a suitable socket connector, for example an E27 connector. The expression “connectable to a mains power supply” is to be understood to mean that the voltage input to the LED lamp can be the mains voltage, i.e. the LED lamp does not need a transformer to perform input voltage conversion. The connector and housing may together form a base of the LED lamp. The LED lamp be may be presumed to be incompatible with a legacy dimmer as described in the introduction. Instead, as indicated above, the control unit of the LED device can regulate the driver(s) to achieve a desired light output level ranging between a minimum light output level to a maximum light output level. As explained in the introduction, such LED lamps are not compatible with legacy phase-cut dimmers. While relatively small phase-cut angles (for example up to about 50°) may not noticeably alter the light output and may not cause long-term damage to the driver, a phase-cut angle that exceeds a critical threshold (for example a phase-cut angle greater than 70°, depending on the lamp driver) may indeed result in damage to the driver, even if the damage is not immediately apparent. Therefore, in the context of the invention, detection of a phase-cut input to the LED lamp is to be understood as detection of such a critical phase-cut input. In this way, the method according to the invention ensures that the LED lamp is prevented from operation with a phase-cut input that exceeds a critical phase-cut angle.
[0012] An advantage of the LED lighting system according to the invention is that the LED lamp can be reliably protected from damage when inadvertently connected to a legacy dimmer. The LED lamp can be prevented from operation with the phase-cut input in an entirely automatic “self-healing” procedure, so that user interaction is not necessary. The lighting system can also be realized to involve the user, so that lighting system provides the further advantage of raising customer awareness regarding the damage that might ensue when an LED lamp is installed in an existing lighting system. The various ways in which operation of the LED lamp can be prevented with a phase-cut input exceeding a critical level will be explained in detail below.
[0013] According to the invention, the LED lamp comprises a driver arrangement with a control unit for controlling the LED lamp according to a signal received from a wireless communication arrangement of an LED lighting system; a phase-cut detector realized to detect a phase-cut input to a driver of the driver arrangement; and a protection circuit realized to prevent operation of the LED lamp with the phase-cut input if the phase-cut angle of the phase-cut input exceeds a critical threshold, wherein said protection circuit is adapted to prevent an exposure of the LED lamp to the phase-cut input.
[0014] An advantage of the LED lamp according to the invention is that, with relatively little effort, the lamp can be reliably protected from damage that would result when it is operated from a phase-cut dimmer. The lamp according to the invention can be prevented from operation with the phase-cut input in a number of ways, as will be explained below. A completely automatic response is also possible, so that the LED lamp according to the invention can be reliably protected from damage without having to rely on the user of the lighting system.
[0015] According to the invention, the method of controlling an LED lighting system comprises the steps of providing a wireless communication arrangement for wireless transfer of signals between devices of the LED lighting system; providing at least one LED lamp connectable to a mains power supply, which LED lamp comprises a control unit for controlling the lamp according to a signal received over the wireless communication arrangement; detecting a phase-cut input to the LED lamp; and preventing operation of the LED lamp with the phase-cut input by preventing an exposure of the LED lamp to the phase-cut input, if the phase-cut angle of the phase-cut input exceeds a critical threshold.
[0016] An advantage of the method according to the invention is that it provides a simple and straightforward way of responding to a phase-cut input to the LED lamp, and can ensure that the LED lamp is protected from a prolonged exposure to such a phase-cut input. The method according to the invention allows the LED lamp to be prevented from operation with the phase-cut input in a fully automatic manner, or in a way that involves an interaction with a user of the lighting system, as will be explained below.
[0017] The dependent claims and the following description disclose particularly advantageous embodiments and features of the invention. Features of the embodiments may be combined as appropriate. Features described in the context of one claim category can apply equally to another claim category.
[0018] The LED lighting system according to the invention provides a way of ensuring that an LED lamp is not damaged when it is inadvertently connected to a legacy dimmer. Therefore, without restricting the invention in any way, the terms “lamp” and “LED lamp” may be used interchangeably in the following, and the LED lighting system may also be referred to as a “lighting system”. Of course, other conventional light sources such as halogen lamps, incandescent lamps, etc. may be connected to a shared power supply of the lighting system. While a conventional light source might draw its power from the same power supply, it is not included in the wireless communication system and is switched on or off using a conventional switch such as a wall-mounted switch.
[0019] In the lighting system according to the invention, the LED lamps each comprise a control unit. The control unit can include a microprocessor realized to process input signals and to generate output signals, and may be referred to as a microprocessor control unit (MCU) in the following. The wireless communication arrangement permits wireless transfer of signals between devices of the lighting system, so that lighting control signals can be received by the control units of the LED lamps of the lighting system. There are various known and established protocols for local communication between wireless devices. For example, low-bandwidth wireless devices can communicate with each other over short distances using the Bluetooth protocol. Other technology standards for communication protocols allow radio frequency wireless communication over greater distances. An example of such a communication protocol is the Zigbee® specification. Communication over longer distances is made possible by a mesh network that is formed by the devices of such a system. In a preferred embodiment of the invention therefore, the devices of the lighting system are realised to exchange data using such a Zigbee® communication protocol, for example Zigbee® Light Link, and the lighting system may be assumed in the following to comprise a hub or bridge that issues radio-frequency (RF) commands to the LED lamps using the appropriate protocol. Such a hub or bridge can also communicate over Ethernet in a wireless local area network (WLAN). To this end, the lighting system preferably comprises a wireless routing device such as a WLAN router. Such a router allows multiple devices to communicate over a wireless local area network, and can be used to extend the lighting system to include any device with internet capability.
[0020] The lighting system according to the invention can be controlled in the usual manner, for example using wall-mounted switches to turn the lamps on and off. However, in a preferred embodiment of the invention, the lighting system includes a communications device of a user of the lighting system. For example, a device such as a tablet computer, smartphone etc., may also be included in the wireless network. For example, the user can install a suitable software application or “app” on his smartphone to communicate with the hub in order to pass lighting commands to one or more LED lamps of the lighting system.
[0021] LEDs lamps are inherently dimmable, and an LED driver can be realized to lower the voltage and/or current to the LEDs in order to achieve the desired light output level. This effect can also be used to obtain a desired light colour when an LED lamp comprises LEDs that emit differently coloured light, for example an LED lamp with red, green and blue LEDs. By adjusting the voltage and/or current to the specific LEDs, essentially any colour can be achieved. In the following, the terms “lamp-specific dimmer setting” and “RF dimmer setting” may be used to distinguish this intentional adjusting of the light output of an LED lamp from an unintentional adjustment by a legacy phase-cut dimmer.
[0022] As described above, a legacy phase-cut dimmer operates by “chopping off” a portion of the rectified mains voltage in order to reduce the average voltage to a conventional dimmable light source. The phase-cut angle of the phase-cut dimmer determines the amount of the rectified voltage that is cut. Therefore, in a preferred embodiment of the invention, the phase-cut detector is realized to detect the phase-cut angle of a phase-cut dimmer. This could be achieved by determining the duration during which the input voltage is essentially zero. The lighting system can then react to protect the LED lamp if the phase-cut angle exceeds a critical threshold. This critical threshold may be chosen to be quite low in order to avoid driving the LED lamp with an input signal that may result in undesirable current spikes or current ripple. For example, any phase-cut angle greater than a maximum permissible angle of 130° may be problematic in the long-term for an LED lamp, and the protection circuit of the lighting system according to the invention can prevent operation of the LED lamp when connected to a phase-cut dimmer that is set at a phase-cut angle exceeding that maximum permissible angle.
[0023] Detecting the duration of the phase-cut is possible, but this approach requires considerable effort. Therefore, the phase-cut detector of the lighting system according to the invention can detect an undesirable or unacceptable phase-cut angle in a number of alternative ways. For example, detection can be based on a characteristic of the phase-cut input. In one preferred embodiment of the invention, the phase-cut detector comprises an undervoltage detection circuit. This approach is based on the knowledge that the average voltage at the output of the dimmer is reduced according to the phase-cut angle. With increasing phase-cut angle, the average voltage decreases. The phase-cut detector can comprise a means of determining the average voltage, and can output a suitable warning signal when the average voltage is less than a certain threshold level.
[0024] In another approach, the phase-cut detector might preferably comprise an overcurrent detection circuit realised to detect a current peak or spike in a relevant part of the lamp circuitry, for example in the current through a driver's output capacitor. Such a current spike is characteristic when a legacy dimmer is used in conjunction with an LED driver, and the “height” of the current spike is related to the phase-cut angle. Such a realisation of the phase-cut detector makes use of this knowledge, and can output a suitable warning signal when the current spike exceeds a certain threshold level.
[0025] Detection of the phase-cut angle is indirect and may be difficult, since a legacy dimmer not only cuts the input, but also distorts its waveform. Furthermore, the input waveform to the LED lamp will also depend on the load presented by the lamp. The relatively simple control based on the average voltage may be insufficient in some situations, since the rectified mains voltage is not only dependent on the dimmer setting, but is also dependent on the lamp load, which in turn is dependent on the RF dimmer setting of the LED lamp. The simple control described above may lead to the lamp being put into its “off” state on account of the low average voltage measurement (an accumulation of a relatively small phase-cut angle and an RF dimmer setting) and being put into its “on” state again on account of the “healthy” average voltage, then being put into its “off ” state again as the average voltage drops, etc. The control cycle would repeat indefinitely, resulting in lamp flicker.
[0026] Therefore, in a further preferred embodiment of the invention, the phase-cut detector of an LED lamp comprises a driver current monitoring circuit for measuring the output current of the lamp's driver, since this is directly related to the lamp's output. Preferably, an averaged or stabilized output current is measured. If the measured current is below a certain threshold, it can be assumed that a phase-cut dimmer is in active use with that lamp. Preferably, the actual RF dimmer setting of the LED lamp is also taken into consideration.
[0027] The lighting system according to the invention can use the information provided by the phase-cut detector to activate the protection circuit, which then responds to prevent further operation of the LED from the phase-cut input. This can be achieved in a number of ways. For example, in a straightforward and simple approach, the protection circuit is realized to generate a control signal to the lamp's driver(s) to place the LED lamp in a standby mode of operation. In standby mode, the LEDs of the LED lamp are effectively “off”, i.e. the driver does not provide the LEDs with current. The protection circuit can do this essentially immediately when it receives a warning signal from the phase-cut detector. The LED lamp is protected from any further exposure to the phase-cut input and any damage to the lamp can be pre-empted.
[0028] In the above example, the user might realize that the LED lamp had been installed in an erroneous setup. However, simply switching the lamp off or into standby might equally well confuse or irritate the user, who may not understand why the lamp has been turned off. Therefore, in a further preferred embodiment of the method according to the invention, the LED lamp is driven to generate a visual warning to a user of the lighting system. For example, in a preferred embodiment of the invention, the LED lamp is operated to output one or more bursts of light essentially immediately when the lamp's control unit detects the presence of a phase-cut input on the power supply to the LED lamp when this is switched on. This visual signal indicates to the user that the setup of the lighting system should be changed. The visual signal can be repeated until the user switches the lamp off, or manually changes the dimmer setting to maximum power input (i.e. a phase-cut angle close to zero, resulting in zero or minimum phase-cut of the power input). If the lamp's control unit detects that no such action has been taken, i.e. the power input to the lamp is still phase-cut, the control unit can then decide to place the LED lamp in a standby mode of operation. Such a situation might arise if the user is not in the same room as the LED lamp, for example when the LED lamp is switched on remotely.
[0029] As described above, the lighting system according to the invention includes a user's communications device such as a tablet computer, smartphone, etc. This allows the hub to inform the user of any problems with one or more of the LED lamps. For example, if a phase-cut input is being applied to one or more of the LED lamps, the control unit of each affected lamp can inform the hub, which in turn can send an appropriate warning message to the app running on the user's smartphone or tablet computer. In a preferred embodiment of the invention, the message comprises a set of instructions to assist the user in correcting a configuration of the lighting system. For example, the message can show the user which lamp is being incorrectly operated, and can suggest a remedy to the user. An exemplary message might suggest to the user to correct the dimmer setting of the dimmer to which the lamp is connected, or to install the lamp in a different lighting fixture. If the user does not respond to such a message within a reasonable length of time, the lamp's control unit may still decide to protect the lamp by disconnecting it or placing it in a standby mode of operation.
[0030] Some types of legacy dimmer comprise a remote-control interface. This type of dimmer can be used in conventional lighting arrangements so that the user can adjust the light output by means of a hand-held remote control. Therefore, in a further preferred embodiment of the invention, the protection circuit is realized to issue a phase-cut angle correction signal over the wireless communication arrangement to such a remote-controlled dimmer device. Preferably, the phase-cut angle correction signal adjusts the phase-cut angle of the remote-controlled dimmer device to a minimum value. For example, if the dimmer is a leading-edge phase-cut dimmer, its phase-cut angle is preferably altered to be as close as possible to 0°. Since the devices in a Zigbee network are made known to each other, it is possible for the lighting system to determine whether the phase-cut dimmer is indeed such a controllable device. In such a situation, therefore, the lighting system can decide to regulate the dimmer itself, and can choose not to issue the visual warning described above. Instead, it may send a notification to the user's communication device, informing him of the dimming instruction.
[0031] In the lighting system according to the invention, adjusting the light output of the LED lamps can be performed over the app running on the user's communications device, for example his smartphone. In another preferred embodiment of the invention, this function can also be performed by a portable dimmer unit capable of wireless communication within the lighting system.
[0032] In the method according to the invention, operation of the LED lamp is interrupted as long as the phase-cut input is critical from the point of view of the lamp's driver. In other words, as long as the phase-cut detector determines that the phase-cut angle exceeds a certain threshold, the protection circuit will ensure that the LEDs remain in their “off” state in order to protect the lamp circuitry. The user may react to the feedback—e.g. the visual signal given by the LED lamp, an alert message displayed by the app running on the user's smartphone or tablet, etc.—and may operate the legacy dimmer to return it to a minimum phase-cut angle setting. In a particularly preferred embodiment of the invention, the method further comprises the steps of detecting a permissible input to the LED lamp, and subsequently resuming operation of the LED lamp. In other words, the phase-cut detector can detect whether the input voltage to the driver is now in an acceptable form, for example with a phase-cut angle that is less than the critical phase-cut angle. The protection circuit can then indicate to the driver that it should turn the LED lamp on again. Preferably, the LED lamp resumes operation at the setting that was initially selected by the user, i.e. with the colour and light output settings that were active prior to the lamp being put into its “off” state.
[0033] Other objects and features of the present invention will become apparent from the following detailed descriptions considered in conjunction with the accompanying drawings. It is to be understood, however, that the drawings are designed solely for the purposes of illustration and not as a definition of the limits of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] FIG. 1 shows a first embodiment of an LED lighting system according to the invention;
[0035] FIG. 2 shows voltage and current waveforms associated with a leading-edge phase-cut dimmer;
[0036] FIG. 3 shows a first embodiment of an LED lamp according to the invention;
[0037] FIG. 4 shows a second embodiment of an LED lamp according to the invention;
[0038] FIG. 5 shows a third embodiment of an LED lamp according to the invention;
[0039] FIG. 6 shows a second embodiment of an LED lighting system according to the invention.
[0040] In the drawings, like numbers refer to like objects throughout. Objects in the diagrams are not necessarily drawn to scale.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0041] FIG. 1 shows a first embodiment of an LED lighting system 1 according to the invention. In this exemplary embodiment, the LED lighting system 1 comprises a protocol bridge 11 such as a Zigbee® bridge, and a router 12 which can communicate with the bridge over a wireless LAN, for example using an Ethernet protocol. The lighting system 1 comprises at least one LED lamp 10 . To keep the drawing simple, only one LED lamp 10 is shown. The LED lamp 10 comprises a driver arrangement 100 with driver and control circuitry. The driver arrangement 100 has a communications interface to allow it to exchange data D 10 11 with the bridge 11 . In this way, the bridge 11 can send commands to the lamp 10 , and the lamp 10 can send a report or feedback to the bridge 11 . Furthermore, each lamp 10 of the lighting system 1 can act as a Zigbee® router in a mesh network and can forward commands (originating from the bridge 11 ) to other lamps of the lighting system 1 . In this way, the physical range of the network can be extended. The bridge 11 and any LED lamps 10 can exchange data D 10 _ 11 using a suitable protocol such as Zigbee® Light Link.
[0042] As explained above, the user of LED lamp 10 can install the lamp 10 in a lighting fixture that is connected to a mains power supply 2 . A phase-cut dimmer 3 such as a wall-mounted dimmer 3 may be already present in the user's lighting setup. If the dimmer 3 is set to perform phase-cut on the mains voltage, the power supply to the lamp 10 will be characterized by a sudden voltage change on the leading edge or on the falling edge, depending on the type of phase-cut dimmer 3 .
[0043] An example of an unacceptable or critical phase-cut input V cut is shown in FIG. 2 . Here, a leading-edge dimmer set at a phase-cut angle φ of about 60° has cut a portion of the mains voltage (indicated by the dotted line) at the beginning of each half-cycle, resulting in the phase-cut input V cut . The result is a sudden voltage change, which in turn results in a spike in the current I spike through the output capacitor of the lamp's driver. The current spike at large phase-cut angles is problematic for the type of filter circuit that is generally used in a low power-factor LED driver design. In such a driver, a pi-filter is used to suppress electromagnetic interference (EMI), with a relatively large capacitor across the outputs of the filter. Such a phase-cut input V cut and the resulting current spike will eventually damage the LED lamp 10 . Furthermore, the phase-cut results in a reduction in average voltage, which in turn increases the ripple current of the LED lamp, which in turn leads to a significant increase in temperature. To avoid damage resulting from current spikes and high temperatures, the LED lamp 10 according to the invention is provided with a phase-cut detector that can detect a phase-cut input to the LED lamp 10 . If the phase-cut detector detects such a phase-cut input, the lighting system 1 applies a protection circuit to prevent operation of the LED lamp 10 with the phase-cut input. The phase-cut detector and protection circuit are explained below. FIG. 2 also indicates an acceptable or uncritical phase-cut input V OK (indicated by the broken line), for which the legacy phase-cut dimmer is set at a relatively small phase-cut angle φ OK of about 20°, corresponding to a low dimmer setting, i.e. maximum or near-maximum light output.
[0044] FIG. 3 shows a first embodiment of an LED lamp 10 according to the invention. This simplified diagram shows a driver arrangement 100 and an LED light source 110 . The driver arrangement 100 comprises a driver 101 , which is shown in a very simplified manner. Its function as a rectifier is indicated, and its output capacitor C is also indicated. A pi-filter for suppressing EMI is not shown, but it may be understood that the driver 101 comprises such a filter and that the output capacitor C is an element of the pi-filter. The LED light source 110 can comprise any number of LEDs in any suitable arrangement (for example white and coloured LEDs which can be mixed to provide a wide range of colours), indicated collectively by the LED symbol in the diagram. A microprocessor control unit 102 (MCU) is used to control the driver 101 to provide voltage and current according to the desired light output (the diagram indicates driver 101 and light source 110 in a very simplified manner; in an actual embodiment, different coloured LED strings are driven using appropriate circuitry to obtain the desired colour mix). As described above, the MCU 102 receives commands D 10 _ 11 from a protocol bridge. The MCU 102 converts these commands D 11 _ 11 into suitable control signals 104 for the lamp's driver(s) 101 . In this exemplary embodiment, a phase-cut detector 103 A is realised to detect an undervoltage V cut at the inputs to the driver 101 . An undervoltage is detected when a phase-cut dimmer between the mains power and the LED lamp 10 has been set to reduce the average voltage. The phase-cut detector 103 A generates a signal 105 A that informs the MCU 102 when an undervoltage is detected, i.e. that the phase-cut angle is unacceptably large. To deal with this situation, the LED lamp 10 comprises a protection circuit 106 . In this exemplary embodiment, the protection circuit 106 is realised as part of the MCU 102 but could of course be realized separately. The protection circuit 106 can be realized in hardware and/or software to react to the undervoltage at the driver inputs. For example, the protection circuit 106 can output a driver control signal 104 which instructs the driver 101 to place the LEDs 110 in standby, thus protecting the lamp circuitry from spike damage. The user may notice that the LED lamp 10 has been turned off. In a further development, the protection circuit 106 can output driver control signals 104 that instruct the driver 101 to cause the LEDs 110 to flash in a controlled manner, for example to flash once every second while at the same time reducing the light output, and then to place the lamp 10 a standby mode. This visual signal can inform the user that the lamp 10 is being “shut down” in a controlled manner, and may prompt him to check the dimmer setting. In a further development, the protection circuit 106 can issue a feedback message D 10 _ 11 to the bridge, which in turn can send a message D 11 _ 12 (as indicated in FIG. 1 ) to the WLAN router. If the user of the lighting system has a smartphone or other device running a suitable app, this can display a message forwarded by the router. For example, the feedback might result in an alert on the smartphone display, informing the user that the LED lamp 10 is connected to a dimmer set to perform phase-cut, and that corrective measures must be taken.
[0045] Of course, any of these responses can be combined in any appropriate manner. For example, to cover situations in which the user is not in the same room as the LED lamp 10 when this is switched on (e.g. in an burglar-deterrent lighting sequence) and therefore does not see the controlled flashing sequence when the lamp 10 is subsequently off again by the protection circuit 106 ; and/or does not look at his smartphone display when the alert is displayed and therefore does not see the warning message, the protection circuit 106 can instruct the driver to place the lamp 10 in standby mode if the phase-cut input is still present after a certain length of time. In this way, the lamp 10 is reliably protected from the adverse effects of a phase-cut input voltage and its high performance and long lifetime are safeguarded.
[0046] FIG. 4 shows a second simplified embodiment of an LED lamp 10 according to the invention, showing an alternative realization of a phase-cut detector 103 B. In this case, the phase-cut detector 103 B is realized as an overcurrent detector 103 B which can detect a spike on the current through the output capacitor C. The presence of such a spike is notified to the MCU 102 in the form of a signal 105 B, and the MCU 102 can react in any of the ways already described in Fig. above 3 .
[0047] FIG. 5 shows a third simplified embodiment of an LED lamp 10 according to the invention, showing a further realization of a phase-cut detector 103 C. In this case, the phase-cut detector 103 C is realized as a driver output current monitor 103 C which monitors the output current 107 of the driver 101 and compares this to an expected value. The driver output current is in the form of a modulated square wave at the switching frequency of the lamp's driver 101 . To monitor the average driver output current, therefore, the phase-cut detector 103 C comprises a first filter module 1031 for filtering and amplifying the driver output current. A further filter module 1032 serves to filter a pulse-width modulated (PWM) dimming signal originating from the MCU 102 , and to bring this to a level corresponding to a maximum acceptable legacy dimmer setting, for example a level corresponding to 70% light output. The filter module outputs are compared in a comparator 1033 , whose output 105 C indicates to the MCU 102 when a phase-cut dimmer with an unacceptably large phase-cut angle is in active use with this lamp 10 . The MCU 102 can respond as described in the preceding two embodiments, for example, the protection circuit 106 can output a driver control signal 104 which instructs the driver 101 to place the LEDs 110 in standby, thus protecting the lamp circuitry from spike damage.
[0048] FIG. 6 shows a second embodiment of an LED lighting system 1 according to the invention. This diagram shows further devices 4 , 5 that can be included as part of the lighting system 1 of FIG. 1 . Here, a smartphone 4 is included in the lighting system 1 by means of an app that runs on the smartphone 4 , and which can exchange data D 4 _ 12 with the WLAN router 12 . A wireless dimmer 5 is also shown. This can be a radio-frequency (RF) controllable legacy “smart dimmer” 5 used to control dimming levels of a conventional light source such as a halogen lamp. Usually, such a dimmer is controlled by a hand-held remote control device. In the lighting system 1 according to the invention, the router 12 can also issue control signals D 5 _ 12 to the dimmer 5 .
[0049] The diagram shows an embodiment in which an LED lamp 10 according to the invention is used to retrofit an existing conventional lighting fixture. If the phase-cut detector of the lamp 10 detects a phase-cut voltage at the driver input and/or a spike on the output capacitor current as described above, the control unit 102 of the lamp 10 can react in any of the ways described above. In addition, the bridge 11 or WLAN router 12 can control the dimmer 5 to reduce the phase-cut angle to a minimum, i.e. to reduce the phase-cut to a minimum. This step can be carried out automatically upon detection of a phase-cut input, or after a certain length of time has elapsed without the user responding to a warning alert or to a flashing of the LED lamp 10 .
[0050] Although the present invention has been disclosed in the form of preferred embodiments and variations thereon, it will be understood that numerous additional modifications and variations could be made thereto without departing from the scope of the invention.
[0051] For the sake of clarity, it is to be understood that the use of “a” or “an” throughout this application does not exclude a plurality, and “comprising” does not exclude other steps or elements. The mention of a “unit” does not preclude the use of more than one unit.
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The invention describes an LED lighting system ( 1 ) comprising a wireless communication arrangement ( 11, 12 ) for wireless transfer of signals (D 10 _ 11 , D 11 _ 12 , D 4 _ 12 , D 5 _ 12 ) between devices ( 10, 11, 12, 4, 5 ) of the LED lighting system ( 1 ); at least one LED lamp ( 10 ) connectable to a mains power supply ( 2 ), which LED lamp ( 10 ) comprises a driver arrangement ( 100 ) with a control unit ( 102 ) for controlling the LED lamp ( 10 ) according to a received signal (D 10 _ 11 ); a phase-cut detector ( 103 A, 103 B, 103 C) realized to detect a phase-cut input (V cut ) to the LED lamp ( 10 ); and a protection circuit ( 106 ) realized to prevent operation of the LED lamp ( 10 ) with the phase-cut input (V cut ) if the phase-cut angle of the phase-cut input (V cut ) exceeds a critical threshold, wherein said protection circuit ( 106 ) is adapted to prevent an exposure of the LED lamp to the phase-cut input. The invention further describes an LED lamp ( 10 ) comprising a driver arrangement ( 100 ); and a method of controlling an LED lighting system ( 1 ).
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U. S. Provisional Application No. 61/095,194, filed Sep. 8, 2008.
FIELD OF THE INVENTION
[0002] The present invention is directed to non-aerosol shaving products that employ technology to provide both heat and lather during use.
BACKGROUND OF THE INVENTION
[0003] The use of reactive chemistry to create self-heating personal care compositions is known. The general approach involves employing a multi-chambered package with one chamber holding an oxidative phase and another chamber holding a reductive phase. Dispensing and mixing the two phases results in heat development through a chemical reaction between the oxidative phase and reductive phase.
[0004] Shaving compositions is one art area that has experienced significant development of self-heating chemistries. The sensation of warmth on skin prior to and/or during shaving can be perceived as highly beneficial by users of exposed blade razors. Consumers believe that heat can accomplish one or more of the following: open pores, soften skin and beard hair, provide a closer and more comfortable shave, reduce irritation, and leave skin refreshed and protected.
[0005] One prior self-heating shaving composition featured a non-aerosol formulation that employed separate non-ionic emulsion bases containing a reductant and oxidant, respectively. By virtue of the non-ionic base and no gas being involved, the formulation was essentially a non-lathering shave product. Despite the benefits of heat associated with the formulation, the majority of consumers still prefer lathering shave preps. Thus, developing a shaving product that combines the sensation of warmth and perceivable lather would be advantageous. The attempts to date however have not been optimal. For example, one prior attempt has employed conventional soap-based formulas pressurized in an aerosol package containing a volatile hydrocarbon propellant. But several disadvantages are realized with this approach, including VOC concern, fast heat dissipation, harshness of the soap base, and complicated/expensive aerosol packaging. Another prior attempt involved incorporating volatile hydrocarbons or fluorinated hydrocarbons in water-base emulsions which would volatilize upon spreading the composition onto one's skin. These formulations proved however to be highly unstable and prone to losing hydrocarbons during storage.
[0006] Accordingly, there is room for improvement in the development of a shaving product that adequately provides both heat and sustained lather.
SUMMARY OF THE INVENTION
[0007] The present invention is directed to self-heating shaving products that feature lather produced by nascent gas release in situ when mixing reductant and oxidant phases. The shaving products employ either a multi-chambered container or two separate containers that hold and dispense a first composition and a second composition. The first composition comprises a reducing agent and a carbon dioxide source, and the second composition comprises an oxidizing agent. The first composition is preferably formulated at a pH of from about 8.5 to about 10.5 to ensure stability of the carbon dioxide source. And the second composition is preferably formulated at a pH of from about 2.8 to about 3.8. When the first and second compositions are combined an exothermic redox reaction occurs to produce heat. Another result of the redox reaction employed in this invention is the formation of acid. As the reaction is completed, the high pH associated with the first composition drops, which in turn drives the release of carbon dioxide to produce the initial lather/foam. To sustain and/or accentuate the initial lather, systems comprising surfactants, opacifiers, and/or polymers are employed.
BRIEF DESCRIPTION OF THE DRAWING
[0008] The FIGURE is a chart illustrating lather dynamics (first 5 minutes) with different reductant formulations.
DETAILED DESCRIPTION OF THE INVENTION
[0009] The present invention may be understood more readily by reference to the following detailed description of illustrative and preferred embodiments. It is to be understood that the scope of the claims is not limited to the specific ingredients, methods, conditions, devices, or parameters described herein, and that the terminology used herein is not intended to be limiting of the claimed invention. Also, as used in the specification, including the appended claims, the singular forms “a,” “an,” and “the” include the plural, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. When a range of values is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent basis “about,” it will be understood that the particular values form another embodiment. All ranges are inclusive and combinable.
[0010] All percentages and ratios used herein are by weight of the first, second or mixed composition, and all measurements made are at 25° C., unless otherwise designated.
[0011] The self-heating shaving products comprise a first composition containing a reducing agent and second composition containing an oxidizing agent, which when combined into a mixed composition generate heat from the exothermic redox reaction. The first composition further comprises a source for generating carbon dioxide to foam or lather the mixed composition. The first and second compositions are kept separate from one another prior to use, preferably through employment of a multi-chambered container/dispenser or two separate containers/dispensers. The containers/dispensers employed for the shaving compositions of the present invention do not require a volatile propellant and are preferably not pressurized in any way. Furthermore, prior to being dispensed, the first and second compositions are maintained at substantially atmospheric pressure.
[0012] Each of the first and second compositions comprises oil-in-water emulsions that could independently be used as a shaving preparation without significant skin irritation. The oil phase of the respective emulsions can include any desired emollient that is safe for use in topical formulas, is compatible with other ingredients of the compositions, and provides the desired aesthetics. Suitable emollients include mineral oil, petrolatum, squalane/squalene, hydrogenated/unsaturated polyisobutene and mixtures thereof. Exemplary compositions contain from about 0.25% to about 15% of the emollient, from about 0.5% to about 12% of the emollient, or from about 0.75% to about 8% of the emollient.
[0013] The first composition comprises a reducing agent. A representative, non-limiting list of suitable reducing agents includes thiosulfate and sulfite compounds, such as sodium sulfite, sodium thiosulfate (e.g., sodium thiosulfate pentahydrate), ammonium thiosulfate, potassium thiosulfate, and thiourea; and compounds with a thiourea backbone, such as 1,5-diethyl-2-thiobarbituric acid or its derivatives, or ascorbic acid. Mixtures of these reducing agents, and other suitable reducing agents, may also be used. In some embodiments, the first composition employs the reducing agent at concentrations from about 2% to about 10%, preferably from about 3% to about 8%, by weight of the first composition.
[0014] A carbon dioxide source is also included in the first composition. The carbon dioxide source can be, for example, carbonate or bicarbonate salts of alkaline or alkaline earth metals, such as sodium, potassium, calcium and magnesium carbonates, and sodium and potassium bicarbonates. Mixtures of these materials can be used, as well as other carbon dioxide sources generally known to the skilled artisan. The carbon dioxide source is included in some first composition embodiments at concentration levels of from about 1% to about 10%, from about 2% to about 7%, and from about 3% to about 5%, by weight of the first composition.
[0015] The first composition is preferably formulated to a pH of from about 8.5 to about 10.5 to ensure stability of the carbon dioxide source during storage. Materials that can be used to adjust the pH include, for example, sodium and potassium hydroxide, calcium oxide, triethanolamine, and sodium and potassium carbonate. Such pH adjusters can be employed at a level for example of from about 2% to about 8%, or from about 3% to about 5%, by weight of the first composition.
[0016] The second composition comprises an oxidizing agent. Suitable oxidizing agents include, but are not limited to, peroxides, such as hydrogen peroxide (typically added as a 35% solution), benzoylperoxide, peroxomonosulfate, peroxodisulfate, urea hydrogen peroxide, and t-butyl peroxide. In some embodiments, the second composition may include from about 2% to about 10% of the oxidizing agent. In certain embodiments, the second composition can include from about 12% to about 16% of an oxidizing agent, such as hydrogen peroxide (35%) (which corresponds to about 4% to about 6% H 2 O 2 active).
[0017] The second composition is preferably formulated to a pH of from about 2.8 to about 3.8, or from about 3.0 to about 3.6. The reason for this preferred range is three-fold: 1) to achieve a final pH of from about 5 to about 7 (or from about 6.0 to about 6.8) of the stoichiometric mixture of the first and second compositions whereby heat production and gas release are satisfactory; 2) to enhance storage stability of the oxidizing agent; and 3) to mitigate the potential for skin irritation when dispensing ratios of the first and second compositions are off target. The pH adjusters of the second composition are mineral acids (e.g., phosphoric acid), at a concentration of 0.25% to 1.5%, and preferably 0.75% to 1.0%. Acid can be partially neutralized by employing sodium tetraborate at around 1-2.5%, so that a pH of 3.0 to 3.4 is achieved. Other pH adjusters can be used, including, for example, disodium or dipotassium phosphate, calcium or magnesium oxide or hydroxide.
[0018] As noted above, the first and second compositions are kept separate from one another prior to use. The volumes of the first and second compositions are included in separate containers or separate chambers of single containers so that they can be dispensed in appropriate relative amounts to provide a stoichiometric exothermic reaction when mixed. As the redox reaction results in the formation of acid, the high pH associated with the first composition drops, which in turn drives the release of carbon dioxide to produce the initial lather/foam. Lather in some of the embodiments typically starts forming about 5-10 seconds after mixing the first and second compositions, with temperature rising to about 35-40° C. during this time frame. The temperature continues to rise, reaching a maximum temperature of about 50-55° C. within 50-60 seconds after mixing and remains at that level for another 10-20 seconds. The lather/foam volume associated with the mixed composition can increase to greater than 5 times the initial dispensed volume. The lather/foam volume at around one minute after dispensing however is not sustained as the mixed composition is spread onto one's skin because the escaping carbon dioxide is not trapped to a significant extent by the mixed emulsion. The lather/foam volume upon spreading can be ⅓ of the peak volume achieved around one minute after dispensing and mixing the first and second compositions. Applicant however discovered a number of different techniques to sustain lather/foam volume, which are discussed in more detail below.
[0019] Particular surfactant systems for each of the first and second compositions is one technique discovered by the Applicant to sustain the carbon dioxide induced lather/foam. Primary surfactants for the first composition include mild non-ionic surfactants free from polyethylene oxides, such as, for example, polyglycerol fatty esters, glycosyl ethers, and sugar esters. Exemplary polyglycerol fatty esters include decaglyceryl dipalmitate, hexaglyceryl myristate, decaglyceryl laurate, hexaglyceryl laurate, and triglyceryl stearate. A representative, non-limiting list of suitable glycosyl ethers includes cetearyl polyglucoside, behenyl polyglucoside, myristyl polyglucoside, and cocoyl polyglucoside. Suitable sugar ester include, but are not limited to, sucrose esters, such as sucrose monostearate and sucrose distearate; and sorbitan esters, such as sorbitan monostearate, sorbitan palmitate, sorbitan oleate, sorbitan sesquioleate, and sorbitan isostearate or esters of mixed structure (e.g., PEG-3 methylglucose distearate). These primary surfactants may be employed at concentration levels of from about 2-8% or 3-5%, by weight of the first composition.
[0020] To boost the initial carbon dioxide induced lather/foam, one or more anionic surfactants can be formulated into the first composition in addition to the non-ionic surfactants discussed above. The one or more anionic surfactants are generally included at a total concentration of up to about 5%, by weight of the first composition. Exemplary anionic surfactants include fatty acyl sulfosuccinates, sarcosinates and lactylates. Di-sodium laureth-2 sulfosuccinate, sodium lauroyl sarcosinate and sodium lauroyl lactylate are some of the preferred anionic surfactants.
[0021] Exemplary surfactant systems for the second composition include a combination of ethers of fatty alcohols and polyoxyethylene with an ethylene oxide chain from 2 to 100 and fatty alkyl chain from 12 to 24. These surfactants are believed to be stable in the presence of the oxidizing agent, and be able to provide a stable shaving composition with desirable viscosity, aesthetics and rinsing properties. One preferred combination is a blend of derivatives with shorter and longer ethylene oxide chains. In certain embodiments, the second composition may include form about 2% to about 8% (or from about 2% to about 6%) of a non-ionic surfactant. In other embodiments, the second composition may include from about 2% to about 6%, preferably from about 3% to about 5%, of a shorter polyethylene oxide chain length non-ionic surfactants, such as Steareth-2. Additionally, the second composition may include from about 1% to about 4%, preferably from about 1.5% to about 3%, of a long polyethylene oxide chain length non-ionic surfactant, such as Steareth-21. In some embodiments, the second composition can include form about 1% to about 6% of one non-ionic surfactant, and from about 1% to about 6% of another, different non-ionic surfactant.
[0022] To stabilize the carbon-dioxide induced foam, Applicant discovered that materials can be employed to increase the viscosity of the liquid surrounding individual bubbles. These materials may include, for example, amphoteric surfactants, such as Cocamidopropyl Betaine or Cocamidopropyl Hydroxysultaine; alkoxylated fatty amides, such as PPG-2 Hydroxyethyl Cocamide, PPG-2 Hydroxyethyl Coco/Isostearamide or PPG-3 Hydroxyethyl Soyamide; or silicone ethers, such as PEG-12 Dimethicone. When employed, these materials are generally included at a level of from about 0.5% to about 3.5%, and preferably from about 1.5% to about 2.0%.
[0023] Certain acidic polysaccharides (e.g., xanthan gum, alginates) can be employed to provide a negative charge to help prevent fusion of adjacent foam bubbles by means of electrostatic repulsion. By virtue of its highly pseudoplastic behavior, inclusion of xanthan gum can also increase the integrity of residual film of the mixed composition on one's skin.
[0024] Opacity is a desired property of lathering shave preparations since it can help with tracking blade strokes on the skin, and since it provides a confidence level that a protective residual film that exists between the blade and the skin. Using surfactants with long, saturated fatty chains, such as C 16 -C 22 can provide such an opacifying effect. Examples of these types of surfactants include Steareth-2, Steareth-21, Cetearyl Glucoside, Arachidyl Glucoside, Sucrose Stearate and Sucrose Distearate, and PEG-3 Methylglucose Distearate. Imparting an opacifying effect can also be achieved by adding specific substances selected from the group comprising long chain fatty alcohols (e.g., cetearyl, stearyl, arachidyl alcohol); fatty esters (e.g., cetearyl stearate, cetearyl octanoate, cetyl palmitate, stearyl behenate, glyceryl distearate, glycol stearate, glycol distearate, PEG-3 Distearate); hydrocarbon waxes; and metal oxides, such as titanium dioxide, zinc oxide and magnesium oxide alone or in combination with a mica carrier. Other materials that can impart opacity can also be employed.
[0025] The rate of carbon dioxide release may also be manipulated to help sustain the lather/foam volume. This can be accomplished by increasing the pH of the mixed composition to a level of from about 6.2 to about 6.8. Increasing the level of alkaline (e.g., triethanolamine) or buffering salts (e.g., bicarbonates) can result in a higher mixed composition pH.
[0026] Bulking materials can be employed to further improve quality of the foam and provide more comfortable shaving. A representative, non-limiting list of suitable bulking materials includes clays, such as sodium potassium aluminum silicate; modified polysaccharides, such as hydroxypropyl starch phosphate and aluminum starch octenyl succinate. By way of example only, the optional bulking materials can be included at a concentration of level of 0.5-3% or 1-2%.
[0027] Several other optional ingredients can be included in one or both of the first composition and the second composition. For example, film-forming materials can be used to impart lubricity. Suitable film-forming materials include, but are not limited to, acrylamide/sodium acrylate/acrylic acid copolymers, sodium polyacrylate, chitosan derivatives (e.g., chitosan lactate or glycolate), associative thickeners (e.g., Polyether-1), natural waxes (e.g., beeswax, candelilla wax hydrocarbons and canauba acid wax), hydrocarbon polymers (e.g., petrolatum, mineral oil, squalane or polyisobutene), and hydrogenated vegetable oils (e.g., hydrogenated castor oil or hydrogenated olive oil). Such film-forming materials can be included at 1-10%.
[0028] To obtain certain targeted heat profiles, it may be advantageous to include a catalyst in the shaving composition. The catalyst is selected to catalyze the exothermic reaction, without deleterious effects on the skin or on the properties of the shave cream. The catalyst is generally included in the first composition that includes the reducing agent. Suitable catalysts for the exothermic reaction include sodium molybdate (e.g., sodium molybdate dihydrate), potassium molybdate, ammonium molybdate, sodium tungstate, potassium tungstate, and mixtures thereof. The first composition generally includes 0.1% to about 1.5%, preferably about 0.2% to about 1.0%, of the catalyst.
[0029] If the exothermic reaction generates an acid, as the reaction of the oxidizing and reducing agents discussed above will generally do, it is preferred that the first composition also include a neutralizing agent (a neutralizer). The neutralizing agent is selected and provided in a sufficient amount to neutralize enough of the acid so that the exothermic reaction is complete and the shaving composition will not irritate the user's skin. Preferably, substantially all of the acid is neutralized. Suitable neutralizing agents include, for example, triethanolamine, oxides (e.g., metal oxides), hydroxides (e.g., metal hydroxides), and metal carbonates, such as carbonates of alkaline metals (e.g., sodium, potassium), alkaline-earth metals (e.g., magnesium, barium), or transition metals (e.g., zinc). For example, the neutralizing agent may include calcium oxide, potassium hydroxide, sodium hydroxide, potassium bicarbonate, sodium bicarbonate or aluminum hydroxycarbonate. In some embodiments, the shaving composition (preferably the first composition) can include from about 0.5% to about 10% of such a neutralizer. For example, the first composition can include about 1% calcium oxide or about 4% triethanolamine.
[0030] The shaving composition may also contain other optional ingredients, including, for example, fragrances, colorants, skin-soothing agents, beard wetting agents, skin conditioning (e.g., exfoliating, moisturizing) agents (e.g., vitamin precursors and derivatives such as, for example, vitamins A, C and E, aloe, allantoin, panthenol, alpha-hydroxy acids, beta-hydroxy acids, phospholipids, triglycerides, botanical oils, amino acids), humectants (e.g., glycerin, sorbitol, pentylene glycol), phosphorus lipids (used, e.g., to encapsulate skin conditioning agents), antioxidants, preservatives, and other such ingredients. It may be desirable to include colorants in one or both of the first and second composition so that the compositions have different appearances. The contrast in appearance can help a user to mix the two compositions together upon dispensing so that an optimal level of heat and lather can be generated prior to and during use of the shaving composition.
EXAMPLES
[0031] The following examples further describe and demonstrate embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention as many variations thereof are possible without departing from the spirit and scope of the invention.
[0000] First Composition Examples Comprising Reducing Agent (values by weight %) Ingredients 1 2 3 4 5 6 7 8 Cetearyl Glucoside 0.5 0.8 1.0 1.0 Sucrose Stearate 1.5 2.0 2.0 2.0 1.5 1.5 1.5 1.5 Decaglyceryl-6 3.0 3.0 3.0 2.0 Palmitate PPG-2 Hydoxyethyl 1.5 1.5 2.0 1.5 2.0 2.0 Coco/Isostearamide Cocamidopropyl Betaine 3.0 2.0 Sodium Lauroyl Lactylate 1.5 Di-sodium Laureth-2 3.0 2.0 3.0 3.0 3.0 Sulfosuccinate Sodium Myristoyl 3.0 Sarcosinate Cetearyl Alcohol 2.4 4.0 4.0 4.0 3.0 4.5 4.5 4.5 Microcrystalline Wax 1.0 Petrolatum 2.0 Hydrogenated Castor Oil 1.5 1.5 1.5 1.0 1.5 1.5 1.5 Polyisobutene & 1.0 1.0 1.5 1.5 1.0 1.0 0.5 Polysorbate-20 & Polyacrylate-13 Polyether-1 0.5 Xanthan Gum 0.4 0.5 0.5 Propyleneglycol 0.5 1.0 0.8 Alginate Hydropropyl Starch Phosphate 2.0 1.5 0.8 0.8 1.5 1.5 Sodium Thiosulfate 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 Sodium Molybdate 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Triethanolamine 4.0 3.0 6.0 4.0 5.0 4.0 4.0 4.0 Sodium Bicarbonate 3.0 3.0 4.0 Potassium Bicarbonate 3.0 3.0 3.0 2.0 3.0 Titanium Dioxide 0.3 0.4 0.4 Titanium Dioxide and Mica 2.0 Perfume 2.0 2.0 2.0 2.0 2.0 1.5 2.0 2.0 Dye Solution, 1% 0.6 0.4 0.3 0.3 0.2 0.05 0.05 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.
The above first composition examples can be made as follows: Dissolve the water-soluble components of the aqueous phase in water with adequate stirring and bring solution to 80° C. Add hydrophobic materials, such as the fatty alcohols, waxes, hydrocarbons, oils, and co-surfactants to the aqueous solution while continuing to stir. Heat the solution up to 85° C., add the non-ionic emulsifier, and then agitate at an increased speed for about 20 minutes. Cool and continue to stir. Add the neutralizer and anionic surfactant. Homogenize the batch at 68-70° C. using immersion or external homogenizer. Add the reducing and catalyst salts at 55-58° C. The polymer/thickener if needed can then be added and mixed in thoroughly. Add the carbon dioxide source to the batch when the batch is at a temperature below 45° C. Add fragrance and dye at 40° C. Homogenize the batch again for 1½ to 2 minutes to create a smooth cream consistency, having a target final viscosity of 35,000-65,000 cst using an RVT spindle #6 at 1 minute and 10 rpm.
[0000] Second Composition Examples Comprising Oxidizing Agent (values by weight %) Ingredients 1 2 3 4 5 Steareth-2 4.2 4.2 4.6 4.2 4.2 Steareth-21 1.8 1.8 2.0 1.8 1.8 Cetearyl Alcohol 2.4 2.8 2.7 2.4 3.0 Microcrystalline Wax 1.0 Polyisobutene 2.9 Petrolatum 2.0 Hydrogenated Castor Oil 2.9 2.4 Beeswax 2.0 Polyisobutene & Polysorbate-20 & 1.0 0.5 Polyacrylate-13 Polyethylene & PTFE 0.5 Titanium Dioxide & Mica 2.0 Phosphoric Acid 1.12 1.12 Sodium Borate 1.8 1.8 Hydrogen Peroxide 4.0 4.0 4.0 4.0 4.0 Dye Solution, 1% 0.4 Water Q.S. Q.S. Q.S. Q.S. Q.S.
The above second composition examples can be made as follows: Dissolve water-soluble materials in water to create aqueous phase and heat to 80° C. The oil soluble materials are then added with agitation. Add the non-ionic emulsifier with increased agitation and mix for 20 minutes at 85° C. Cool the mixture to 65° C. and homogenize briefly. Next, add the pH adjuster/buffering agent and then the phosphoric acid. Cool mixture to 40-42° C. and then add the hydrogen peroxide. The polymer/thickener, if one is desired, can then be added. Homogenize the final mixture at 38-40° C. to a smooth cream consistency, having a target final viscosity of 35,000-55,000 cst using an RVT spindle #6 at 1 minute and 10 rpm.
[0032] Three samples of first and second compositions, as described herein, were made and evaluated for foam/lather sustainment upon dispensing and mixing the two compositions. The figure illustrates the foam volume dynamics beginning at time zero and extending out to 5 minutes. As one can see from the figure, the samples substantially maintained the level of foam from a 30 second time measurement point to a five minute time measurement point.
[0033] The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”
[0034] All documents cited in the Detailed Description of the Invention are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention. To the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
[0035] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
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Non-pressurized shaving compositions are described that provide a warm/hot sensation during use as the result of an exothermic redox reaction. The compositions are post-foaming via nascent gas release in situ due to the generation of carbon dioxide. The carbon dioxide induced foam is maintained for several minutes after the compositions are dispensed, whereby the compositions are capable of providing both a warm sensation and sustained lather, a balance which heretofore has been a significant challenge.
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FIELD OF THE INVENTION
[0001] The present invention relates to processes for the preparation of (R)-1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanol, 1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanone, and intermediates thereof, which are useful in the synthesis of inhibitors of TPH1 for the treatment of, for example, gastrointestinal, cardiovascular, pulmonary, inflammatory, metabolic, low bone mass diseases, serotonin syndrome, and cancer.
BACKGROUND OF THE INVENTION
[0002] Two vertebrate isoforms of TPH, namely TPH1 and TPH2, have been identified. TPH1 is primarily expressed in the pineal gland and non-neuronal tissues, such as enterochromaffin (EC) cells located in the gastrointestinal (GI) tract. TPH2 (the dominant form in the brain) is expressed exclusively in neuronal cells, such as dorsal raphe or myenteric plexus cells. TPH catalyzes the hydroxylation of tryptophan in the biosynthesis of 5-HT. Thus, the pharmacological effects of 5-HT can be modulated by agents affecting TPH.
[0003] TPH1 inhibitors are known in the art. Spirocyclic compounds disclosed in U.S. Ser. No. 14/477,948, filed Sep. 5, 2014, can inhibit TPH1 and were found to reduce peripheral serotonin levels in animal models. The preparation of these compounds can include the coupling of an alcohol with a chloro-substituted heteroaromatic compound in the presence of base to yield an ether intermediate that can be used to make the final TPH1 inhibitor product. A particular chiral alcohol useful in the synthesis of TPH1 inhibitors is (R)-1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanol (see Formula A below). According to U.S. Ser. No. 14/477,948, this chiral alcohol is made by the coupling of phenyl boronic acid with (R)-1-(2-bromo-4-chlorophenyl)-2,2,2-trifluoroethanol. Alternative processes for the preparation of the compound of Formula A are provided herein.
SUMMARY OF THE INVENTION
[0004] The present invention provides processes for preparing (R)-1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanol (Formula A) and 1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanone (Formula B):
[0000]
[0000] as described herein.
DETAILED DESCRIPTION
[0005] The present invention provides processes for preparing (R)-1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanol (Formula A) and 1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanone (Formula B) as set out, for example, in Scheme I, wherein X is selected from Br and I.
[0000]
[0006] In some embodiments, the invention relates to a process for preparing a compound of Formula A:
[0000]
[0000] comprising, reacting a compound of Formula 1-4:
[0000]
[0000] wherein X is selected from Br and I, with phenylboronic acid to produce the compound of Formula A.
[0007] In some aspects of these embodiments, X is I. In other aspects of these embodiments, X is Br.
[0008] In some aspects of these embodiments, the reacting can be carried out under Suzuki coupling conditions such as in the presence of a Pd catalyst, for example, Pd 2 (dppf)Cl 2 . In further aspects of these embodiments, the reacting can be carried out in the presence of a solvent comprising, for example, dioxane and/or aqueous sodium carbonate. In further aspects of these embodiments, to facilitate the reacting, the coupling can be carried out at elevated temperature such as from 80 to 100° C. or at about 90° C.
[0009] In some embodiments, the compound of Formula 1-4:
[0000]
[0010] wherein X is selected from Br and I,
[0011] is prepared by reducing a compound of Formula 1-3:
[0000]
[0012] in the presence of a chiral catalyst.
[0013] In some aspects of these embodiments, X is I. In other aspects of these embodiments, X is Br.
[0014] In some aspects of these embodiments, the chiral catalyst comprises iridium such as the Ir catalyst that can be prepared by combining dichloro(pentamethylcyclopentadienyl)iridium(III) dimer with (1R, 2R)-(−)-N-(4-toluenesulfonyl)-1,2-diphenylethylenediamine. In some aspects of these embodiments, the reduction is carried out at elevated temperature such as at about 30-50° C. or at about 40° C. In further aspects of these embodiments, the reduction is carried out in the presence of formate as a reductant. The formate can be in the form of salt such as a potassium salt or sodium salt. In further aspects of these embodiments, the reduction is carried out in the presence of a solvent which, for example, can comprise acetonitrile.
[0015] In some embodiments, the compound of Formula 1-3:
[0000]
[0016] wherein X is selected from Br and I,
[0017] is prepared by combining a compound of Formula 1-2:
[0000]
[0018] with trifluoromethyltrimethylsilane (TMSCF 3 ).
[0019] In some aspects of these embodiments, X is I. In other aspects of these embodiments, X is Br.
[0020] In some aspects of these embodiments, the combining is carried out in the presence of CsF. In further aspects of these embodiments, the combining is carried out at a reduced temperature such as at about −10 to 10° C., or at about 0° C. In further aspects of these embodiments, the combining is carried out in the presence of a solvent optionally comprising, for example, an aromatic solvent like toluene. In further aspects of these embodiments, the combining further comprises the step of adding tetra-n-butylammonium fluoride (TBAF), for example, after the compound of Formula 1-2 is combined with TMSCF 3 .
[0021] In some embodiments, the compound of Formula 1-2:
[0000]
[0022] wherein X is selected from Br and I,
[0023] is prepared by coupling a compound of Formula 1-1:
[0000]
[0024] with N,O-dimethylhydroxylamine hydrochloride.
[0025] In some aspects of these embodiments, X is I. In other aspects of these embodiments, X is Br.
[0026] In some aspects of these embodiments, the coupling is carried out in the presence of a tertiary amine such as triethylamine (TEA). In further aspects of these embodiments, the coupling is carried out in the presence of a peptide coupling reagent such as (1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate) (HATU). In further aspects of these embodiments, the coupling is carried out using oxalyl chloride. In further aspects of these embodiments, the coupling is carried out in the presence of a solvent optionally comprising, for example, dimethylformamide (DMF), or, for example, dichloromethane (CH 2 Cl 2 ).
[0027] In some embodiments, the invention relates to a process for preparing a compound of Formula B:
[0000]
[0000] wherein X is selected from Br and I,
comprising reacting a compound of Formula 1-3:
[0000]
[0000] with phenylboronic acid to produce the compound of Formula B;
[0028] In some aspects of these embodiments, X is I. In other aspects of these embodiments, X is Br.
[0029] In some aspects of these embodiments, the reacting can be carried out under Suzuki coupling conditions such as in the presence of a Pd catalyst, for example, Pd 2 (dppf)Cl 2 . In further aspects of these embodiments, the reacting can be carried out in the presence of a solvent comprising, for example, dioxane and/or aqueous sodium carbonate. In further aspects of these embodiments, to facilitate the reacting, the coupling can be carried out at elevated temperature such as from 80 to 100° C. or at about 90° C.
[0030] In some embodiments, the invention relates to a process for preparing a compound of Formula A:
[0000]
[0031] comprising reducing a compound of Formula B:
[0000]
[0032] in the presence of a chiral catalyst.
[0033] In some aspects of these embodiments, the chiral catalyst comprises iridium such as the Ir catalyst that can be prepared by combining dichloro(pentamethylcyclopentadienyl)iridium(III) dimer with (1R, 2R)-(−)-N-(4-toluenesulfonyl)-1,2-diphenylethylenediamine. In further aspects of these embodiments, the reduction is carried out at elevated temperature such as at about 30-50° C. or at about 40° C. In further aspects of these embodiments, the reduction is carried out in the presence of formate as a reductant. The formate can be in the form of salt such as a potassium salt or sodium salt. In further aspects of these embodiments, the reduction is carried out in the presence of a solvent which, for example, can comprise acetonitrile.
[0034] In some embodiments, the present invention is directed to a compound of Formula A prepared by a process described herein.
[0035] In some embodiments, the invention is directed to a compound of Formula B:
[0000]
[0036] In some embodiments, the invention is directed to a compound of Formula B prepared by a process described herein.
[0037] In some embodiments, the invention is directed toward a compound of Formula 1-4:
[0000]
[0038] wherein X is selected from Br and I.
[0039] In some aspects of these embodiments, X is I. In other aspects of these embodiments, X is Br.
[0040] In some embodiments, the invention is directed to a compound of Formula 1-4 prepared by a process described herein.
[0041] In some embodiments, the invention is directed toward a compound of Formula 1-3:
[0000]
[0042] wherein X is selected from Br and I.
[0043] In some aspects of these embodiments, X is I. In other aspects of these embodiments, X is Br.
[0044] In some embodiments, the invention is directed to a compound of Formula 1-3 prepared by a process described herein.
[0045] In some embodiments, the invention is directed toward a compound of Formula 1-2:
[0000]
[0046] wherein X is selected from Br and I.
[0047] In some aspects of these embodiments, X is I. In other aspects of these embodiments, X is Br.
[0048] In some embodiments, the invention is directed to a compound of Formula 1-2 prepared by a process described herein.
[0049] It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, can also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, can also be provided separately or in any suitable subcombination. While certain of the processes steps are illustrated in Scheme I above, it is intended that the individual process steps may be claimed individually or in any combination. It is not intended that the processes be limited to an overall process having each and every step depicted in Scheme I.
[0050] The term “compound,” as used herein, is meant to include all stereoisomers, geometric isomers, tautomers, and isotopes of the structures depicted. Compounds herein identified by name or structure as one particular tautomeric form are intended to include other tautomeric forms unless otherwise specified. Compounds herein identified by name or structure without specifying the particular configuration of a stereocenter are meant to encompass all the possible configurations at the stereocenter. For example, if a particular stereocenter in a compound of the invention could be R or S, but the name or structure of the compound does not designate which it is, than the stereocenter can be either R or S.
[0051] The term “compound,” as used herein, is further meant to include all isotopes of atoms occurring in the structures depicted. Isotopes include those atoms having the same atomic number but different mass numbers. For example, isotopes of hydrogen include tritium and deuterium.
[0052] In some embodiments, the compounds disclosed herein are substantially isolated. By “substantially isolated” is meant that the compound is at least partially or substantially separated from the environment in which it was formed or detected. Partial separation can include, for example, a composition enriched in the compounds of the invention. Substantial separation can include compositions containing at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, or at least about 99% by weight of the compounds of the invention, or salt thereof.
[0053] As used herein, the phrase “elevated temperature” refers to a temperature higher than about room temperature (20-26° C.).
[0054] As used herein, the phrase “reduced temperature” refers to a temperature lower than about room temperature.
[0055] As used herein, the phrase “Suzuki coupling conditions” refers to reaction conditions that result in the formation of a carbon-carbon bond between aromatic moieties, one of which includes a halogen substituent and the other which includes a boronic acid or boronate substituent, where the reaction is carried out in the presence of a Pd(0) catalyst.
[0056] As used herein, the phrase “chiral catalyst” is a substance that pushes a reaction to favor one stereoisomer over another. In some embodiments, the chiral catalyst is a chiral coordination complex, such as a chiral coordination complex of iridium.
[0057] The present application also includes salts of the compounds described herein. In some embodiments, the salts are pharmaceutically acceptable salts which are conventional non-toxic salts of the parent compound formed, for example, from non-toxic inorganic or organic acids. Lists of suitable salts are found in Remington's Pharmaceutical Sciences, 17 th ed., Mack Publishing Company, Easton, Pa., 1985, p. 1418 and Journal of Pharmaceutical Science, 66, 2 (1977), each of which is incorporated herein by reference in its entirety. The phrase “pharmaceutically acceptable” is employed herein to refer to those compounds, materials, compositions, and/or dosage forms which are, within the scope of sound medical judgment, suitable for use in contact with the tissues of human beings and animals without excessive toxicity, irritation, allergic response, or other problem or complication, commensurate with a reasonable benefit/risk ratio.
[0058] The processes described herein can be monitored according to any suitable method known in the art. For example, product formation can be monitored by spectroscopic means, such as nuclear magnetic resonance spectroscopy (e.g., 1 H or 13 C), infrared spectroscopy, spectrophotometry (e.g., UV-visible), or mass spectrometry; or by chromatography such as high performance liquid chromatography (HPLC) or thin layer chromatography. The compounds obtained by the reactions can be purified by any suitable method known in the art. For example, chromatography (medium pressure) on a suitable adsorbent (e.g., silica gel, alumina and the like), HPLC, or preparative thin layer chromatography; distillation; sublimation, trituration, or recrystallization. The purity of the compounds, in general, are determined by physical methods such as measuring the melting point (in case of a solid), obtaining a NMR spectrum, or performing a HPLC separation. If the melting point decreases, if unwanted signals in the NMR spectrum are decreased, or if extraneous peaks in an HPLC trace are removed, the compound can be said to have been purified. In some embodiments, the compounds are substantially purified.
[0059] Preparation of compounds can involve the protection and deprotection of various chemical groups. The need for protection and deprotection, and the selection of appropriate protecting groups can be readily determined by one skilled in the art. The chemistry of protecting groups can be found, for example, in Wuts and Greene, Greene's Protective Groups in Organic Synthesis, 4 th Ed., John Wiley & Sons: New York, 2006, which is incorporated herein by reference in its entirety.
[0060] The reactions of the processes described herein can be carried out in suitable solvents which can be readily selected by one of skill in the art of organic synthesis. Suitable solvents can be substantially non-reactive with the starting materials (reactants), the intermediates, or products at the temperatures at which the reactions are carried out, i.e., temperatures which can range from the solvent's freezing temperature to the solvent's boiling temperature. A given reaction can be carried out in one solvent or a mixture of more than one solvent. Depending on the reaction step, suitable solvent(s) for that particular reaction step can be selected. Example solvents include water, alkanes (such as pentanes, hexanes, heptanes, cyclohexane, etc., or a mixture thereof), aromatic solvents (such as benzene, toluene, xylene, etc.), alcohols (such as methanol, ethanol, isopropanol, etc.), ethers (such as dialkylethers, methyl tent-butyl ether (MTBE), tetrahydrofuran (THF), dioxane, etc.), esters (such as ethyl acetate, butyl acetate, etc.), halogenated hydrocarbon solvents (such as dichloromethane (DCM), chloroform, dichloroethane, tetrachloroethane), dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetone, acetonitrile (ACN), hexamethylphosphoramide (HMPA) and N-methyl pyrrolidone (NMP). Such solvents can be used in either their wet or anhydrous forms.
EXAMPLES
[0061] The invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of non-critical parameters which can be changed or modified to yield essentially the same results.
[0062] 1 H NMR Spectra were acquired on a Varian Mercury Plus 400 MHz spectrometer. For typical 1 H NMR spectra, the pulse angle was 45 degrees, 8 scans were summed and the spectral width was 16 ppm (−2 ppm to 14 ppm). Typically, a total of about 32768 complex points were collected during the 5.1 second acquisition time, and the recycle delay was set to 1 second. Spectra were collected at 25° C. 1 H NMR Spectra were typically processed with 0.3 Hz line broadening and zero-filling to about 131072 points prior to Fourier transformation. Chemical shifts were expressed in ppm relative to tetramethylsilane. The following abbreviations are used herein: br=broad signal, s=singlet, d=doublet, dd=double doublet, ddd=double double doublet, dt=double triplet, t=triplet, td=triple doublet, tt=triple triplet q=quartet, m=multiplet.
[0063] Liquid chromatography—mass spectrometry (LCMS) experiments to determine retention times and associated mass ions were performed using an Agilent Zorbax Bonus RP (reverse phase) column, 2.1×50 mm, 3.5 μm particle size, at a temperature of 50° C. and at a flow rate of 0.8 mL/min, 2 μL injection, mobile phase: (A) water with 0.1% formic acid and 1% acetonitrile, mobile phase (B) MeOH with 0.1% formic acid; retention time given in minutes. Method details: (I) ran on a Binary Pump G1312Bwith UV/Vis diode array detector G1315C and Agilent 6130 mass spectrometer in positive and negative ion electrospray mode with UV-detection at 220 and 254 nm with a gradient of 50-95% (B) in a 2.5 min linear gradient (II) hold for 0.5 min at 95% (B) (III) decrease from 95-5% (B) in a 0.1 min linear gradient (IV) hold for 0.29 min at 5% (B).
Example 1
Preparation of (R)-1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanol (Formula A)
[0064]
[0065] The compound of Formula A was prepared as described below (see also Scheme I above) using synthetic intermediates 1-1, 1-2, 1-3, and 1-4.
[0000] Step 1: 4-chloro-2-iodo-N-methoxy-N-methylbenzamide (1-2, X=I)
[0000]
[0066] To a solution of 4-chloro-2-iodobenzoic acid (1-1, X=I) (CAS#:13421-13-1; Aldrich, SKU: 560146) (3 g, 10.62 mmol) and N,O-dimethylhydroxylamine hydrochloride (CAS#: 6638-79-5; Sigma Aldrich, SKU: D163708) (1.2 g, 12.31 mmol) in dimethylformamide (DMF) (30 mL), was added dropwise triethyl amine (TEA) (7.4 mL, 53.14 mmol), followed by the addition of (1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate) (HATU) (6.1 g, 16.05 mmol). The reaction mixture was stirred at RT for 16 h and then diluted with CH 2 Cl 2 and H20, and the aqueous layer was extracted with CH 2 Cl 2 (4×20 mL). The combined organic layers were washed with brine, dried over Na 2 SO 4 , filtered, concentrated in vacuo and purified by silica gel chromatography (ethyl acetate/hexanes 1:4) to afford the title compound as a white solid (3.2 g. LCMS (MH+): 325.9. 1 H NMR (400 MHz, CDCl 3 -d): δ3.11-3.38 (m, 3H), 3.47-3.90 (m, 3H), 7.20 (d, J=8 Hz,1H), 7.37 (d, J=2 Hz, 1H), 7.84 (s,1H).
[0000] Step 2: 1-(4-chloro-2-iodophenyl)-2,2,2-trifluoroethanone (1-3, X=I)
[0000]
[0067] To a solution of 4-chloro-2-iodo-N-methoxy-N-methylbenzamide (1-2, X =I) (Prepared in Step 1: 1.9 g, 5.84 mmol) and CsF (222 mg, 1.46 mmol) in toluene (5 mL), was added dropwise trifluoromethyltrimethylsilane (TMSCF3) (2.2 mL, 14.88 mmol) at 0° C. The reaction mixture was then warmed to RT and stirred at that temperature for 20 h. Then, water (6 mL) and tetra-n-butylammonium fluoride (TBAF) (6 mL, 1 M in THF) were added to the reaction mixture, and the reaction mixture was heated to 50° C. for 2 h. The reaction mixture was then cooled to RT and extracted with ethyl acetate (3×20 mL). The combined organic layers were washed with brine, dried over Na 2 SO 4 , filtered, concentrated in vacuo and purified by silica gel chromatography (100% hexanes) to provide the title compound as a yellow oil (1.39 g). LCMS (MH+): 334.9. 1 H NMR (400 MHz, CDCl 3 -d): δ7.51 (dd, J=10, 6 Hz,1H), 7.37 (dd, J=10, 7 Hz, 1H), 7.84 (d, J=2 Hz,1H).
[0000] Step 3: (R)-1-(4-chloro-2-iodophenyl)-2,2,2-trifluoroethanol (1-4)
[0000]
[0068] To a solution of 1-(4-chloro-2-iodophenyl)-2,2,2-trifluoroethanone (1-3, X=I) (Prepared in Step 2; 4.0 g, 11.9 mmol) in CH 3 CN (20 mL) was added chiral iridium catalyst (20 mL of a 0.1 mM aqueous solution, prepared by mixing dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (CAS#: 12354-84-6, 4.0 mg, 0.005 mmol) and (1R, 2R)-(−)-N-(4-toluenesulfonyl)-1,2-diphenylethylenediamine (CAS# 144222-34-4, Strem Chemicals catalogue #07-2371, 3.6 mg, 0.009 mmol) in water (40 mL) and heating the resultant mixture to 40° C. for 3 h). The reaction mixture was then charged with potassium formate (HCOOK) (5.03 g, 59.80 mmol), and heated at 40° C. for 12 h. Then the reaction mixture was cooled to RT and diluted with ethyl acetate and saturated aqueous solution of NaCl. Layers were separated and the aqueous layer was extracted with ethyl acetate (4×30 mL). The combined organic layers were washed with brine, dried over Na 2 SO 4 , filtered, and concentrated in vacuo to afford the title compound as a yellow solid (4.1 g, crude) that was used in the following steps without further purification. LCMS (MH+): 336.9. 1 H NMR (400 MHz, CDCl 3 -d): δ3.5 (bs, 1H), 5.10 (dd, J=10 Hz, 6 Hz, 1H), 7.29 (dd, J=10, 6 Hz,1H), 7.45 (dd, J=10, 7 Hz,1H),7.71 (d, J=2 Hz,1H).
[0069] Confirmation of the (R) configuration was confirmed by Mosher Ester analysis. To a solution of (R)-1-(4-chloro-2-iodophenyl)-2,2,2-trifluoroethanol (50 mg, 0.15 mmol) in tetrahydrofuran (THF) (1 mL, anhydrous) was added 4-dimethylaminopyridine (23 mg, 0.19 mmol) and (R)-(−)-α-methoxy-α-(trifluoromethyl)phenylacetyl chloride (36 μL, 0.19 mmol). The resulting mixture was stirred at room temperature for 1 h then filtered. The filtrate was concentrated and purified by preparative thin layer chromatography (TLC) (ethyl actate:hexanes/1:40) to afford (R)-(R)-1-(4-chloro-2-iodophenyl)-2,2,2-trifluoroethyl 3,3,3-trifluoro-2-methoxy-2-phenylpropanoate (50 mg, 0.09 mmol, 98% e.e. which was confirmed by 1 H NMR).
[0000] Step 4: (R)-1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanol (Formula A)
[0070] A solution of (R)-1-(4-chloro-2-iodophenyl)-2,2,2-trifluoroethanol (1-4) (3.1 g, 9.21 mmol), phenylboronic acid (CAS#: 98-80-6; Sigma Aldrich, SKU P20009) (1.2 g, 10.2 mmol), and Pd(dppf)Cl 2 (CAS#72287-26-4; Sigma Aldrich SKU: 697230) (337 mg, 0.46 mmol) in dioxane (30.0 mL) and Na 2 CO 3 (10.0 mL, 2.0 M aqueous solution) was purged with Na three times, and the resultant reaction mixture was heated to 90° C. for 2 h. The reaction mixture was then cooled to RT and diluted with CH 2 Cl 2 and water. Layers were separated and the aqueous layer was extracted with CH 2 Cl 2 (3×50 mL). The combined organic layers were washed with brine, dried over Na 2 SO 4 , filtered, and purified by silica gel chromatography (ethyl actate/hexanes 1/10) to afford the title compound as a white solid (2.4 g over 2 steps). 1 H NMR (400 MHz, CDCl 3 -d): δ3.51 (m, 1H), 5.08-5.13 (q, J=20, 7 Hz,1H),7.26-7.30 (m,4H), 7.42-7.46 (m, 3H), 7.70 (d,J=8 Hz,1H). The (R) configuration of the title product was confirmed by Mosher Ester analysis (98% e.e.) as described above for the product of Step 1: (R)-1-(4-chloro-2-iodophenyl)-2,2,2-trifluoroethanol.
Example 2
Preparation of 1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanone (Formula B)
[0071]
[0072] The compound of Formula B was prepared as described below (see also Scheme I above) using synthetic intermediates 1-1, 1-2, and 1-3.
[0000] Step 1: 4-chloro-2-iodo-N-methoxy-N-methylbenzamide (1-2, X=I)
[0000]
[0073] To a solution of 4-chloro-2-iodobenzoic acid (1-1, X=I) (296 g, 1.1 mol) in CH 2 Cl 2 (3 L) and DMF (2 mL) was added oxalyl dichloride (266.1 g, 2.1 mol) dropwise at 0° C. over a period of 1 h. The resultant reaction mixture was stirred at 0° C. for 2 h and then concentrated in vacuo. The residue was dissolved in CH 2 Cl 2 and concentrated twice. Then the residue was dissolved in CH 2 Cl 2 (1 L) and cooled to 0° C., followed by the dropwise addition of a mixture of N,O-dimethylhydroxylamine hydrochloride (Sigma Aldrich, SKU: D163708; 112.4 g, 1.15 mol) in CH 2 Cl 2 (1 L) and triethyl amine (1 L, 3.15 mol) at 0° C. over a period of 1 h. The reaction mixture was then warmed to RT and stirred at that temperature for 16 h. After this time, the mixture was diluted with H 2 O and the aqueous layer was extracted with CH 2 Cl 2 . The combined organic layers were washed with brine, dried over Na 2 SO 4 , filtered, concentrated in vacuo and purified by silica gel chromatography (ethyl acetate/hexanes 1/4) to afford the title compound (320 g) as a white solid LCMS (MH+): 325.9. 1 H NMR (400 MHz, CDCl 3 -d): δ3.11-3.38 (m, 3H), 3.47-3.90 (m, 3H), 7.20 (d, J=8 Hz, 1H), 7.37 (d, J=2 Hz, 1H), 7.84 (s, 1H).
[0000] Step 2: 1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanone (Formula B)
[0074] A solution of 1-(4-chloro-2-iodophenyl)-2,2,2-trifluoroethanone (1-3, X=I, prepared in Example 1, Step 2) (145 g, 0.43 mol), phenylboronic acid (CAS#: 98-80-6; Sigma Aldrich, SKU P20009; 55.5 g, 0.455 mol) and Pd(dppf)C12 (CAS#72287-26-4; Sigma Aldrich SKU: 697230; 9.5 g, 0.013 mol) in dioxane (1450 mL) and Na 2 CO 3 (435 mL, 2.0 M aqueous solution) was purged with Na and stirred at 90° C. for 2 h. After this time, the reaction mixture was cooled to RT and then diluted with H 2 O. Layers were separated and the aqueous layer was extracted with ethyl acetate and the combined organic layers were washed with brine, dried over Na 2 SO 4 , filtered, concentrated in vacuo and purified by silica gel chromatography (100% hexanes) to afford the title compound (115 g) as a white solid. LCMS (MH+): 284.66. 1 H NMR (400 MHz, CDCl 3 -d): δ7.23-7.27 (m, 2H), 7.42-7.44 (m, 3H), 7.47-7.49 (m, 2H), 7.67-7.70 (m,1H)
Example 3
Preparation of (R)-1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanol (Formula A)
[0075]
[0076] The compound of Formula A was prepared as described below (see also Scheme I above) using the compound of Formula B as synthetic starting material.
[0077] To a 22 L 3-necked reactor, fitted with a mechanical stirrer, a temperature probe, and a N 2 inlet, were charged sequentially dichloro(pentamethyl cyclopentadienyl)iridium (III) dimer ([Cp*IrCl2]2, 1.52 g, 1.90 mmol, CAS: 12354-84-6), (1R,2R)-(−)-(4-toluenesulfonyl)-1,2-diphenylethylenediamine (1.52 g, 4.15 mmol, CAS: 144222-34-4, Strem Chemicals catalogue #07-2371) and water (8 L) at RT. The resulting reaction mixture was heated to 40° C. for 3 h to provide a homogeneous orange solution. To this active catalyst solution at the current temperature (40° C.), was added potassium formate (1476 g, 17.55 mol), and a solution of 1-(2-phenyl-4-chlorophenyl)-2,2,2-trifluoroethanone (compound of Formula B prepared in Example 2) (1000 g, 3.51 mol) in CH 3 CN (8 L). The reaction mixture was then stirred at 40° C. for 2 h and then cooled to RT and the layers were separated. The aqueous layer was extracted with MTBE (2×3 L) and the combined organic layers were dried over Na 2 SO 4 , filtered, and concentrated in vacuo to provide (R)-1-(2-phenyl-4-chlorophenyl)-2,2,2-trifluoroethanol (1006 g) as a thick yellow oil used without further purification.
[0078] Various modifications of the invention, in addition to those described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. Each reference, including all patent, patent applications, and publications, cited in the present application is incorporated herein by reference in its entirety.
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The present invention relates to processes for the preparation of (R)-1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanol, 1-(5-chloro-[1,1′-biphenyl]-2-yl)-2,2,2-trifluoroethanone, and intermediates thereof, which are useful in the preparation of inhibitors of TPH1 for the treatment of, for example, gastrointestinal, cardiovascular, pulmonary, inflammatory, metabolic, low bone mass diseases, serotonin syndrome, and cancer.
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FIELD OF THE INVENTION
[0001] The present invention is a tool and a method for use of the tool to assist in the application of a flowable substance and more specifically, is an actuator for sealing a bag into which the flowable substance is placed to assist in forcing the flowable substance therefrom.
BACKGROUND OF THE INVENTION
[0002] Flowable substances such as mortar are used to fill gaps such as between bricks in a facade. For example in the case of a brick facade that is being built or subsequently pointed, the gap must have mortar, or more particularly masonry cement, forced into the gap to the width of the brick. Generally, the process of filing the gap involves using a trowel to push mortar off a mortarboard into the gap. This process is labor intensive utilizing highly skilled labor and is extremely time consuming.
[0003] In addition, as the mortar is pushed into the gap, it is inevitable that some mortar will spill over onto the face of the brick, i.e. a finished surface of the brick that is viewed. Removal of the mortar from the face can be difficult sometimes involving an acid and potentially damaging to the brick as well as the mortar. This cleaning process is not only potentially dangerous but also expensive.
[0004] New brick products developed for architectural applications also have gaps that must be filled with mortar. Facade brick mounted on a sheet are one example. Sheet mounted facade brick comprises some number of brick faces, i.e. thin bricks, mounted on a single sheet with proper spacing. Installation of the product involves mounting the sheet to a surface and filling the gaps between the brick faces with mortar. The finished surface is therefore an actual brick face and mortar, and the finished surface cannot be distinguished from a normal brick facade. The placement of the mortar within the gaps has the associated problems discussed above.
[0005] Bags have been developed for pushing mortar into gaps. The bags are shaped like a frustum of a cone, i.e. conical with a large opening at one end tapering to small opening at the other end. Mortar is placed in the bag through the large opening and the large opening is folded; e.g., twisted, etc. The folding of the bag simultaneously seals the large opening and puts pressure on the mortar in the bag forcing the mortar to exit the bag through the small opening. As those who have ever used such a bag can attest, forcing the material from the bag requires considerable strength, and it can be difficult to control the outflow of the flowable substance through the small opening.
[0006] Based on the foregoing, it is an objective of the present invention to provide a tool and a method of use to overcome the problems associated with the prior art.
SUMMARY OF THE INVENTION
[0007] The invention is an actuator that facilitates the use of a bag having two openings into which a flowable substance can be placed. More specifically, the actuator is placed across the bag clamping one of the openings shut after which the actuator is progressively rotated whereby the bag rolls up about the actuator putting pressure on the flowable substance therein such that it is forced out of the bag through the other opening. The actuator includes a base that has a body with a handle that has a shape that permits a torque, i.e. leverage, to be applied to the body. The leverage gives a mechanical advantage during rolling to assist in rotating the actuator thereby giving a more continuous and constant pressure on the flowable substance therein for a uniform flow of the flowable substance through the other opening. An arm is attached to the base by a hinge such that the arm and base can be placed generally parallel one to the other and define a slot. The arm is secured to the base by a clasp. In one embodiment, the arm and body are hinged at one end and the clasp secures the other end of the arm to the other end of the body. In this embodiment, the arm, body, and clasp define the slot.
[0008] In a mortar applicator, a bag is placed in the slot of the actuator. The bag, which has a large and a small opening and mortar therein, is placed in the actuator such that the actuator clamps shut the large opening of the bag effectively trapping the mortar in the bag between the actuator and the small opening. The bag is designed to hold mortar and the actuator should clamp the bag sufficiently to prevent the mortar from exiting the bag through the large opening. In the preferred embodiment, the bag would only be partially filled such that the actuator could be placed on the bag and rotated through at least one revolution prior to exerting any pressure on the mortar. Therefore, the sealing of the bag to prevent the mortar from exiting the bag through the large opening could be accomplished by the actuator cooperating with the bag folded about it.
[0009] It is preferred, but not required, that the bag be conical shaped with two openings making the bag a frustum of cone. The size of the cone as well as the openings is application dependent.
[0010] The slot of the actuator should be sufficient to accommodate the entire bag where the clamp is to be placed on the bag. The actuator is advantageously placed perpendicular to the longitudinal axis of the bag. Further, it is preferred that the slot be at least as long as the bag is wide. For a frustum of cone bag, the width of the bag is the distance across the large opening when the bag is laid flat. This will assure that when the bag is rolled around the actuator all of the contents of the bag will receive uniform pressure.
[0011] In the method of using the mortar applicator, a bag is obtained having a large and small opening. Mortar is placed in the bag through the large opening and then the large opening is sealed with the actuator. The actuator is then rotated thereby rolling the bag up around the actuator. As the bag is rolled up, pressure is exerted on the mortar therein forcing the mortar to exit the bag through the small opening.
[0012] While the present invention has been discussed in the context of mortar, any flowable substance such cement, grout, or plaster could be used. It should be remembered, however, that the viscosity of the flowable substance is application dependent and ideally the viscosity of the flowable substance should be such that the substance is generally forced from the bag as opposed to naturally flows out of the bag, if conditions permitted it.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] [0013]FIG. 1 is a perspective view of the actuator of the present invention.
[0014] [0014]FIG. 2 is a perspective view of the actuator of FIG. 1 with a bag positioned therein.
[0015] [0015]FIG. 3 is a side view of the actuator and bag of FIG. 2 with a flowable substance in the bag and the actuator rotated one revolution.
DETAILED DESCRIPTION OF THE INVENTION
[0016] As shown in FIG. 1 the actuator generally referred to by reference number 10 is comprised of a base 12 hingeably connected to an arm 14 . The base 12 includes a body 16 coupled to a handle 18 . The hinge 20 is integrated into the handle 18 . The body 16 and the arm 14 are held together by a clasp 22 , and the body 16 , the arm 14 , and the clasp 22 cooperate to define a slot 24 . The handle 18 is shaped such that a moment arm 26 (depicted with dotted lines) is created about a rotational axis 28 thereby permitting a torque to be applied to the actuator 10 . The clasp 22 is an L-shaped body that is pivotally connected to the body 16 and rotates as indicated by the arrow R 1 .
[0017] The moment arm 26 permits a mechanical advantage in rotating the actuator 10 . This mechanical advantage reduces the overall force that must be applied thereby allowing for a more consistent and uniform flow of the flowable substance from a bag, discussed below.
[0018] In FIG. 2, a bag 30 has been placed in the slot 24 of the actuator 10 . The bag 30 is conically shaped having a large opening 32 and a small opening 34 . In use, a flowable substance (not shown) would be placed in the bag 30 through the large opening 32 and the actuator 10 would secure the flowable substance in the bag 30 , i.e. prevent the flowable substance from exiting the bag 30 through the large opening 32 . The slot 24 is sized to clamp the bag 30 thereby sealing the large opening 32 . The seal is not a hermitic, but is sufficient to prevent the back flow of the flowable substance in the bag 30 . In sealing the bag 30 it must be remembered that the bag 30 rotates about actuator 10 (see FIG. 3) in operation. The folding of the bag 30 resulting from the rotation can assist in sealing the bag 30 , therefore, the seal provided by the actuator 10 could be minimal.
[0019] The slot 24 of the actuator 10 should be sufficient to accommodate the entire bag where the actuator 10 is to be placed. The actuator 10 is advantageously placed perpendicular to the longitudinal axis of the bag 30 . Further, it is preferred that the slot 24 be at least as long as the bag 30 is wide. For a conical bag 30 , the width of the bag 30 is the distance across the large opening 32 when the bag 30 is laid flat. This will assure that when the bag 30 is rolled around the actuator 10 , all of the contents of the bag 30 receives uniform pressure.
[0020] Continuing with FIG. 3, a flowable substance 36 is positioned within the bag 30 , and the bag 30 is positioned in the slot 24 . In this figure, the actuator 10 has been rotated one revolution about a rotational axis R 2 such that the actuator 10 is putting pressure on the flowable substance 36 such that the flowable substance 36 is forced out through the smaller opening 34 . It is important that the smaller opening 34 be sized appropriately. The flowable substance 36 will have a viscosity. The smaller opening 34 should be sized considering the viscosity such that the flowable substance 36 is generally retained in the bag 30 even through the smaller opening 34 is positioned at a point below the flowable substance 36 , i.e. the flowable substance 36 should be generally forced out of the bag 30 and not merely flow out.
[0021] It is preferred that the bag 30 is a frustum of cone. The size of the cone and the openings therein are application dependent. The small opening should be sized based on the viscosity of the flowable substance such that the flowable substance is forced from the bag as opposed to naturally flows from the bag.
[0022] Referring to FIGS. 1, 2, and 3 , the method of the present invention involves obtaining a bag 30 having two opening 32 and 34 , one larger than the other. Obtaining an actuator 10 having a base 12 with a body 16 and a handle 18 wherein the handle 18 has a shape to permit a torque to be applied to the body 16 , and an arm 14 hingeably connected to the base 12 wherein the body 16 and the arm 14 cooperate to define a slot 24 . The body 16 and the arm 14 also have a clasp 22 for securing the arm 14 relative to the body 16 .
[0023] A flowable substance 36 is placed in the bag 30 through the larger opening 32 . The actuator 10 is attached to the bag 30 at a position adjacent the large opening 32 , thereby trapping the flowable substance 36 within the bag 30 . The actuator 10 should be placed such that the bag 30 will roll up nicely about the actuator 10 , i.e. within the length of the actuator 10 . In the case of a conical shaped bag 30 , the actuator 10 would be advantageously placed along a circular cross-section.
[0024] The actuator 10 is then rotated thereby rolling the bag 30 up about the actuator 10 in the direction of the smaller opening 34 . The rolling up of the bag 30 puts pressure on the flowable substance 36 therein, thereby forcing the flowable substance 36 out through the smaller opening 34 . As those skilled in the art will appreciate, the order of the steps above is not necessary required. As an example, the actuator 10 could be obtained after the flowable substance 36 is placed in the bag 30 ; therefore, the order of the steps should not be considered limiting unless required.
[0025] Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible. For example, while frustum of cone bags have been shown other shaped bags with two openings are considered within the scope of the invention. As an another example, the preferred embodiment of the slot 24 is described within the Detailed Description as being formed between the body 16 and an arm 14 . In alternative embodiments, a slot 24 can be disposed within the body 16 , thereby avoiding the use of an arm 14 . Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred version contained herein.
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The invention disclosed is an actuator for use with a bag having two openings therein wherein the actuator seals one opening and assists in forcing the flowable substance out of the bag. The actuator is demonstrated with a generally conically shaped bag used with mortar such as masonry cement. The bag provides method for applying a continuous constant pressure to the bag thereby forcing the mortar out in a continuous and constant flow.
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BACKGROUND
Utility and recreation vehicles, including pick-up trucks and medium weight flat bed trucks, often include a bed having partial sidewalls. Such sidewalls extend at least three feet from the floor of the bed. To accommodate loads requiring higher sidewalls, a plurality of post bores are positioned along the length of the sidewalls. These post bores are sized to receive a post forming extensions of the sidewalls. When not in use, such post bores include a drill port located in the bottom of the post bores to permit drainage.
Regardless of whether the bed of such vehicles include sidewall extensions, it is becoming more commonplace for states to enact laws requiring loads be secured within the bed. In the past, load binding cables were often strung between the post bores of opposing sidewalls and were secured to the post bores by a clip, such as an S-shaped clip, attached to opposite ends of the load binding cables. In other arrangements, the ends of load binding cables were either tied to opposite sides of the beds or where attached to an overhang located at the top of opposed sidewalls. Although effective, existing methods of attaching such load binding cables to the bed of a vehicle are not without their problems.
As an example, the clip of the load binding cable may slip from its attachment point to the bed. In other examples, tying the ends of the load binding cables to opposing sidewalls did not provide a secure coupling of the load binding cable to the sidewalls. As such, there exists a need for a low cost and effective tie down assembly for a vehicle.
SUMMARY
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
A tie down assembly for a vehicle is provided. The tie down assembly includes a retention body and an anchor assembly. The anchor assembly is slidably disposed within the retention body for reciprocating movement between a release position and a restraint position. The tie down assembly also includes a stop secured to the anchor assembly. The stop is positioned on the anchor assembly for releasably locking with a portion of the retention body when the anchor assembly is in the restraint position.
DESCRIPTION OF THE DRAWINGS
The foregoing aspects and many of the attendant advantages of this invention will become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is an isometric view of a tie down assembly constructed in accordance with one embodiment of the present disclosure;
FIG. 2 is a partially exploded isometric view of the tie down assembly of FIG. 1 ;
FIG. 3 is a cross-sectional side planar view of the tie down assembly of FIG. 1 , showing the tie down assembly is a release position; and
FIG. 4 is a cross-sectional side planar view of the tie down assembly of FIG. 3 , showing the tie down assembly is a restraint position.
DETAILED DESCRIPTION
A tie down assembly 20 constructed in accordance with one embodiment of the present disclosure may be best understood by referring to FIGS. 1-4 . The tie down assembly 20 is illustrated and referenced with respect to providing a portable anchor point of a vehicle (not shown) having sidewalls 22 . Such well-known sidewalls 22 include an attachment bore 24 located either within the sidewall 22 itself or within a post bore (not shown) extending vertically through the top of the sidewall 22 . It should be apparent that the location of the attachment bore 24 is for illustrative purposes only and is not intended to be limiting.
The tie down assembly 20 includes an anchor assembly 30 , a retention body 32 , and a stop 34 . The anchor assembly 30 includes an eyelet 40 and a cord section 42 . The well-known eyelet 40 is either integrally formed with one end of the cord section 42 or is attached to the end of the cord section by any well-known manner, such as crimping.
The cord section 42 is suitably manufactured from a braided material or may be a section of solid material, such as plastic. Disposed in an end of the cord section 42 opposite from the eyelet 40 is a stiffening member 44 . The stiffening member 44 , which is optional, is used to assist in stiffening the cord section 42 as the anchor assembly 30 is reciprocated between a release position and a restraint position, as described in greater detail below.
The stop 34 is suitably manufactured from a high strength multiple plastic material, such as polyvinyl chloride. In one embodiment, the stop 34 is bell-shaped in configuration, such that the stop increases is cross-sectional diameter along an axis extending longitudinally through the stop 34 from a first diameter to a second diameter. As a non-limiting example, the stop 34 increases from a smaller diameter to a larger diameter, thereby resulting in the bell-shaped configuration.
The stop 34 is disposed on the end of the cord section 42 opposite from the eyelet 40 in any well-known manner, such as molding the stop 34 around the cord section 42 . In another embodiment, the stop 34 includes first and second housings 34 a and 34 b secured in placed by an o-ring 36 . As disposed on the cord section 42 , the smaller diameter portion is positioned toward the eyelet 40 and, therefore, increases in diameter, such that the stop 34 translates into the retention body 32 , narrow end first.
The retention body 32 includes a collar 50 and a gripping portion 52 . The collar 50 and gripping portion 52 are suitably integrally formed from a plastic, such as polyvinyl chloride. Although a retention body 32 having an integrally formed collar section 50 and a gripping portion 52 is preferred, other embodiments, such as an embodiment that includes separately formed collars and gripping portions press fitted together, are also within the scope of the present disclosure.
As may be best seen by referring to FIGS. 1 and 2 , the gripping portion 52 includes a plurality of splits 56 to allow the gripping portion 52 to be splayed radially as the anchor assembly 30 is translated within the retention body 32 .
The retention body 32 may include an optional shank portion 54 either integrally formed or press fitted into the collar 50 on a side of the collar 50 opposite of the gripping portion 52 . The optional shank portion 54 is used to assist in retaining the retention body 32 against the attachment bore 24 as the anchor assembly 30 is reciprocated between the release and the restraint positions.
Operation of the tie down assembly 20 may be best understood by referring to FIGS. 3 and 4 . In operation, the stop 34 and gripping portion 52 are inserted into the attachment bore 24 of the vehicle. After the tie down assembly 20 is inserted into the attachment bore 24 , an operator pulls with one hand on the eyelet 40 to translate the anchor assembly within the retention body in a first direction causing the stop 34 to be pulled inwardly of the gripping portion 52 . At the same time, the retention body 32 is held with the other free hand of the operator within the attachment bore 24 and the operator continues to pull on the cord section 42 to securely draw the stop 34 within the gripping portion 52 . This action causes the gripping portion to splay radially and, therefore, adjustable to resist movement of the stop 34 as it translates in the first direction.
The radial splaying action of the gripping portion 52 against the perimeter of the attachment bore 24 causes the gripping portion 52 to be in an interference fit with the attachment bore 24 to restrain the gripping portion 52 within the attachment bore 24 . Further, the stop 34 creates an interference fit with the gripping portion 52 to resist further movement of the stop 34 as it translates in the first direction. Because of the pinching action between the gripping portion 52 and the stop 34 against the perimeter of the attachment bore 24 , the anchor assembly 20 , in this restraint position, is prevented from further translation relative to the retention body 32 . As such, a rope or other load binding member may be looped through and attached to the eyelet 40 , thereby defining a convenient, removable tie down assembly 20 for a vehicle.
To release the tie down assembly 20 from the restraint position, the cord section 42 is translated within the retention body 32 toward the vehicle, thereby pushing the stop 34 outwardly from within the gripping portion 52 and decreasing the diameter of the gripping portion 52 such that the entire anchor assembly 20 may be withdrawn from the attachment bore 24 .
While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.
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A tie down assembly for a vehicle is provided. The tie down assembly includes a retention body and an anchor assembly. The anchor assembly is slidably disposed within the retention body for reciprocating movement between a release position and a restraint position. The tie down assembly also includes a stop secured to the anchor assembly. The stop is positioned on the anchor assembly for releasably locking with a portion of the retention body when the anchor assembly is in the restraint position.
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RELATED APPLICATION
U.S. Pat. application Ser. No. 07/536,771 filed on Jun. 12, 1990 now U.S. Pat. No. 5,133,434.
This U.S. Patent application corresponds to German Patent application No. P 40 19 221 and U.S. Kingdom patent application No. 9013477.6, now published as GB 2 234 038 A.
BACKGROUND OF THE INVENTION
The present invention relates to a variable damping force shock absorber.
Variable damping force shock absorbers are well known. Japanese Utility Model First (unexamined Publication No. 58-92537 discloses a variable damping force shock absorber. This known shock absorber comprises a pressure cylinder forming working chamber having first and second portions to store damping fluid. The absorber further comprises a first control valve for controlling the flow of damping fluid between the first and second portions of the working chamber during compression of the shock absorber. A second control valve is further provided for controlling the flow of damping fluid between the first and second portions of the working chamber during rebound of the shock absorber. A bypass passage has a port opening to the first portion and a valve port opening to the second portion. An externally controllable valve is provided to open or close the valve port. This externally controllable valve is adjusted to selectively change the damping characteristics of the shock absorber. The damping characteristics of this known shock absorber are not satisfactory since there is a point of inflection if a damping force characteristic curve is drawn.
An object of the present invention is to provide a variable damping force shock absorber which provides the damping characteristics without any point of inflection nor at least any noticeable point of inflection.
SUMMARY OF THE INVENTION
According to the present invention, a variable damping force shock absorber is provided with:
a sleeve having an axial bore,
a valve body fixedly coupled with said sleeve, said valve body being formed with an outer groove, an inner groove surrounded by said outer groove, and outer valve seat disposed adjacent the outer periphery of said outer groove, an inner valve seat disposed between sad outer and inner grooves;
a damping valve element cooperating with said outer and inner valve seats to cover said outer and inner grooves;
said sleeve having a first radial port communicating with said inner groove, a second radial port communication with said outer groove, a third radial port communicating with said inner groove;
an adjustable flow restrictor moveably disposed in said axial bore of said sleeve and having a first passage and a second passage, said adjustable flow restrictor having a first position wherein said first and second passages are out of communication with said first, second and third radial ports, thereby to cover said first, second and third radial ports, a second position wherein said first passage establishes a fluid communication between said first and second radial ports, thereby to establish fluid communication between said inner groove and said outer groove, and a third position wherein said second passage communicates with said third port.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view, partly broken away, of an embodiment of a variable damping force shock absorber according to the present invention;
FIG. 2 is an enlarged longitudinal cross section taken along the line II--II of FIG. 4;
FIG. 3 is an enlarged longitudinal cross section taken along the line III--III of FIG. 4;
FIG. 4 is a cross section taken through the line IV--IV of FIG. 2 with unnecessary part removed to clearly illustrate positional relationship between ports,
FIGS. 5, 6 and 7 illustrate three typical angular positions of a rotary valve; and
FIG. 8 illustrates a famility of damping characteristic curves provided by the embodiment according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, a first embodiment of a variable damping force shock absorber according to the present invention is described. The shock absorber comprises an elongated tubular pressure cylinder 11 defining a damping fluid containing working chamber 100. Disposed within the working chamber 100 is an inner tubular cylinder 1. Disposed within the inner cylinder 1 is a reciprocal piston 5. A piston rod 6 extends through a guide member 2 closing one end of the inner cylinder 1, and a dirt shield 7. The piston rod 6 is fixedly secured to a bottom plate 7a of the dirt shield 7 by means of a nut 7b. The cylinder 11 is connected to a body of a vehicle, while the dirt shield 7 is connected to a wheel axle assembly of the vehicle.
The guide member 2 is formed with a through axial bore 2a for allowing extension of the piston rod 6 and closes a lower end, viewing in FIG. 1, of the inner cylinder 1. The inner cylinder 1 has an upper end, viewing in FIG. 1, provided with a base 3 which will be later described. The inner cylinder tube 1 is filled with damping fluid and divided by the piston 5 into an upper chamber A and a lower chamber B, viewing in FIG. 1. The guide member 2 has a real retainer 4 for carrying an oil seal 4a sealably engaging the piston rod 6. The seal retainer 4 is threadably and sealably engaging a lower open end, viewing in FIG. 1, of the cylinder 11 to close the lower open end thereof. The cylinder 11 extends upwardly further than the inner cylinder 1 does. The outer cylinder 11 has an upper open end, viewing in FIG. 1, closed by a lid 11a integral with an attachment 11c with an external thread which is used for mounting the shock absorber to the vehicle body. An actuator 32 is fixedly disposed in the outer cylinder tube 11 near the lid and connected to the base 3 via a control rod 31 extending through a support sleeve 12.
The dirt shield 7 is provided with a bound stop rubber 15 at the bottom plate 7a thereof. The shield 7 also has a lower spring seat 9 for bearing a lower end of a suspension spring, not shown. Defined between the cylinder 1 and 11 is an annular outer chamber C. The annular outer chamber C has a lower end portion, viewing in FIG. 1, communicating with the lower chamber B via the guide member 2 and an upper end portion, viewing in FIG. 1, communicable with the upper chamber A under the control of the base 3. Between the base 3 and the actuator 32 is defined a reservoir for damping fluid pressurized with a confined gas.
Referring to FIGS. 2 and 3, the support sleeve 12 has a reduced diameter end portion 12a with a shoulder. Abutting on this shoulder is a retainer 13. Between this retainer 13 and a retainer 25 on a nut 26 threadably engaged with the reduced diameter and portion 12a are main components of the base 3. The base 3 comprises first and second bodies 22 and 16 defining therebetween a chamber E. This pressure chamber E is in fluid communication with a second portion, i.e., the chamber C, of the working chamber 100 via a passage 22c formed through the first body 22.
As best seen in FIG. 4, the second body 16 is formed with a coaxial inner and outer ring grooves 16c and 16d. The inner groove 16c is not continuous and is partially open radially and inwardly. Provided between the grooves 16c and 16d is an inner valve seat 16e and provided near the outer periphery of the outer ring groove 16d is an outer valve seat 16f. These valve seats 16e and 16f cooperate with a deflectable valve element to form a second damping valve 15. Similarly, the first body 22 is formed with coaxial inner and outer grooves 22 d and 22e. The inner groove 22d is not continuous and partially open radially and inwardly. Provided between the grooves 22d and 22e is an inner valve seat 22f and provided near the outer periphery of the outer ring groove 22e is an outer valve seat 22g. These valve seats 22f and 22g cooperate with a deflectable valve element to form a first damping valve 21.
The first body 22 is sealably engaged with the inner wall of the cylinder 11 to separate the chambers C and D from each other. The second body 16 is sealably received by the first body 22 to separate the chambers D and E from each other. A coupling sleeve 27 interconnects the bottom portion of the first body 22 and the top portion of the inner cylinder 1 to separate the chambers A and C from each other. A first check valve 23 is provided in fluid communication with the chamber A, and a passage 22b is formed through the first body 22 in fluid communication with the chamber D and the first check valve 23. With t his check valve 23, there occurs a one-way flow of damping fluid through the passage 22b from the chamber D to the chamber A if a pressure drop occurs in the chamber A. Similarly, a second check valve 17 is provided in fluid communication with the chamber E, and a passage 16b is formed through the second body 16 in fluid communication with the chamber D and the second check valve 17. With this check valve 17, there occurs a one-way flow of damping fluid through the passage 16b from the chamber D to the chamber E and in turn to the chamber C if a pressure drop occurs in the chamber C.
In FIGS. 2 and 3, reference numerals 14, 18, 20 and 24 designate washers, and the reference numeral 19a retainer.
As will be readily seen from FIG. 4, there is a pressure chamber 200 defines by the inner groove 16c, the inner valve seat 16e, the reduced diameter end portion 12a of the support sleeve 12 and the second damping valve 15. This pressure chamber 200 is in fluid communication, via ports 16a of the second body 16, chamber E and passage 22c, with a second portion, i.e., the chamber C, of the working chamber 100. The pressure chamber 200 is in fluid communication with the second damping valve 15. Similarly, there is a pressure chamber 202 defined by the inner groove 22d, the inner valve seat 22f, the reduced diameter end portion 12a of the support sleeve 12 and the first damping valve 21. This pressure chamber 202 is in fluid communication, via ports 22 a of the first body 22, with a first portion, i.e., the chamber A, of the working chamber 100. The pressure chamber 202 is in fluid communication with the first damping valve 21.
Rotatably disposed within an axial bore 12e of the support sleeve 12 is an angularly adjustable flow restrictor 28. The flow restrictor 28 is supported by two thrust bushings 29 and 30. As best seen in FIGS. 3 and 4, the support sleeve 12 is formed with two pairs of diametrically opposed upper radial ports 12c in fluid communication with the pressure chamber 200 of the second damping valve 15. It is also formed with another two pairs of diametrically opposed lower radial ports 12din fluid communication with the pressure chamber 202 of the first damping valve 21. In addition, the sleeve 12 is also formed with a pair of diametrically opposed radial ports 12b in fluid communication with the chamber D. As readily seen from FIG. 3, the two of the radial ports 12c are in axial alignment with two of the radial ports 12d, while the other two end other former in alignment with the other two of the latter. The flow restrictor 28 is formed with two diametrically opposed axial transfer passages 28a for regulating a fluid flow communication between the mating radial ports 12c and 12d. From the preceding description, it will be appreciated that there is established a bypass passageway by the radial ports 12c, 12d and the axial transfer passages 28a when the axial transfer passages 28a are in communication with the radial ports 12c and 12d. This bypass passageway provides a fluid communication between the first portion, i.e., the chamber A, of the working chamber 100 and the second portion, i.e., the chamber C, of the working chamber 100 (see phantom lines arrows I and L).
Referring to FIGS. 2 and 4, the support sleeve 12 is formed with two pairs of diametrically opposed upper radial ports 12f and 12g. As best seen in FIG. 4, two radial ports 12f are in fluid communication with the pressure chamber 200 of the second damping valve 15, while the other two radial ports 12g are in fluid communication with the annular groove 16d. In addition, the support sleeve 12 is formed with two pairs of diametrically opposed lower radial ports 12h and 12j. Similarly, two radial ports 12h are in fluid communication with the pressure chamber 222 of the first damping valve 21, while the other two radial ports 12j are in fluid communication with the annular groove 22e. The radial ports 12f and 12h are in axial alignment with each other, and thus the radial ports 12g in axial alignment with each other. The flow restrictor 28 is also formed with two upper radial transfer passage 28b for regulating a fluid flow communication between the mating radial ports 12f and 12g. It is also formed with two lower radial transfer passages 28c for regulating a fluid flow communication between the mating radial ports 12h and 12j.
Under the control of the actuator 32, the flow restrictor 28 is angularly adjustable to any one of angular positions including three positions as illustrated in FIGS. 5, 6 and 7. FIG. 5 shows the closed position in which there is no flow of damping fluid through the axial transfer passages 20a since the ports 12c and 12d are out of alignment with the axial transfer passage 28a, and there are closed flow paths (see arrows K and H in FIG. 2) which allow flows of fluid out of the pressure chambers 200 and 202 toward their outer ring grooves 16d and 23e since the radial ports 12f and 12g are out of alignment with the radial transfer passages 28b and the radial ports 12h and 12j out of alignment with the radial transfer passages 28c. Viewing in FIGS. 5, 6 and 7, turning the flow restrictor 28 counterclockwise to the position as illustrated in FIG. 6, there is a flow of damping fluid through each of the radial transfer passages 28b and 28c and a flow of damping fluid through each of the axial transfer passages is about to begin. Turning further counterclockwise causes an increase in flow of damping fluid through each of the axial transfer passages 28a. FIG. 7 illustrates a position where there are maximum fluid flows of damping fluid through each of the axial transfer passages 28a and each of the axial transfer 28 b and 28c. From this description in connection with FIGS. 5, 6 and 7, it will be appreciated that the flow restrictor 28 is operable to selectively change a ratio between a flow sectional area of the flow of damping fluid through the radial transfer passage and that through the axial transfer passage.
Referring to FIGS. 2 and 3, during rebound of the shock absorber, the second damping valve 15 controls a first flow of damping fluid (see a phantom line drawn arrow J in FIG. 2) from the second portion, i.e., the chamber C, of the working chamber 100 toward the second portion, i.e., the chamber D, of the working chamber 100, the flow restrictor 28 regulates a second flow of damping fluid (see a phantom line drawn arrow L in FIG. 3) through the bypass passageway, and the flow restrictor 28 also regulates a third flow of damping fluid (see a phantom line drawn arrow K in FIG. 2) out of the pressure chambers 200 and 202 toward the first portion, i.e., the chamber D, of the working chamber 100. During compression of the shock absorber, the first damping valve 21 controls a first flow of damping fluid (see a phantom line drawn arrow G in FIG. 2), the flow restrictor 28 regulates a second flow of damping fluid (see phantom line drawn arrow I in FIG. 3) through the bypass passageway, and the flow restrictor 28 also regulates a third flow of damping fluid (see a phantom line drawn arrow H in FIG. 2).
FIG. 8 show a family of damping characteristic curves provided according to the present invention by varying angular position of the flow restrictor 28. As will be appreciated from these characteristic curves, there are no inflection points in damping characteristics.
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A variable damping force shock absorber comprises a pressure cylinder forming a working chamber having first and second portions operable to store damping field. A valve is provided to control a first flow of damping fluid between said first and second portions of said working chamber during compression or rebound of the shock absorber. A bypass passageway is in fluid communication with the first and second portions of the working chamber. An angularly adjustable flow restrictor is provided for regulating a second flow of damping fluid through the bypass passageway. A pressure chamber is in fluid communication with the first (or the second portion) of the working chamber and the valve. The flow restrictor is operable to regulate also a third flow of damping fluid displaced out of the pressure chamber.
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FIELD OF INVENTION
This invention relates to metal door frames of the type shown and described in U.S. Pat. No. 3,107,759 issued Oct. 22, 1963 to Robert L. Day and Harry L. Williams, and entitled PREFABRICATED DOOR FRAME AND MOLDING STRUCTURE.
BACKGROUND OF THE INVENTION
The metal door frame structure shown and described in the Day-Williams patent in addition to frame parts, includes trim parts. The frame parts are three in number, a header and two vertical jamb members all having corresponding U-shape cross-sectional configuration. The flanges of the frame parts extend upwardly and outwardly from the wall opening to extend along the wall surfaces on opposite sides of the wall. The trim parts are held by clips in such manner that the outer portions of the trim parts extend beyond the edges of the frame parts to engage the wall, thereby providing a neat finished appearance. The Day-Williams design utilizes a trim clip formed by lancing and curling metal from the frame flange itself.
Two curls result, one of which extends beyond the frame flange and is actually punched back into the frame flange itself. While the design is one of the most successful frame structures of the past ten years, maintenance of dies is believed to be a problem.
The reason is that proper operation of the dies depends upon the edge of the frame flange being in the right place for interengagement with the outer trim clip curl. This in turn depends upon the frame being made to close tolerances during roll forming operations. Of course, supplementary trimming of the frame edge could be part of the manufacturing routine, but at substantial cost.
The primary object of this invention is to provide a frame structure that is at least the equal of the successful Day-Williams design, but which does not require the frame to be made to close tolerances. Accordingly, ordinary roll forming techniques can be used, and edge trimming is not required. A companion object of the present invention is to provide a separate clip structure for trim parts that in a simple way firmly and with position accuracy, connects with the frame flange all independently of the flange edge.
SUMMARY OF THE INVENTION
The foregoing objects are made possible by an arrangement in which each trim clip is clasped and interlocked by companion locking tabs struck from the flange itself. The taps are located accurately relative to the corner at the base of the flange, independently of the position of the flange edge. For this purpose, the tabs are struck by the use of a die that has a surface upon which the connecting portion of the frame part rests and that has tool or metal cutting parts that move on an axis parallel to and in fixed spaced relationship to the said frame surface. All of the clips are thereby accurately in line and accurately placed independently of the flange edge.
BRIEF DESCRIPTION OF THE DRAWINGS
A detailed description of the invention will be made with reference to the accompanying drawings wherein like numerals designate corresponding parts in the several figures.
FIG. 1 is a front elevational view of a door frame and molding structure embodying the present invention.
FIG. 2 is an enlarged isometric view of the companion frame and trim parts.
FIG. 3 is an enlarged transverse cross sectional view of the door frame structure taken along a plane corresponding to line 3--3 of FIG. 1.
FIG. 4 is a side elevational view of the frame part before the clip is installed.
FIG. 5 is a view similar to FIG. 4, but showing the clip securely clasped in place.
FIG. 6 is a plan elevational view of the clip, shown separate from the frame structure.
FIGS. 7 and 8 are detail sectional views taken along planes corresponding to lines 7--7 and 8--8 of FIG. 5.
FIG. 9 is a top plan view of a die for punching the mounting holes for the clips, the central portion of the die being broken away.
FIG. 10 is an enlarged transverse sectional view taken along a plane corresponding to line 10--10 of FIG. 9.
FIG. 11 is a fragmentary sectional view showing the tool advances position.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In FIG. 1 there is illustrated a wall W having an opening O framed by the door frame structure F. The frame is designed to support a door, not shown. Three frame parts 12, 14 and 16, preferably made of relatively heavy gauge roll formed steel, extend along one side, the top and the other side of the wall opening.
The frame parts 12, 14, and 16 as shown in FIGS. 2 and 3 are generally of channel shaped cross-sectional configuration, flanges on opposite sides extending from corners C. The flanges fall along the wall surfaces on opposite sides of the opening. Nails N (FIG. 2) pass through holes in the frame parts to secure them to the wall. The side frame parts preferably interlock the corresponding ends of the top frame part by means not shown.
The heads of the nails N, sight holes S and raw edges E of the frame flanges are concealed by trim molding parts. A set of three such parts 18, 20 and 22 is provided for the frame flanges on one side of the wall opening. A similar set is provided for the frame flanges on the other side. The trim parts are of like shallow channel-shaped cross sectional configuration. One leg 24 of each trim part is slightly longer than the other leg 26. The trim parts extend along the corresponding flanges to form a facing. The shorter leg 26 contacts the frame flange near the corner C, and the other shorter leg 24 contacts the wall W just beyond the frame edge E. The ends of the trim parts are mitred as shown in FIG. 1 to form a neat joint.
In order to hold the trim parts in place, the frame flanges carry a series of clips 30. As shown in FIG. 1, these clips are located in spaced aligned relationship along the length of the frame flanges.
Each clip 30, as shown in FIGS. 5 and 8, has an outer curl 32 and an inner curl 34 about which the opposite legs 24 and 26 of the trim part are respectively snapped. The trim part legs 24 and 26 have reentrant ends 36 and 38 that snap about the under surfaces of the curls. The outer curl 32 of each clip extends just beyond the frame edge E so that the longer trim part leg 24 extends beyond the flange edge E. The clip is shown in full detail in FIGS. 4, 5, 6 and 7.
The clip 30 is made from an initially flat, short strip of material die formed to provide curls 32 and 34 at opposite ends. The clip is made longitudinally rigid by a central rib 40 that extends from one curl to the other. The outer curl 32 fits into a shallow notch V at the flange edge F. The underside of the outer curl contacts the bottom and sides of the notch. The clip is held in contact with the frame flange by a pair of arcuate tabs T lanced from the flange. The tabs could be rectangular. The arcuate tabs leave two semicircular apertures H. A clip is dropped between the upwardly bent tabs T.
The base ends of the tabs T, as shown in FIGS. 5 and 7, actually interfit shallow recesses 44 (see also FIG. 6) located on opposite sides of the clip. With the clips positioned, the tabs are bent, staking the clip in place. By virtue of the interlocking relationship, the clip is accurately located. Engagement between the clip curl 32 and the notch V assists in determining an accurate clip location. The tabs when bent back lie along, but not over, the central reinforcing rib 40.
The tabs T and the notch V are located on the frame flange not by reference to the edge E, but instead by reference to the corner C. Accordingly, the outermost portions of all of the outer clip curls precisely parallel the corner C. The fit of the trim parts is thus quite independent of the exact corner-to-corner dimension of the frame edge. In practice, the depth of the notches V may vary slightly if the edge E is not precisely parallel the corner C. The notch depth may also vary from piece to piece. Close tolerances are unnecessary.
The manner in which the corner C is used as a reference for the metal cutting operations is shown in FIGS. 9, 10 and 11. In FIG. 10, companion die parts 50 and 52 for lancing the tabs T and notch V are shown. These parts are guided for movement toward and away from each other. The die part 50 is an elongate anvil member secured along the lower side of an inclined bed 54. The other die part 52 is a punch support member guided for rectilinear movement along the slant of the bed toward and away from a punch plate 56 secured to the anvil. The punch support member 52 is guided by blocks 58 and 60 (FIG. 9) secured to the bed.
A series of punch support members 52 are provided whereby all of the tabs and notches in the flange are simultaneously formed. As many supporting blocks are provided as required by the number of punch support members. The anvil member 50 and punch plate 56 cooperate with all of the punch support members 52. Each punch support member carries a punching tool that has one part designed to cut the tabs T and another part designed to cut the notch V. A slidable guide plate 64 assists in maintaining the punch tool in proper alignment with the punch support member.
The central connection portion of the frame part F to be punched rests upon the top inclined surfaces of all punch support members 52 and upon the guide plates 64. The flange to be cut hangs between the companion die parts, the edge E being free. With the die open, one flange of the frame part is dropped into position. A top plate 66 secured to the top of the anvil member 50 slightly overhangs the punch plate 56 in order to provide a seat for the frame corner C. The frame falls into place under the influence of gravity. The punch plate 56 forms a stop for the flange.
The punch support members 52 are moved to close by a common mechanism. In the present instance, a series of crank links 68 are provided and connected to a common operating rod 70 in turn powered by a hydraulic motor 72.
The position of each punch 62 relative to the top surface of the punch support member 52 is accurately controlled. Accordingly, the position of the hole H and notch V is accurately determined relative to the corner C since the corner is a part of the under surface of the frame part that rests upon the top of the punch support member.
After one frame flange is punched, the frame part is turned to punch the other. The nail holes and sight holes can be punched at the same time by means not shown.
The frame part is prepared for reception of the clips 30 by very simple tooling. After the tabs T and notches V are cut, the tabs T are bent upwardly and the clips positioned. A simple press closes on the tabs, and the frame part is completed.
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A metal door frame has trim molding applied to its flanges by the aid of separate clips. Each clip interfits an aperture in the flange and a notch at the flange edge. The aperture and the notch are punched in the flange so that the spacing thereof from the corner of the flange is constant whereby alignment of the clips is assured notwithstanding lack of critical dimensional control of the flange.
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FIELD OF INVENTION
The present invention relates to two crystalline forms of the compound pinocembrin, and active pharmaceutical ingredients, pharmaceutical compositions and dosage forms containing the two crystalline forms of pinocembrin, and the use thereof for manufacture of pharmaceutical compositions and treating diseases, and the method for preparing the two crystalline forms of pinocembrin.
BACKGROUND OF THE INVENTION
Pinocembrin (chemical name: 5,7-dihydroxy-2-phenyl-4-chromanone) is a flavone compound, widely found in the nature. Its chemical structure is as below:
exiting in 1-isomer, d-isomer, 1-isomer- or d-isomer-enriched mixture, and racemate.
Previous pharmacological experiments showed that pinocembrin had strong bacteriostasis, antivirus, and antifungal activities. For example, honey, a Chinese traditional health care food, is rich in pinocembrin. So eating honey sugar frequently is not only harmless to the teeth, but also can sterilize the oral cavity, for example, relieving oral ulcer and accelerating wound healing. Chinese Patent CN1695608A, titled “Use of pinocembrin for manufacture of pharmaceutical compositions for preventing and treating diseases related to nerve cell injury” [1] , disclosed the use of pinocembrin for manufacture of pharmaceutical compositions for preventing or treating diseases related to cerebral ischemia, sequelae of cerebral ischemia, nerve cell injury and function alteration.
DESCRIPTION OF THE INVENTION
It was found surprisingly by the inventors that pinocembrin had two different crystalline forms α and β, and the inventors developed the preparations thereof. The inventors also found that there was a significant difference between the two crystalline forms in the uptake by organism, wherein the uptake rate of β crystalline form was greater than that of α crystalline form, for example, the uptake rate of β crystalline form can be 2 times or more greater than that of α crystalline from. The biological activities thereof in medicament therapy are different due to differences in drug blood concentrations.
One embodiment of the present invention provides α crystalline form, β crystalline form, or the mixture of α crystalline form and β crystalline form in different proportions, with respect to pinocembrin. Preferably, these crystalline forms or the mixture thereof contains no crystal water or other organic solvents.
One embodiment of the present invention provides the method for preparing α crystalline form, β crystalline form, or the mixture of α crystalline form and β crystalline form of pinocembrin in different proportions.
One embodiment of the present invention provides a pharmaceutical composition comprising pure α crystalline form, pure β crystalline form, or the mixture of α crystalline form and β crystalline form of pinocembrin in different proportions. The pharmaceutical composition can also comprise one or more pharmaceutically acceptable carriers. There is no limitation on the pharmaceutically acceptable carriers, provided that they are suitable for formulation and would not substantially affect the effect of pinocembrin crystalline form of the present invention.
One embodiment of the present invention relates to dosage forms comprising the pinocembrin crystalline forms solid. There are no limitations on specific dosage forms. For example, they can be tablets, capsules, pills, injections, sustained-release preparations, controlled-release preparations and the like.
One embodiment of the present invention provides use of the crystalline forms solid of pinocembrin, including α crystalline form, β crystalline form or the mixture of α crystalline form and β crystalline from in different proporations, for bringing about difference of drug uptake in treatment.
One embodiment of the present invention relates to the use of α crystalline form, β crystalline form, or the mixture of α crystalline form and β crystalline form of pinocembrin in different proportions in the manufacture of a medicament for treating diseases related to cerebral ischemia or a medicament for preventing diseases related to cerebral ischemia by protecting neurovascular unit function.
One embodiment of the present invention provides the use of pinocembrin for protecting neurovascular unit function in the treatment of diseases related to cerebral ischemia, and for improving the blood concentration in an organism due to the crystal form effect.
Morphologic Features of a Sample of α Crystalline Form of Pinocembrin According to an Embodiment:
For a sample of α crystalline form of pinocembrin obtained according to an embodiment of the present invention, when analyzed by X-ray single crystal diffraction, it showed monoclinic crystal system symmetry, the space group was P2 1 /c, and the crystal cell parameter values were as follows: a=5.189 Å, b=24.149 Å, c=10.472 Å, α=90°, β=102.31° and γ=90°.
FIG. 1 is an illustration showing the relative configuration of the molecule, FIG. 2 is an illustration showing the stereo-structure projection of the molecule, FIG. 3 is an illustration showing the unit cell stacking of the molecule along the a axis. Table 1 shows atomic coordinate parameters and equivalent temperature factors. Table 2 shows bond length values of bonding atoms. Table 3 shows bond angle values of bonding atoms. As some carbon atoms of B ring adopt a disordered orientation state, the four atoms of C 2′ , C 3′ , C 5′ and C 6′ occupy two positions, with an occupancy rate of 0.5 respectively.
Formula 1 relative molecule configuration of α crystalline form of pinocembrin
TABLE 1
Atomic coordinate parameters (relative coordinate) of a
sample of α crystalline form of pinocembrin
tem-
per-
ature
occu-
fac-
pan-
x
y
z
tors
cy
O 1
−.2023(8)
−.6574(2)
−.7376(4)
3.4(2)
1.0
O 2
−.4261(9)
−.8310(2)
−.5601(4)
4.3(2)
1.0
O 3
−.8660(9)
−.6732(2)
−.3557(4)
4.2(2)
1.0
O 4
−.6128(8)
−.7370(2)
−.4969(4)
3.6(2)
1.0
C 2
−.4094(24)
−.6318(3)
−.6954(12)
3.5(8)
1.0
C 3
−.5019(13)
−.6513(3)
−.5885(6)
3.6(3)
1.0
C 4
−.4859(12)
−.7131(3)
−.5720(6)
3.0(3)
1.0
C10
−.3269(12)
−.7427(2)
−.6435(6)
2.8(3)
1.0
C 5
−.2968(12)
−.8009(2)
−.6366(6)
3.1(3)
1.0
C 6
−.1407(13)
−.8289(2)
−.7054(6)
3.3(3)
1.0
C 7
−.0117(12)
−.7979(2)
−.7862(6)
3.1(3)
1.0
C 8
−.0336(12)
−.7405(2)
−.7966(6)
2.8(3)
1.0
C 9
−.1894(12)
−.7138(2)
−.7262(6)
2.9(3)
1.0
C 1′
−.4049(18)
−.5701(3)
−.7176(9)
6.7(5)
1.0
C 2′
−.316(5)
−.5292(7)
−.6099(19)
7.4(2)
0.5
C 3′
−.326(5)
−.4730(7)
−.6436(21)
7.4(1)
0.5
C 4′
−.3988(18)
−.4566(3)
−.7567(10)
7.5(1)
1.0
C 5′
−.456(5)
−.4929(8)
−.8580(22)
7.9(2)
0.5
C 6′
−.435(6)
−.5510(7)
−.8288(23)
7.8(2)
0.5
C 2″
−.194(4)
−.5453(7)
−.6870(25)
7.1(1)
0.5
C 3″
−.178(4)
−.4859(7)
−.700(3)
7.3(2)
0.5
C 5″
−.630(4)
−.4859(7)
−.7856(22)
7.4(1)
0.5
C 6″
−.640(4)
−.5432(6)
−.7752(22)
8.8(1)
0.5
H 2
−.591
−.644
−.779
7.6
1.0
H 3A
−.701
−.637
−.587
5.0
1.0
H 3B
−.369
−.632
−.502
5.0
1.0
H 6
−.116
−.874
−.697
4.3
1.0
H 8
.070
−.717
−.861
3.6
1.0
HO 2
−.525
−.802
−.507
3.2
1.0
HO 3
−.775
−.699
−.420
3.2
1.0
H 2′
−.177
−.548
−.528
3.2
0.5
H 3′
−.160
−.447
−.578
3.2
0.5
H 4′
−.430
−.413
−.771
3.2
1.0
H 5′
−.591
−.477
−.952
3.2
0.5
H 6′
−.533
−.577
−.908
3.2
0.5
H 2″
−.095
−.557
−.569
3.2
0.5
H 3″
−.072
−.456
−.601
3.2
0.5
H 5″
−.723
−.469
−.896
3.2
0.5
H 6″
−.742
−.570
−.857
3.2
0.5
TABLE 2
Bond length values of bonding atoms of a sample of α crystalline form
of pinocembrin (Å)
Bonding Atoms
Bond Length
Bonding Atoms
Bond Length
O(1)—C(2)
1.391(9)
C(6)—C(7)
1.402(8)
O(1)—C(9)
1.369(7)
C(6)—H(6)
1.098(16)
O(2)—C(5)
1.360(7)
C(7)—0(3)
1.351(7)
O(2)—Ho(2)
1.090(20)
C(7)—C(8)
1.393(8)
O(3)—C(7)
1.351(7)
C(8)—C(9)
1.366(8)
O(3)—Ho(3)
1.100(21)
C(8)—H(8)
1.099(23)
O(4)—C(4)
1.268(7)
C(1′)—C(2′)
1.497(22)
C(2)—C(3)
1.391(11)
C(1′)—C(6′)
1.230(30)
C(2)—C(1′)
1.509(10)
C(2′)—C(3′)
1.399(25)
C(2)—H(2)
1.183(24)
C(2′)—H(2′)
1.090(30)
C(3)—C(4)
1.503(8)
C(3′)—C(4′)
1.229(24)
C(3)—H(3A)
1.087(21)
C(3′)—H(3′)
1.160(30)
C(3)—H(3B)
1.109(21)
C(4′)—C(5′)
1.360(30)
C(4)—C(10)
1.420(8)
C(4′)—H(4′)
1.072(17)
C(10)—C(5)
1.416(8)
C(5′)—C(6′)
1.430(3)
C(10)—C(9)
1.417(8)
C(5′)—H(5′)
1.150(3)
C(5)—C(6)
1.371(8)
C(6′)—H(6′)
1.080(3)
TABLE 3
Bond angle values of bonding atoms of a sample of α crystalline form
of pinocembrin (°)
Bond angle
Bond angle
Bonding atoms
value
Bonding atoms
value
C(2)—O(1)—C(9)
116.2(5)
C(5)—C(6)—H(6)
121.2(13)
C(5)—O(2)—Ho(2)
107.8(11)
C(7)—C(6)—H(6)
121.1(13)
C(7)—O(3)—Ho(3)
113.3(11)
O(3)—C(7)—C(6)
116.2(5)
C(4)—O(4)—Ho(2)
102.1(9)
O(3)—C(7)—C(8)
121.3(5)
C(4)—O(4)—Ho(3)
117.2(8)
C(6)—C(7)—C(8)
122.5(5)
O(1)—C(2)—C(3)
121.9(7)
C(7)—C(8)—C(9)
118.3(5)
O(1)—C(2)—C(1′)
110.5(6)
C(7)—C(8)—H(8)
120.8(10)
O(1)—C(2)—H(2)
101.5(12)
C(9)—C(8)—H(8)
120.9(10)
C(3)—C(2)—C(1′)
118.5(7)
O(1)—C(9)—C(10)
121.4(5)
C(3)—C(2)—H(2)
99.1(13)
O(1)—C(9)—C(8)
116.5(5)
C(1′)—C(2)—H(2)
99.8(11)
C(10)—C(9)—C(8)
122.1(5)
C(2)—C(3)—C(4)
114.0(6)
C(2)—C(1′)—C(2′)
123.3(10)
C(2)—C(3)—H(3A)
113.3(13)
C(2)—C(1′)—C(6′)
120.9(11)
C(2)—C(3)—H(3B)
104.8(14)
C(1′)—C(2′)—C(3′)
117.4(16)
C(4)—C(3)—H(3A)
109.6(10)
C(1′)—C(2′)—H(2′)
111.2(16)
C(4)—C(3)—H(3B)
107.7(10)
C(2′)—C(3′)—C(4′)
122.9(16)
H(3A)—C(3)—H(3B)
106.9(15)
C(2′)—C(3′)—H(3′)
113.0(20)
O(4)—C(4)—C(3)
120.1(5)
C(4′)—C(3′)—H(3′)
115.5(20)
O(4)—C(4)—C(10)
122.2(5)
C(3′)—C(4′)—C(5′)
121.0(13)
C(3)—C(4)—C(10)
117.6(5)
C(3′)—C(4′)—H(4′)
117.3(16)
C(4)—C(10)—C(5)
123.0(5)
C(5′)—C(4′)—H(4′)
121.5(16)
C(4)—C(10)—C(9)
120.0(5)
C(4′)—C(5′)—C(6′)
118.0(18)
C(5)—C(10)—C(9)
117.0(5)
C(4′)—C(5′)—H(5′)
116.5(18)
O(2)—C(5)—C(10)
119.8(5)
C(6′)—C(5′)—H(5′)
120.9(24)
O(2)—C(5)—C(6)
117.9(5)
C(1′)—C(6′)—C(5′)
123.9(17)
C(10)—C(5)—C(6)
122.3(5)
C(1′)—C(6′)—H(6′)
117.0(19)
C(5)—C(6)—C(7)
117.8(5)
C(5′)—C(6′)—H(6′)
113.9(25)
Note: in table 2 and 3, for the atoms C 2′ , C 3′ , C 5′ and C 6′ of B ring, only the bond length and bond angle values of one position are given in Table 2 and 3.
Powder (polycrystal) X-ray diffraction (CuK α radiation) was performed on the α crystalline form solid of pinocembrin, and the diffraction peak locations: 2-Theta value (°) or d value (Å), and the relative strength of diffraction peak: peak height value (Height %) or peak area value (Area %) show the following characteristics (see Table 4, FIG. 4 ).
TABLE 4
characteristic peak values of powder X-ray diffraction
for a sample of α crystalline form of pinocembrin
Peak
2-Theta
d(Å)
Height %
Area %
1
7.32
12.07
100.0
100.0
2
9.37
9.44
2.3
2.5
3
11.30
7.82
2.1
2.2
4
13.93
6.35
1.5
2.5
5
14.65
6.04
27.3
27.1
6
17.04
5.20
5.5
8.7
7
17.31
5.12
11.8
18.2
8
17.80
4.98
5.6
26.6
9
18.16
4.88
2.2
1.8
10
18.83
4.71
1.6
2.1
11
21.47
4.13
0.9
0.5
12
22.06
4.03
12.5
13.8
13
22.40
3.97
2.2
2.4
14
23.09
3.85
2.6
2.0
15
23.74
3.74
1.8
1.6
16
25.83
3.45
1.5
1.8
17
27.30
3.26
7.2
9.6
18
27.51
3.24
7.1
14.1
19
28.29
3.15
5.7
6.4
20
29.53
3.02
1.7
1.9
21
30.88
2.89
0.8
1.0
22
34.51
2.60
1.2
1.2
23
35.37
2.54
0.5
0.6
24
37.21
2.41
2.4
2.4
25
38.27
2.35
0.8
1.4
26
40.53
2.22
0.5
0.8
27
41.40
2.18
0.3
0.3
28
42.09
2.15
1.1
1.1
29
45.96
1.97
2.8
3.2
30
46.67
1.94
0.5
0.7
31
56.49
1.63
0.3
0.5
In an embodiment of the present invention, when analyzed by DSC, α crystalline form solid of pinocembrin shows a decalescence transition temperature of about 206° C. (see FIG. 5 ).
IR analysis with KBr pellet was performed on α crystalline form solid of pinocembrin (see FIG. 6).The characteristic peaks were as follows: 3090.6, 3011.6, 2889.1, 2747.4, 2636.2, 1631.5, 1602.5, 1584.3, 1487.7, 1466.2, 1454.5, 1435.6, 1354.9, 1302.4, 1257.0, 1217.0, 1168.2, 1088.6, 1064.9, 1028.0, 1014.6, 1001.3, 975.8, 918.0, 887.7, 861.8, 825.9, 789.9, 766.4, 715.2, 698.1, 663.7, 646.7, 620.3, 587.3, 574.9, 560.5, 526.9 and 487.9 cm −1 , wherein the peaks of 2891.1, 2747.4, 2636.2, 1631.5 and 1354.9 cm −1 were the main characteristic peaks of α crystalline form solid of pinocembrin.
Morphologic Features of a Sample of β Crystalline Form of Pinocembrin According to an Embodiment:
For β crystalline form of pinocembrin obtained according to an embodiment of the present invention, when analyzed by powder (polycrystal) X-ray diffraction (CuK α radiation), it showed the diffraction peak location:2-Theta value (°) or d value (Å) and the relative strength of diffraction peak: peak height value (Height %) or peak area value (Area %), shown as the following characteristic peak values (see Table 5, FIG. 7 )
TABLE 5
characteristic peak values of powder X-ray diffraction
for a sample of β crystalline form of pinocembrin
Peak
2-Theta
d(Å)
Height %
Area %
1
7.33
12.06
100.0
66.5
2
9.41
9.40
6.2
4.9
3
11.33
7.81
6.1
4.5
4
14.07
6.29
2.9
2.2
5
14.69
6.03
27.2
17.6
6
17.49
5.07
63.9
100.0
7
19.01
4.67
2.8
1.5
8
21.49
4.13
0.1
0
9
22.11
4.02
12.9
11.2
10
23.17
3.84
19.4
9.5
11
25.91
3.44
3.3
2.5
12
27.41
3.25
31.7
27.4
13
28.31
3.15
19.0
15.1
14
29.51
3.02
1.6
0.3
15
31.03
2.88
0.7
0.4
16
34.47
2.60
1.0
1.5
17
35.45
2.53
0.4
0.2
18
37.24
2.41
1.5
0.7
19
38.15
2.36
1.2
0.9
20
40.61
2.22
3.1
2.8
21
42.83
2.11
1.5
1.4
22
44.89
2.02
1.6
1.3
23
46.01
1.97
2.4
1.8
24
50.36
1.81
0.7
0.8
25
56.63
1.62
1.0
0.9
In an embodiment of the present invention, when analyzed by DSC, β crystalline form solid of pinocembrin shows a decalescence transition temperature of about 204° C. (see FIG. 8 ).
IR analysis with KBr pellet was performed on β crystalline form solid of pinocembrin according to an embodiment of the present invention (see FIG. 9 ). The characteristic peaks were as follows: 3090.8, 2890.0, 2748.9, 2638.3, 1633.5, 1602.9, 1585.0, 1487.9, 1466.1, 1454.3, 1344.4, 1302.7, 1216.7, 1168.2, 1088.4, 1065.5, 1028.8, 1014.3, 1001.5, 975.8, 917.8, 888.2, 861.8, 826.6, 789.1, 766.6, 741.1, 715.4, 698.0, 663.7, 646.0, 620.5, 587.9, 574.8, 560.9, 527.2 and 488.4 cm −1 , wherein the peaks of 2890.0. 2748.9. 2638.3, 1633.5 and 1344.4 cm −1 were the main characteristic peaks of β crystalline form solid of pinocembrin.
Method for Preparing a Sample of α Crystalline Form of Pinocembrin According to an Embodiment of the Present Invention
(1) dissolving a sample completely in a solvent selected from the group consisting of methanol, ethanol, chloroform, acetone, ethyl acetate, n-butanol, isopropanol, acetonitrile, THF, dioxane, 95% ethanol, glacial acetic acid, formic acid, ether, dichloromethane, toluene, benzene, n-hexane, cyclohexane, dioxane, DMF, petroleum ether, ammonia, n-propanol, or a mixture thereof, then,
(a) placing the mixture in a condition of temperature 4-50° C. and relative humidity 10%-75% to allow recrystallization for 1 to 60 days, or
(b) adding water to allow precipitate, then obtaining α crystalline form of pinocembrin through filtration under reduced pressure, freeze-drying or cold spray.
Method for Preparing a Sample of β Crystalline Form of Pinocembrin According to an Embodiment of the Present Invention
using a sample of α crystal form solid as the material, then
obtaining a sample of β crystalline form of pinocembrin through
(a) crystal transition by grinding, or
(b) dissolving the material completely in a solvent of pyridine or DMSO, adding water to allow precipitate, and performing filtration under reduced pressure, freeze-drying or cold spray.
Pharmacodynamics Characteristics of Pinocembrin Sample:
Pure α crystalline form, pure β crystalline form or the mixture of α and β crystalline forms of pinocembrin in any proportion according to the present invention have an effect on treating diseases related to cerebral ischemia or preventing diseases related to cerebral ischemia by protecting neurovascular unit function.
There is a difference in bioavailability between pure α crystalline form and pure β crystalline form of present invention. For oral administration, the bioavailability of β crystalline form is more than 2 times higher than that of α crystalline form. For a mixture of the two crystalline forms in any proportion, the bioavailability thereof can vary, dependent on different contents of β crystalline form.
Dosage and Preparation Characteristics:
For a pharmaceutical composition or a preparation comprising pure α crystalline form, pure β crystalline form or a mixture thereof in any proportion of pinocembrin according to an embodiment of present invention, daily dosage is 5˜250 mg, based on pinocembrin crystalline forms solid. Preparations include tablets, capsules, pills, injections, sustained-release preparations, controlled-release preparations and the like.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration showing the relative configuration of the molecule.
FIG. 2 is an illustration showing the stereo-structure projection of the molecule.
FIG. 3 is an illustration showing the unit cell stacking of the molecule (along the a axis).
FIG. 4 is a powder X-ray diffraction pattern for a sample of α crystalline form of pinocembrin.
FIG. 5 is a DSC trace for a sample of α crystalline form of pinocembrin.
FIG. 6 is an infrared absorption spectra for a sample of α crystalline form of pinocembrin.
FIG. 7 is a powder X-ray diffraction pattern for a sample of β crystalline form of pinocembrin.
FIG. 8 is a DSC trace for a sample of β crystalline form of pinocembrin.
FIG. 9 is an infrared absorption spectra for a sample of β crystalline form of pinocembrin.
DETAILED DESCRIPTION OF THE INVENTION
The following exemplary examples are provided for the purpose of better description of the present invention, however, it should be appreciated that the present invention is not limited to the given examples.
Instruments and Test Conditions for the Following Examples:
1. Monocrystal X-ray analysis
Instrument: MAC DIP-2030K area detector Test condition: tube voltage: 50 KV, tube flow: 80 mA, ω scanning, MoK α , 2θ≦50.0°, scan range: 0-180°, pivot angle: 6°, step: 6°, scan rate: 1.8°/min.
2. Powder X-ray analysis
Instrument: Rigaku D/max 2550 powder X-ray diffractometer Test conditions: voltage: 40 KV, current: 150 mA, scan rate: 8°/min.
3. DSC analysis
Instrument type: Seiko Instruments Inc. Differential Scanning Calorimeter Test conditions: purge gas: N 2 , heating rate: 10° C. /min. Temperature range: 25-250° C.
4. IR absorbance spectra
Instrument Nicolet FT-IR spectrometer: IMPACT 400 Test conditions: KBr pellet
5. HPCL analysis
Instrument: SHIMADZU LC-10Avp high performance liquid chromatography, SPD-M10Avp diode array detector, CLASS-VP chromatography data system; column: Alltch C 18 (5μ, 150×4.6 mm); test conditions: column temperature: room temperature; wavelength: 290 nm; mobile phase: methanol/phosphate saline pH 3.0 (64/36); flow rate : 1.0 mL/min; injection volume: 20 μL; injection concentration: 500.0 μg/mL
Preparation 1: Synthesis of Pinocembrin Sample
To 1000 ml hydrogenation reaction kettle, was added 5 g (19.7 mmol) of 5,7-dihydroxyflavone, 650 ml of anhydrous ethanol, and 1.5 g of 10% palladium on carbon. Under a hydrogen pressure of 0.13 Mpa, the reaction was performed for 4 h at 40° C. When the reaction was finished, the palladium on carbon was filtered. The filtrate was concentrated, then separated and purified by column chromatography (eluted by methanol:acetic ether:petroleum ether=2:10:100 (V:V:V)) under vacuum. The solvent was evaporated to dryness, and 3.9 g of white amorphous solid powder was obtained (purity: 98.6%, detected by HPLC) in a yield of 52% [2] .
Preparation of a Sample of α Crystalline Form of Pinocembrin
EXAMPLE 1
Method 1 for Preparing a Sample of α Crystalline Form of Pinocembrin
5 g pinocembrin sample was added to 20 ml of 95% ethanol, and was heated to be dissolved completely, then cooled to room temperature and allowed to stand for 24 h. White solid was precipitated, and was filtered and dried. 4.5 g of white crystalline (purity: 98.8%, detected by HPLC) was obtained in a recovery of 90%.
The obtained crystalline was analyzed by X-ray single crystal diffraction. It showed monoclinic symmetry, space group was P2 1 /c, and the crystal cell parameter values were a=5.189 Å, b=24.149 Å, c=10.472 Å, α=90°, β=102.31° and γ=90°.
Powder (polycrystal) X-ray diffraction (CuK α radiation) was performed on the obtained crystalline. The characteristic peak values of the diffraction peak location: 2-Theta value (°) or d value (Å) and the relative strength of diffraction peak: peak height value (Height %) or peak area value (Area %) were shown in Table 4, and the obtained trace was shown in FIG. 4 .
DSC analysis was performed on the obtained crystalline, and decalescence transition temperature was 206° C.
IR analysis with KBr pellet was performed on the crystalline obtained, and the characteristic peaks were as follows: 3090.6, 3011.6, 2889.1, 2747.4, 2636.2, 1631.5, 1602.5, 1584.3, 1487.7, 1466.2, 1454.5, 1435.6, 1354.9, 1302.4, 1257.0, 1217.0, 1168.2, 1088.6, 1064.9, 1028.0, 1014.6, 1001.3, 975.8, 918.0, 887.7, 861.8, 825.9, 789.9, 766.4, 715.2, 698.1, 663.7, 646.7, 620.3, 587.3, 574.9, 560.5, 526.9 and 487.9 cm −1 .
The above spectra data showed that the crystalline form obtained in the present example was α crystalline form.
EXAMPLES 2 TO 10
Methods 2 to 10 for Preparing a Sample of α Crystalline Form of Pinocembrin
Referring to the preparation method of Example 1, using ethyl acetate, chloroform, acetone, acetonitrile, THF, ether, benzene, cyclohexane or DMF as the solvent, white crystalline of pinocembrin was obtained. The results of the experiments were shown in table 6. Powder X-ray diffraction, DSC and IR analysis were performed on the obtained crystalline, and the results showed that the crystalline form was α crystalline form of pinocembrin.
TABLE 6
Results of the preparation of samples of α crystalline form of
pinocembrin
reaction
product weight
HPLC purity
recovery
example
solvent
(g)
(%)
(%)
2
ethyl acetate
4.40
99.0
88
3
chloroform
4.30
98.7
86
4
acetone
4.30
99.1
86
5
acetonitrile
4.20
98.9
84
6
THF
4.25
98.8
85
7
ether
4.35
98.6
87
8
benzene
4.20
98.9
84
9
cyclohexane
4.20
98.6
84
10
DMF
4.20
98.7
84
EXAMPLE 11
Method 11 for Preparing the Sample of α Crystalline Form of Pinocembrin
5 g pinocembrin sample was dissovled in 100 ml mixture of 95% ethanol and acetone (95% ethanol:acetone=1:1) completely at room temperature, then 100 ml water was added under stirring, and white precipitate appeared. The precipitate was filtered under reduced pressure and dried to obtain 4.00 g white crystalline (purity: 98.7%) in a recovery of 80.0%. Powder X-ray diffraction, DSC and IR analysis were performed on the obtained crystalline form, and the results showed that the crystalline form obtained was α crystalline form of pinocembrin.
EXAMPLES 12 TO 16
Methods 12 to 16 for Preparing a Sample of α Crystalline Form of Pinocembrin
Referring to the preparation method of Example 1, using the mixture of isopropanol and THF (isopropanol:THF=2:1), the mixture of acetonitrile and DMF (acetonitrile:DMF=4:1), the mixture of methanol and acetone (methanol:acetone=3:2), the mixture of ethanol and acetonitrile (ethanol:acetonitrile=1:1), and the mixture of ethanol, acetone and glacial acetic acid (ethanol:acetone:glacial acetic acid=2:1:0.1) as the solvents, white crystalline of pinocembrin was obtained. The results of the experiments were shown in Table 7. Powder X-ray diffraction, DSC and IR analysis were performed on the obtained crystalline, and the results showed that the crystalline form obtained was α crystalline form of pinocembrin.
TABLE 7 Results of samples of α crystalline form of pinocembrin reaction product weight HPLC purity recovery example solvent (g) (%) (%) 12 2:1 isopropanol-THF 4.00 98.8 80 13 4:1 acetonitrile-DMF 3.80 98.7 76 14 3:2 methanol-acetone 3.90 98.9 78 15 1:1 ethanol-acetonitrile 4.05 99.0 81 16 2:1:0.1 ethanol-acetone-glacial 4.10 98.9 82 acetic acid
Preparation of a Sample of β Crystalline Form of Pinocembrin
EXAMPLE 17
Method 1 for Preparing a Sample of β Crystalline Form of Pinocembrin:
10 g sample of α crystalline form of pinocembrin was placed in a mortar, grinded evenly in the same direction for 1 hour at room temperature, and white crystalline was obtained, which is different from α crystalline form.
Powder (polycrystal) X-ray diffraction (CuK α radiation) was performed on the obtained crystalline. The characteristic peak values of the diffraction peak location:2-Theta value (°) or d value (Å) and the relative strength of diffraction peak: peak height value (Height %) or peak area value (Area %), were shown in Table 5, and the obtained trace was shown in FIG. 7 .
DSC analysis was performed on the obtained crystalline, and decalescence transition temperature was 204° C., as showed in the DSC trace.
IR analysis with KBr pellet was performed on the crystalline obtained, and the characteristic peaks were as follows: 3090.8, 2890.0, 2748.9, 2638.3, 1633.5, 1602.9, 1585.0, 1487.9, 1466.1, 1454.3, 1344.4, 1302.7, 1216.7, 1168.2, 1088.4, 1065.5, 1028.8, 1014.3, 1001.5, 975.8, 917.8, 888.2, 861.8, 826.6, 789.1, 766.6, 741.1, 715.4, 698.0, 663.7, 646.0, 620.5, 587.9, 574.8, 560.9, 527.2 and 488.4 cm −1 .
The above spectra date showed that the crystalline form obtained in the present example was β crystalline form.
EXAMPLE 18
Method 2 for Preparing β Crystalline Form of Pinocembrin
At room temperature, 5 g pinocembrin sample was dissolved in 75 ml DMSO, then to which 150 ml of water was added under stirring, and white precipitate appeared. The precipitate was filtered and dried to obtain 4.2 g white crystalline (purity: 98.8%, detected by HPLC) in a recovery of 84.0%. Powder X-ray diffraction, DSC and IR analysis were performed on the obtained crystalline, and the results showed that the crystalline form obtained was β crystalline form of pinocembrin.
EXAMPLE 19
Method 3 for Preparing a Sample of β Crystalline Form of Pinocembrin
Except that pyridine was used as the solvent, the same preparation method as that of Example 18 was used, and 8.8 g white crystalline was obtained (purity: 98.6%, detected by HPLC) in a recovery of 88.0%. Powder X-ray diffraction, DSC and IR analysis were performed on the obtained crystalline, and the results showed that the crystalline form obtained was β crystalline form of pinocembrin.
EXAMPLE 20
Method for Preparing a Sample of Pinocembrin Mixture of α Crystalline Form and β crystalline form in a ratio 1:1
10 g of pinocembrin sample α and β crystalline form were respectively weighed and placed into a sealable vessel. The vessel was sealed and shook to mix the solid evenly. The mixture sample of α and β crystalline form in a ratio 1:1 was obtained.
Formulation
EXAMPLE 21
Method 1 for Preparing a Combined Pharmaceutical Preparation (Tablet)
The samples of pure α crystalline form, pure β crystalline form, or solid mixture of (α+β) crystalline form (α:β=1:1) of pinocembrin were mixed with excipients in different proportions to obtain a solid of the combined pharmaceutical active ingredients. Tablets containing 5˜60 mg of active ingredients were prepared. The tablet formula were given in Table 8.
TABLE 8
Preparation formula for combined pinocembrin tablets
amount (g/1000 tablets)
Formula
Formula
Formula
Formula
Formula
Formula
Formula
components
1
2
3
4
5
6
7
Pinocembrin (g)
5.0
10.0
20.0
30.0
40.0
50.0
60.0
Lactose (g)
100.0
100.0
100.0
100.0
100.0
100.0
100.0
Starch (g)
35
30
20
10
—
—
—
Low-substituted
3.0
3.0
3.0
3.0
3.0
3.0
3.0
hydroxypropyl
cellulose (g)
MCC (g)
—
—
—
—
3.0
3.0
3.0
Talc powder (g)
6.0
6.0
6.0
6.0
6.0
6.0
6.0
Magnesium
1.0
1.0
1.0
1.0
1.0
1.0
1.0
stearate (g)
1% Sodium
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.
hydroxymethyl
cellulose
The detailed preparation method was as follows: mixing the excipients with pinocembrin evenly, then adding appropriate amount of 1% sodium hydroxymethyl cellulose solution to make a dough. The dough was screened to obtain granules. The wet granules were dried and sieved. Then magnesium stearate and talc powder were added and mixed evenly, and the product was obtained by tabletting.
EXAMPLE 22
Method 2 for Preparing a Combined Pharmaceutical Formulation (Capsule)
The samples of pure α crystalline form, pure β crystalline form, or solid mixture of (α+β) crystalline form (α:β=1:1 or 1:3) of pinocembrin were mixed with excipients in different proportions to obtain a solid of the combined pharmaceutical active ingredients. The capsules containing 5˜60 mg of active ingredients were prepared. The capsule formulas were given in Table 9.
TABLE 9
Preparation formulas for combined pinocembrin capsules
Amount (g/1000 capsules)
Formula
Formula
Formula
Formula
Formula
Formula
Formula
components
1
2
3
4
5
6
7
Pinocembrin
5.0
10.0
20.0
30.0
40.0
50.0
60.0
(g)
Lactose(g)
—
—
—
—
—
—
—
Starch(g)
100.0
100.0
100.0
100.0
—
—
—
MCC(g)
—
—
—
—
70.0
60.0
50.0
Magnesium
1.0
1.0
1.0
1.0
1.0
1.0
1.0
stearate(g)
1% Sodium
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.
q.s.
hydroxymethyl
cellulose
The detailed preparation method was as follows: mixing the excipients with pinocembrin evenly, then appropriate amount of 1% sodium hydroxymethyl cellulose solution was added to make wet granules, the wet granules were dried and sieved. Then magnesium stearate was added and mixed evenly, and the product was obtained by filling the mixture above into empty capsules. Alternatively, without granulation, the product was obtained by filling the excipients and pinocembrin into empty capsules directly, after they were mixed evenly and sieved.
EXAMPLE 23
Method 3 for Preparing Combined Pharmaceutical Formulation (Injection Solution and Freeze-dried Powder for Injection)
Pure α crystalline form, pure β crystalline form, or solid mixture of (α+β) crystalline form (α:β=1:1) of pinocembrin were mixed with excipients in different proportions to obtain a solid of the combined pharmaceutical active ingredients. Then the injections containing 5˜60 mg of active ingredients per ampoule were obtained. The injection formulas were given in Table 10.
TABLE 10 Preparation formula for combined pinocembrin injections Formula Formula Formula Formula components 1 2 3 4 Pinocembrin (g) 1 1 1 1 Hydroxypropy1-β-cyclodextrin (g) 40 40 20 20 Distilled water (ml) 400 100 10000 10000 Ethanol (ml) 20 20 20 20 Sodium chloride (g) 90 Dextrose (g) 500
Formula 1: Preparation of Pinocembrin Injection Solution
(1) To 400 ml of distilled water, 40 g of hydroxypropyl-β-cyclodextrin was added and dissolved with stirring; (2) To 20 ml ethanol, 1 g of pinocembrin was added and dissolved, then the obtained solution was added into the hydroxypropyl-β-cyclodextrin solution mentioned above; (3) The mixed solution was stirred magnetically for 20 min at 40˜50° C. When the solution became clear and transparent, 0.5 g of actived carbon for injection was added. Then the mixture was heated to 80° C. with stirring and kept at this temperature for 15 min, then the carbon was filtered. The filtrate was subpackaged into ampoule at 4 ml each. Pinocembrin injection solution was obtained after sterilizing at 121° C. for 15 min.
Formula 2: Preparation of Pinocembrin Freeze-dried Powder for Injection
(1) In the sterile room, 40 g of hydroxypropyl-β-cyclodextrin was weighed and dissolved in water to make 150 ml solution. 0.1 g actived carbon was added, and the mixture was heated to mild boiling for 15 min, and then the carbon was filtered out; (2) 1 g of pinocembrin was dissolved in 20 ml anhydrous ethanol, then the obtained solution was added into the hydroxypropyl-β-cyclodextrin solution mentioned above; (3) The mixture was stirred magnetically for 20 min at 40˜50° C.- When the solution became clear and transparent, the inclusion complex solution of pinocembrin in hydroxypropyl-β-cyclodextrin was obtained; (4) Water was added to the inclusion complex solution to 200 ml. The mixture was filtered through 0.22 μm filter membrane. The filtrate was subpackaged into vial of 10 ml (2 ml/vial), and placed into freeze dryer to freeze-dry. The sterile powder for injection was obtained after the vials' stoppers were sealed.
Formula 3: Preparation of Pinocembrin Sodium Chloride Infusion
(1) To 200 ml of distilled water, 20 g of hydroxypropyl-β-cyclodextrin was added and dissolved with stirring. 0.5 g actived carbon for infusion was added. The mixture was heated to 80° C. with stirring and kept at this temperature for 15 min, then the carbon was filtered; (2) 1 g of pinocembrin was weighed and dissolved in 20 ml anhydrous ethanol, then the obtained solution was poured into the hydroxypropyl-β-cyclodextrin solution mentioned above; (3) The mixture was stirred magnetically for 20 min at 40˜50° C. When the solution became clear and transparent, the inclusion complex solution of pinocembrin in hydroxypropyl-β-cyclodextrin was obtained; (4) Water was added to the inclusion complex solution to 800 ml. After adding 90 g sodium chloride for injection, the solution was adjusted to a pH of 8˜9 and diluted to 10000 ml with water. Then 10 g actived carbon for injection was added, and stirred for 20 min; (5) After the carbon was removed, the solution was subpackaged in 100 ml per bottle. The product was obtained after sterilizing at 121° C. for 30 min.
Formula 4: Preparation of Pinocembrin Dextrose Infusion
(1) 20 g of hydroxypropyl-β-cyclodextrin was added to 200 ml of distilled water and dissolved with stirring. 0.5 g actived carbon for infusion was added. The mixture was heated to 80° C. by stirring and kept at this temperature for 15 min, then the carbon was filtered; (2) 1 g of pinocembrin was dissolved in 20 ml anhydrous ethanol, then the obtained solution was poured into the hydroxypropyl-β-cyclodextrin solution mentioned above; (3) The mixture was stirred magnetically for 20 min at 40˜50° C. When the solution became clear and transparent, the inclusion complex solution of pinocembrin in hydroxypropyl-β-cyclodextrin was obtained; (4) Water was added to the inclusion complex solution to 800 ml. After adding 500 g glucose for injection, the solution was adjusted to a pH of 8˜9 and diluted to 10000 ml with water. Then 10 g actived carbon for injection was added, and stirred for 20 min; (5) After the carbon was removed, the solution was subpackaged in 100 ml per bottle. The product was obtained after sterilizing at 121° C. for 30 min.
EXAMPLE 24
In vivo Absorption and Blood Concentration Characteristics for Pinocembrin Solid Active Ingredient of α and β Crystalline Forms:
18 of SD rats, female and male each half, with body weight of 230˜250 g, were randomized into 3 groups, with 6 rats each group and female half. After 10 hours of fasting but free water intake, the rats were administrated with pinocembrin solid active ingredient powder of α, β or 1:1 (α+β) mixed crystalline forms, at a dose of 50 mg/kg to stomach. Then the arterial blood samples at different times were taken and the contents of pinocembrin were determined. The result showed that for pinocembrin of different crystalline forms, at the same dosage by oral administration, the blood concentrations and the time to reach the peak concentration were different, wherein the blood concentration of α crystalline form was obviously lower than that of β crystalline form.
TABLE 11
Blood concentrations at different time for rats having been administered
orally with pinocembrin samples of different crystalline forms (detected
by HPLC, peak area value)
time
crystalline forms
10 min
20 min
30 min
40 min
β crystalline from
13.2
48.6
14.6
14.2
1:1 (α + β) crystalline
8.5
15.6
7.9
7.1
forms
α crystalline form
3.8
9.7
4.4
3.5
Note:
the blood concentrations listed in the table were the average for the rats in each group.
REFERENCES
1. Chinese patent: publication number CN1695608A
2. Cheng Yonghao, etc. synthesis of 5,7-dihydricflavanone, chemical reagents, 2006, 28(7): 437
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Two crystalline forms of pinocembrin of formula (I): α and β, their preparation and their use for manufacture of pharmaceutical compositions. There exists difference between them in bioavailability. They are used for treating and preventing cerebral ischemic diseases by protective action of neurovascular unit, and enhancing blood drug level in vivo.
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RELATED APPLICATION
Variable Support Shoe, Ser. No. 310,836,filed Feb. 14, 1989.Related copending application Ser. No. 310,836 filed Feb. 14, 1989,shows the use of an air pump and air bladder arrangements, integral with an athletic shoe, to provide increased support to the foot and ankle in an athletic shoe during activity, and decreased pressure and support during periods of inactivity.
FIELD OF THE INVENTION
The present invention relates to an orthopaedic device, and specifically to an ankle brace for stabilizing an ankle before and after injury. In particular, the ankle brace of the present invention stabilizes the ankle against inversion and eversion and anterior subluxation while allowing normal dorsiflexion and plantarflexion movement.
BACKGROUND OF THE INVENTION
It has previously been proposed to provide an ankle brace or orthopaedic apparatus, including air inflatable bladders as shown in Glenn W. Johnson, Jr.'s U.S. Pat. Nos. 4,280,489,granted July 28, 1981,and No. 4,628,945,granted Dec. 16, 1986in which the apparatus is intended to be worn within a separate shoe and is inflatable with an external source of air pressure or is preinflated. In addition, various arrangements have been proposed for ventilating shoes by circulating air through the shoes. Typical patents showing this type of arrangement include M. Dunker, U.S. Pat. No. 2,552,711;D. W. Oltrogge, U.S. Pat. No. 2,560,591;A. C. Crawford, U.S. Pat. No. 2,676,422;C. N. Eaton, U.S. Pat. No. 3,029,530;E. Karras, U.S. Pat. No. 3,331,146;and James Faiella, U.S. Pat. No. 4,414,760.These patents disclose the use of an air pumping arrangement actuated by foot pressure for circulating air through a shoe, but do not include any orthopaedic support functions. Reference is also made to German publication designated OffenlegungSschrift No.2321817,published Nov. 15, 1973.That publication shows a ski boot with a rigid sole and a pump mounted in the sole. The pump can be latched to an inactive state when the inflatable pads are pressurized.
After injury to an ankle, such as a fracture or severe ankle sprain, it may be necessary to completely immobilize the ankle through the use of a molded plaster or resin cast. However, once the injury has been stabilized, recovery may be hastened by removing the molded plaster or resin cast and using a removable functional walking brace so that the ankle can be exercised during healing. Also, if the injury is not severe enough to require complete immobilization, it may only be necessary to use a functional walking brace to stabilize the ankle against inversion (the foot rolling inward), eversion (the foot rolling outward) or anterior subluxation (partial dislocation) while still permitting the normal dorsiflexion and plantarflexion forward and rearward motion of the lower leg relative to the foot) movement of the ankle. However, less pressure and support is required when resting. Furthermore, it is undesirable to have the feet or ankles subject to substantial pressure while resting as this may inhibit circulation during rest periods.
It is therefore desirable to have an ankle brace which provides greater support and pressure to the ankle during walking and the like and less pressure upon the ankle and foot during periods of rest.
SUMMARY OF THE INVENTION
The present invention is a new and improved ankle brace which provides varying amounts of pressure and support to the foot and ankle. The brace has two side supports with inflatable bladders attached to the supports. The brace also includes a pump which is activated by walking or running and supplies air to the inflatable bladders. Also included are means for securing the side supports to firmly encase the ankle. The means for securing the side supports could be an arrangement of straps and D-rings, straps and velcro type fasteners or other appropriate systems.
The air bladders may have a high pressure release valving arrangement, and also be provided with bleed arrangements so that the bladders may not be inflated above a predetermined pressure and so that the air pressure in the bladders will gradually leak out over a period of time.
One-way valves may be provided, both at the inlet to the pump and at the outlet therefrom, leading to the air bladders. With the pump located under the user's foot, pressure will be drawn in whenever the foot is raised, and air will be pumped out to the air bladders whenever the foot engages the ground and the pump chamber is compressed. The bladders may have a bleed valve arrangement as mentioned above which may be either in the form of a specific physical valve, or this function may be provided through a series of small holes extending through the surface of the bladders.
The pump may be in the form of a relatively flat chamber underlying the heel of the user, and is normally resiliently biased so that the air chamber is expanded. Then, when the person's foot is applied downward onto the chamber, it is compressed and the air is forced into the support bladders. Subsequently, when the foot is raised, the pump chamber expands under the resilient force, and air is sucked into the pump chamber. This process is repeated until the support bladders reach their full rated pressure. At this pressure level, the release valve may prevent further build-up of pressure within the bladders, thus controlling the level of pressure against the ankle and foot and the resultant support.
The valves may be implemented by separate valves which may be purchased independently and installed in the interconnecting tubing, or they may be implemented by integral plastic parts in the form of flaps or resiliently mounted plugs which close and open to control the air flow in a manner similar to the separate or independent valves.
At the outlet from the pump, a single one-way valve may be provided or, alternatively, separate one-way valves may extend to each of the support bladders.
The advantage of the system of the present invention is that full support to the ankle and foot is provided when the user is active but, when the user is resting, the bladder arrangements permit a reduction of pressure in the bladders. Heavy support pressure is not applied during resting periods, and circulation is not impaired. Some level of support may be maintained by the use of a compressible filler dispensed within the bladders or outside the bladders. This system prevents undesired eversion, inversion and anterior subluxation caused by activity while allowing for reduced pressure during rest periods.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of the ankle brace as it would appear while being worn with the shoe cut away for clarity.
FIG. 2 is a cross-sectional view taken along plane indicated at II--II in FIG. 1.
FIG. 3 is a partially cut-away view of the ankle brace as it would appear while being worn.
FIG. 4 is an overhead view of the pump with two inlet valves.
FIG. 5 is an overhead view of the pump.
FIG. 6 is a partially exploded view of the present invention.
FIG. 7 shows a cross sectional view of a flap type valve taken along plan 7--7 in FIG. 4.
FIG. 8 is a cross sectional view of a flap type valve taken along the plane VIII--VIII shown in FIG. 7.
DETAILED DESCRIPTION
With reference to FIGS. 1 and 6, the ankle brace of the present invention includes a pair of side supports 10 and 12 preferably made of vacuum molded plastic, having sufficient thickness and other properties so that they are relatively stiff or rigid; and they are shaped so as to fit about the lower leg and ankle and are at least eight inches in length. Inflatable bladders 20 and 21 (shown in FIGS. 2 and 3) are mounted on the side supports 10 and 12 on the side of the side support which faces in toward the leg. The inflatable bladders 20 and 21 can be attached to the side supports 10 and 12 by double-sided adhesive or any other suitable means. The inflatable bladders can be formed from two sheets of plastic heat-sealed along their edges to form an inflatable bag.
The side supports may be securely attached around the leg and ankle using the two securing straps 31 and 32 as shown in the cross-sectional view of FIG. 2 and the cut-away view of FIG. 3. These straps also include velcro portions on their outside surfaces as shown by velcro material 33 and with velcro material 34 at the end portion of the straps. The velcro 34 is attached to the side support 10. As shown in FIGS. 1 and 2, the straps may be tightly drawn around the leg and secured using the velcro material so that the ankle brace securely and firmly supports the ankle.
Interconnecting the two side supports 10 and 12 toward their bottoms is the bottom strap 40. Attached to the bottom strap 40 is a pad member 55, made of a flexible cushioning type material such as polyurethane foam. The bottom strap 40 may include a surface 49 of velcro material with the bottom strap being adjustable through the use of double openings 41 and 42 in the side supports. The ends of the bottom strap 40 may be fixed in position with the use of additional velcro material 44 located on the outside of the side support members as shown in FIG. 3 on side support member 10.
FIG. 1 shows the pump 50 located under the pad member 55 and connected to the bottom strap 40. As shown in FIG. 1, the pump 50 would be located under the wearer's heel. Referring now to FIG. 5, the pump 50 has an inlet valve 70, and an outlet valve 65. The pump also includes a variable volume air chamber 80 having upper and lower flexible sidewalls, and a biasing material 95 which may be a resilient flexible porous pad, and which normally biases the chamber 80 to its expanded volume configuration. When a wearer steps down on the pump 50, the outlet valve 65 opens, and the inlet valve 70 is closed. When the foot is raised, the resilient pad expands the chamber 80, drawing air in through the inlet valve 70, while the outlet valve 65 is closed. Inlet valve 70 and outlet valve 65 may be ball and spring-type valves, but it is to be understood that any appropriate type of one-way valve could be employed.
Extending upward from the outlet valve 65 are two small diameter tubes 61' and 62', each of which is connected to one of the inflatable bladders 20. Alternatively, separate one-way valves 66 and 67, shown in FIG. 4, could be placed in each of the small diameter tubes instead of using one outlet valve 65. It should be noted that the resilient pad 95 used to bias the variable volume air chamber 80 could be replaced with a metal spring, or other suitable resilient material which would bias the chamber to its expanded volume configuration when the user raises his foot and releases pressure from the pump.
FIGS. 4 and 5 show two alternative placements of the inlet valves of the pump 50. FIG. 4 shows the inlet valve 70 replaced with dual inlet valves 71 and 72 placed to either side of the front of the pump. FIG. 5 shows the inlet valve 70 placed toward the wearer's instep in the front of the pump. Also shown in FIG. 4 are the two small diameter tubes 61 and 62 as they could be arranged if each contained an outlet valve 66 and 67 similar to outlet valve 65.
The two inlet valves 71 and 72 of FIG. 4 could alternatively be of a fairly flat flap-type valve. Such a valve is pictured in FIGS. 7 and 8. In such a valve, air drawn in as indicated by the arrow forces the two sealing flaps 13 and 14, which are normally biased together, apart which allows the air to flow through the valve. Air forced in the direction opposite to that indicated by the arrow, toward the flaps, forces flaps 13 and 14 together and they create a substantially airtight seal. This flap-type valve could be made of flexible plastic or rubber and may be more comfortable than a rigid valve when used under the wearer's foot. FIGS. 1 and 6 show the release valve 98, which is an over pressure release and a bleed valve for the inflatable bladder 20. More specifically, a slight amount of air is permitted to bleed from the valve 98 continuously over prolonged periods of time. Further, the relief valve 98 changes state to release air from the inflatable bladder when pressure supplied by the pump becomes excessive, so the maximum pressure level is not exceeded within the inflatable bladders when the wearer of the ankle brace is active.
As an alternative to the bleed function which may be included in relief valve 98, the bladders 20 may be provided with a number of very small holes 96 shown in FIG. 6. The holes 96, which may be in the nature of pinholes, may provide the bleed function which may otherwise be accomplished through the relief valve 98. Also, the position of the relief valve 98 is not necessarily limited to the position shown.
An alternative embodiment of the present invention further includes a closed cell foam pad disposed within the inflatable bladder 20. This is shown in FIG. 6 as 99. The pad can be used to provide a minimum level of support and padding. Alternatively, the pad may be attached to the outside of inflatable bladders 20 and 21 on the side towards the wearer's leg as indicated by 22 and 23 in FIG. 2. The pad may also be open cell foam and may be placed between the bladders and the side supports (not shown).
In conclusion, it is to be understood that the foregoing detailed description relates to a presently preferred embodiment of the present invention. Various changes and modifications may be made without departing from the spirit and scope of the present invention. Thus, by way of example and not of limitation, the various valve structures which have been shown as separate elements may be implemented by constructions formed from the materials out of which the pump and/or bladders are made. Thus, plastic flaps may form one-way valve constructions as shown in FIGS. 7 and 8 and the pressure release valve may be formed of a plastic, rubber or other material which is resiliently biased closed, and forced open when a predetermined level of pressure is reached. Also, the release valve 98 may be preset to a maximum pressure at which it will release air from the inflatable bladder or it may be adjustable. It is further noted that a pump or bellows may be located under the arch or forefoot, instead of or in addition to that located under the heel, as shown in the drawings. Accordingly, the present invention is not limited to the constructions precisely as shown in the drawings or described in the detailed description.
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An ankle brace having two relatively rigid side supports with inflatable bladders attached to them. The side supports are connected at their bottom by a flexible strap upon which is mounted an air pump. The air pump is activated by walking and running and inflates the air bladders mounted on the side supports. The side supports are held firmly in place about the lower leg and ankle by straps. A relief valve and/or pin holes in the bladders prevent excessive pressure in the bladders and provide reduced support when the user is not active.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a U.S. National Stage application of International Application No. PCT/EP2014/070777 filed Sep. 29, 2014, which designates the United States of America, and claims priority to DE Application No. 10 2013 220 426.4 filed Oct. 10, 2013, the contents of which are hereby incorporated by reference in their entirety.
TECHNICAL FIELD
[0002] The present disclosure relates to a method for operating a vehicle, and more specifically to a driver assistance systems and methods for a vehicle.
BACKGROUND
[0003] DE 10 2010 048 103 A1 discloses a method for recuperating kinetic energy from a motor vehicle to optimize based on energy, wherein the method comprises the existence of at least one predetermined condition during the journey of the motor vehicle prompting the ascertainment of an optimum braking distance in respect of recuperable energy, and generation of a signal for the vehicle driver that notifies him, in respect of at least one measure for or while braking the motor vehicle, of the form in which said measure needs to be performed so that braking takes place over the optimum braking distance.
SUMMARY
[0004] The teachings of the present disclosure may allow further improved operation of the vehicle.
[0005] A method for operating a vehicle, wherein the vehicle has a recuperation unit designed to recuperate kinetic energy from the vehicle and an output apparatus designed to output driving information, has—in some embodiments—the following steps. Ascertainment of at least one first parameter denoting possible imminent actuation of the recuperation unit is effected. In addition, ascertainment of whether actuation of the recuperation unit is imminent, on the basis of the at least one ascertained first parameter, is effected. If it is ascertained that actuation of the recuperation unit is imminent, ascertainment of a probable profile for a speed of the vehicle during the ascertained imminent actuation of the recuperation unit on the basis of a prescribable level of a recuperation intensity of the recuperation unit during the ascertained imminent actuation of the recuperation unit is effected. In addition, output of at least one second parameter, denoting the ascertained probable profile of the speed of the vehicle during the ascertained imminent actuation of the recuperation unit, by means of the output apparatus is effected.
[0006] In some embodiments, the method allows further improved operation of the vehicle. This is effected particularly by virtue of the ascertainment of whether actuation of the recuperation unit is imminent, the ascertainment of a probable profile for the speed of the vehicle during the ascertained imminent actuation of the recuperation unit on the basis of the prescribable level of the recuperation intensity of the recuperation unit and the output of the at least one second parameter, denoting the ascertained probable profile of the speed of the vehicle, by means of the output apparatus. This is based on the consideration that actuation of the recuperation unit leads to the braking of the vehicle, which varies depending on the level of the recuperation intensity of the recuperation unit.
[0007] Some embodiments can be used to ascertain the probable profile of the speed of the vehicle during the imminent actuation of the recuperation unit. In addition, the occupants of the vehicle, particularly the driver of the vehicle, can be provided with information about the ascertained probable profile of the speed by virtue of the output of the at least one second parameter. As a result, the driver of the vehicle can adjust the driving behavior in a further improved manner to suit the respective instantaneous driving situation.
[0008] Some embodiments of the method additionally involve ascertainment of a probable braking path for the vehicle during the ascertained imminent actuation of the recuperation unit on the basis of the prescribable level of the recuperation intensity of the recuperation unit during the ascertained imminent actuation of the recuperation unit. Furthermore, the method involves output of at least one third parameter, denoting the ascertained probable braking path of the vehicle during the ascertained imminent actuation of the recuperation unit, by means of the output apparatus. As a result, the occupants of the vehicle, particularly the driver of the vehicle, can, in said driving situation, additionally be provided with information about the ascertained probable braking path of the vehicle, for example the length thereof, and the driver of the vehicle can therefore react to the respective driving situation to a further improved extent.
[0009] The ascertainment of the probable braking path of the vehicle may particularly involve ascertainment of a distance within which the speed of the vehicle falls below a predetermined threshold value during the ascertained imminent actuation of the recuperation unit. As a result, the driver of the vehicle can, on the basis of the predetermined threshold value, be provided with information about the distance after which the vehicle, during the actuation of the recuperation unit, comes to a standstill, travels at walking speed or reaches a minimum speed, for example, before recuperation is effected.
[0010] Some embodiments additionally involve ascertainment of at least one operating parameter for an energy storage apparatus for storing energy recuperated by means of the recuperation unit. In such embodiments, the ascertainment of the probable profile of the speed of the vehicle during the ascertained imminent actuation of the recuperation unit is additionally effected on the basis of the at least one ascertained operating parameter. This is based on the consideration that the level of the recuperation intensity of the recuperation unit can vary on the basis of the respective instantaneous operating state of the energy storage apparatus. The ascertainment of the at least one operating parameter of the energy storage apparatus allows such variation in the recuperation intensity as a result of a corresponding selection of the prescribable level of the recuperation intensity to be advantageously taken into account for the ascertainment of the probable profile of the speed of the vehicle.
[0011] In addition, ascertainment of at least one fourth parameter, selected from the group consisting of an instantaneous mass of the vehicle, an instantaneous tire pressure of at least one tire of the vehicle and an instantaneous attitude of a chassis of the vehicle, can be effected. In some embodiments, the ascertainment of the probable profile of the speed of the vehicle during the ascertained imminent actuation of the recuperation unit is additionally effected on the basis of the at least one ascertained fourth parameter. The cited parameters typically have an influence on the braking behavior of the vehicle, which influence can be taken into account for the ascertainment of the probable profile of the speed of the vehicle.
[0012] Some embodiments additionally involve ascertainment of a route profile and/or of an instantaneous road condition of a road on which the vehicle is traveling. The ascertainment of the probable profile of the speed of the vehicle during the ascertained imminent actuation of the recuperation unit may be additionally effected on the basis of the ascertained route profile and/or the ascertained instantaneous road condition. This is again based on the consideration that the cited parameters have an influence on the braking behavior of the vehicle. These embodiments therefore allow further improved ascertainment of the probable profile of the speed of the vehicle.
[0013] The ascertainment of the route profile of the road on which the vehicle is traveling can involve particularly ascertainment of a gradient or slope of the road. The ascertainment of the instantaneous road condition of the road on which the vehicle is traveling can involve ascertainment of a parameter denoting an instantaneous coefficient of friction of the road, for example. Said parameter may be reduced on the basis of instantaneous ambient conditions, particularly on the basis of an instantaneous weather condition in the region of the surroundings of the vehicle, for example on the basis of rain, snow or black ice.
[0014] The ascertainment of the probable profile of the speed of the vehicle during the ascertained imminent actuation of the recuperation unit can involve ascertainment of a plurality of probable profiles for the speed of the vehicle on the basis of a plurality of different recuperation intensities of the recuperation unit during the ascertained imminent actuation of the recuperation unit. As already explained, the level of the recuperation intensity of the recuperation unit can vary. This can be advantageously taken into account in the cited embodiment. Hence, the driver of the vehicle can be provided with information about different speed profiles of the vehicle during the ascertained imminent recuperation mode.
[0015] Some embodiments additionally involve ascertainment of a probable profile of an acceleration of the vehicle, a rate of change of the speed of the vehicle over time, during the ascertained imminent actuation of the recuperation unit on the basis of the prescribable level of the recuperation intensity of the recuperation unit during the ascertained imminent actuation of the recuperation unit. In addition, the method may involve output of at least one fifth parameter, denoting the ascertained probable profile of the acceleration of the vehicle during the ascertained imminent actuation of the recuperation unit, by means of the output apparatus. As a result, the occupants of the vehicle, particularly the driver of the vehicle, can, in the cited driving situation, additionally be provided with information about the ascertained probable acceleration or braking behavior of the vehicle, and the driver of the vehicle can therefore react to the respective driving situation to a further improved extent.
[0016] In some embodiments, the ascertained probable profile of the speed of the vehicle is transmitted to at least one driver assistance system of the vehicle and/or to at least one further vehicle. As a result, the operation of the driver assistance system can be adjusted to suit the respective ascertained probable profile of the speed of the vehicle, or further road users can be provided with information about the probable profile of the speed of the vehicle. In addition, the ascertained probable braking path of the vehicle and/or the ascertained probable profile of the acceleration of the vehicle during the ascertained imminent actuation of the recuperation unit can be transmitted to the at least one driver assistance system of the vehicle and/or to the at least one further vehicle.
[0017] In some embodiments, the ascertainment of the at least one first parameter involves ascertainment of traffic regulations that apply in a region of instantaneous surroundings of the vehicle. As a result, it is a simple matter to ascertain whether braking of the vehicle and associated actuation of the recuperation unit are imminent.
[0018] The ascertainment of traffic regulations that apply in a region of the instantaneous surroundings of the vehicle can include ascertainment of at least one traffic regulation, selected from the group consisting of a speed limit, a traffic priority rule and a switching phase of a light signal installation. The cited traffic regulations are of particular significance for whether braking of the vehicle as a result of actuation of the recuperation unit is imminent.
[0019] In addition, it is possible to ascertain whether the traffic regulation can probably be observed as a result of sole actuation of the recuperation unit or whether this requires manual braking, for example, additional braking by the driver of the vehicle, and/or an increase in recuperation power or an increase in the level of the recuperation intensity of the recuperation unit.
[0020] In addition, the ascertainment of traffic regulations that apply in a region of the instantaneous surroundings of the vehicle can be effected on the basis of data ascertained by at least one sensor of the vehicle, for example, on the basis of images taken by at least one optical camera of the vehicle, and/or on the basis of data received by at least one communication unit of the vehicle, such as data received by a radio reception unit, a mobile radio reception unit, a vehicle-to-vehicle communication unit and/or a vehicle-to-infrastructure communication unit, and/or on the basis of map data stored in the memory apparatus. This allows reliable ascertainment of the traffic regulations that apply in the region of the instantaneous surroundings of the vehicle. The memory apparatus may be part of a navigation system, particularly a navigation system of the vehicle itself. In addition, the memory apparatus may be a memory apparatus external to the vehicle. The memory apparatus external to the vehicle is part of a server in this case, for example. As a result, the map data can be provided in a form that is as up to date as possible.
[0021] In some embodiments, the ascertainment of the at least one first parameter involves ascertainment of a degree of depression of a gas pedal of the vehicle. As a result, it is a simple matter to ascertain whether actuation of the recuperation unit is imminent.
[0022] Some embodiments may include a computer program product having a computer-readable medium and program code that is stored on the computer-readable medium and that, when executed on a computation unit, instructs the computation unit to carry out a method according to one of the cited embodiments.
[0023] Some embodiments may include a driver assistance system for a vehicle. The driver assistance system has an output apparatus that is designed to output driving information. In addition, the driver assistance system has a computation unit and a computer program product according to the embodiment cited above.
[0024] The computer program product and the driver assistance system have the advantages already cited in connection with the corresponding method, and these advantages will not be explained again at this juncture in order to avoid repetition.
[0025] The output apparatus may particularly have a head-up display. As a result, the driver of the vehicle can be provided with information about the ascertained probable profile of the speed of the vehicle during the ascertained imminent actuation of the recuperation unit without this involving the driver averting his gaze from the instantaneous events for a driver.
[0026] In the embodiments described above, the vehicle may be a motor vehicle, for example an automobile or a truck, the motor vehicle typically being in the form of an electric vehicle or in the form of a hybrid vehicle.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Example embodiments of the teachings of the present disclosure will now be explained in more detail with reference to the appended figures.
[0028] FIG. 1 shows a flowchart for a method for operating a vehicle in one embodiment;
[0029] FIG. 2 shows a driver assistance system for a vehicle in one embodiment;
[0030] FIG. 3A shows driving information that is output by means of the output apparatus shown in FIG. 2 in a first representation;
[0031] FIG. 3B shows driving information that is output by means of the output apparatus shown in FIG. 2 in a second representation.
DETAILED DESCRIPTION
[0032] FIG. 1 shows a flowchart for a method for operating a vehicle in one embodiment. The vehicle has a recuperation unit that is designed to recuperate kinetic energy from the vehicle, for example a regenerative brake in the form of an electric drive motor of the vehicle that is operated as a generator. In addition, the vehicle has an output apparatus that is designed to output driving information. The output apparatus is preferably in the form of a visual output apparatus, for example in the form of a head-up display of the vehicle. Typically, the vehicle is a motor vehicle, such as an automobile or a truck. The motor vehicle may particularly be in the form of an electric vehicle or in the form of a hybrid vehicle.
[0033] A step 40 involves, during a driving mode of the vehicle, ascertainment of at least one first parameter denoting possible imminent actuation of the recuperation unit.
[0034] By way of example, the ascertainment of the at least one first parameter may involve ascertainment of traffic regulations that apply in a region of instantaneous surroundings of the vehicle, particularly ascertainment of at least one traffic regulation, selected from the group consisting of a speed limit, a traffic priority rule and a switching phase of a light signal installation.
[0035] In this case, the ascertainment of traffic regulations that apply in a region of the instantaneous surroundings of the vehicle can be effected on the basis of data ascertained by at least one sensor of the vehicle, particularly on the basis of images taken by at least one optical camera of the vehicle, and/or on the basis of data received by at least one communication unit of the vehicle, particularly on the basis of data received by a radio reception unit, a mobile radio reception unit, a vehicle-to-vehicle communication unit and/or a vehicle-to-infrastructure communication unit, and/or on the basis of map data stored in the memory apparatus.
[0036] In addition, the ascertainment of the at least one first parameter can involve ascertainment of a degree of depression of a gas pedal of the vehicle.
[0037] A step 50 involves taking the at least one first parameter ascertained in step 40 as a basis for ascertaining whether actuation of the recuperation unit is imminent. By way of example, imminent actuation of the recuperation unit can be ascertained if a speed limit is ascertained in the region of surroundings lying ahead of the vehicle and an instantaneous speed of the vehicle exceeds the value of the ascertained speed limit. Furthermore, imminent actuation of the recuperation unit can be ascertained if an instantaneous speed of the vehicle exceeds a speed that is appropriate for traveling on a route section lying ahead of the vehicle, for example an imminent curve. In addition, imminent actuation of the recuperation unit can be ascertained if a light signal installation, for example a traffic light installation, situated in the region of the surroundings lying ahead of the vehicle outputs a stop order phase for the vehicle. In addition, imminent actuation of the recuperation unit can be ascertained if release of the gas pedal is ascertained. If step 50 involves the ascertainment that actuation of the recuperation unit is not imminent, steps 40 and 50 are carried out as a repeat.
[0038] If, by contrast, step 50 involves the ascertainment that actuation of the recuperation unit is imminent, then a step 60 involves ascertainment of a probable braking path for the vehicle during the ascertained imminent actuation of the recuperation unit and of a probable profile of a speed and of an acceleration of the vehicle on the ascertained braking path of the vehicle on the basis of a prescribable level of a recuperation intensity of the recuperation unit during the ascertained imminent actuation of the recuperation unit. By way of example, the prescribable level of the recuperation intensity of the recuperation unit corresponds to a recuperation intensity that recuperates a maximum quantity of energy.
[0039] The ascertainment of the probable braking path of the vehicle can particularly involve ascertainment of a distance within which the speed of the vehicle during the ascertained imminent actuation of the recuperation unit falls below a predetermined threshold value, for example 6 km/h.
[0040] The ascertainment of the probable braking path of the vehicle and of the probable profile of the speed and also of the acceleration of the vehicle during the ascertained imminent actuation of the recuperation unit can additionally be effected on the basis of at least one ascertained operating parameter of an energy storage apparatus for storing energy recuperated by means of the recuperation unit. By way of example, if the energy storage apparatus is in the form of a storage battery, then it is possible for an instantaneous temperature and/or an instantaneous state of charge of the storage battery to be ascertained and for a value for the prescribable level of the recuperation intensity of the recuperation unit during the ascertained imminent actuation of the recuperation unit to be determined therefrom.
[0041] In addition, the ascertainment of the probable braking path of the vehicle and of the probable profile of the speed and also of the acceleration of the vehicle during the ascertained imminent actuation of the recuperation unit can additionally be effected on the basis of an ascertained instantaneous mass of the vehicle, an ascertained instantaneous tire pressure of at least one tire of the vehicle and/or an ascertained instantaneous attitude of a chassis of the vehicle.
[0042] In addition, the ascertainment of the probable braking path of the vehicle and of the probable profile of the speed and also of the acceleration of the vehicle during the ascertained imminent actuation of the recuperation unit can additionally be effected on the basis of an ascertained route profile and/or an ascertained instantaneous road condition of a road on which the vehicle is traveling.
[0043] A step 70 involves output of at least one second parameter, denoting the ascertained probable profile of the speed of the vehicle during the ascertained imminent actuation of the recuperation unit, a third parameter, denoting the ascertained probable braking path of the vehicle during the ascertained imminent actuation of the recuperation unit, and a fifth parameter, denoting the ascertained probable profile of the acceleration of the vehicle during the ascertained imminent actuation of the recuperation unit, by means of the output apparatus.
[0044] In addition, in the embodiment shown, a step 80 involves transmission of the ascertained probable profile of the speed and of the acceleration of the vehicle and also of the ascertained probable braking path of the vehicle to at least one driver assistance system of the vehicle and/or to at least one further vehicle.
[0045] The embodiments described above are therefore used to output, for example to display, both the probable speed and the probable remaining path of the vehicle during the recuperation. These data can be made available to the driver and in the vehicle, or to the surroundings thereof, for example. In particular, these data can be presented in a head-up display and laid directly on the road image, and/or overlaid with the road image. Hence, the driver can directly identify what distance, for example in meters, the vehicle will still cover if it continues to recuperate without interruption.
[0046] As a result of capture of relevant environmental data, such as gradient of the road, condition, coordinates, for example, and of relevant vehicle data, such as current speed, mass, tire pressure and recuperation power, it is possible to predict the speed of the vehicle for the next few meters.
[0047] As a result of the ascertainment of the probable recuperation path, not only is it possible for the driver to be advised of an optimum recuperation starting time, it is also possible for the data to be made available to the vehicle if the vehicle has an autonomous or semiautonomous driving mode of operation. The vehicle can then begin recuperative braking at the recuperation starting time.
[0048] In this case, the aforementioned sensors of the vehicle recognize when stopping or braking will be necessary, for example at a junction or set of traffic lights, at an entrance to a village or an imminent speed limit.
[0049] This recognition is possible by means of radar and/or camera sensors and/or GPS data, particularly navigation data, for example. Both the driver and the vehicle, if said vehicle is driving in automated fashion, receive an output indicating when the optimum time for recuperation will be, at which the greatest possible amount of energy can be supplied. In this case, the head-up display, for example, is used to display the starting time, at which the driver or the vehicle will demand no more drive power for the vehicle and recuperation is begun. This can be accomplished by means of a bar display with an associated speed, for example, and additionally or alternatively be presented in color, with a presentation in red denoting a high speed and a presentation in green denoting an idling mode, for example.
[0050] Further presentation options, which can also be combined, are audible signals, a numerical presentation in the head-up display and/or vibration of the gas pedal or buildup of a boosted back pressure, and/or a display in a combined instrument of the vehicle by means of graphical representations.
[0051] The driver can also be notified in a purely audible manner, for example by a “gong”, and by virtue of a light flashing.
[0052] The provision of such a display can motivate the driver firstly in favor of recuperation technology and awareness of recuperation. By way of example, this means that the driver can recognize whether his vehicle is still rolling toward a red set of traffic lights at an appropriate speed or whether he needs to depress the gas pedal again. This means that it is possible to prevent a needless demand for drive power for the vehicle, for example.
[0053] The display can therefore be used to optimize the recuperation power, since it is thereby made clear to the driver when the vehicle comes to a standstill or continues to travel just at a walking pace.
[0054] As a result, it is additionally possible for the driver to recognize whether he has to brake or whether his vehicle is coming to a standstill exclusively by virtue of the recuperation. This means that it is again possible for a maximum amount of energy to be supplied to the energy storage apparatus, for example a vehicle battery, and for wear on the vehicle brake and also on the tires of the vehicle to be reduced when the driver recognizes that even light braking is not absolutely necessary.
[0055] In addition, the direct incorporation of the remaining range during recuperation into the head-up display affords interference-free and constantly visible perception.
[0056] FIG. 2 shows a driver assistance system 12 for a vehicle 1 in one embodiment. In the embodiment shown, the vehicle 1 is a motor vehicle in the form of an automobile. For reasons of clarity, the vehicle 1 and the further components are presented schematically in FIG. 2 .
[0057] The vehicle 1 has a recuperation unit 2 that is designed to recuperate kinetic energy from the vehicle 1 . By way of example, the recuperation unit 2 is in the form of a regenerative brake in the form of an electric drive motor of the vehicle 1 that is operated as a generator. In addition, the vehicle 1 has an energy storage apparatus 4 , for example at least one storage battery or at least one capacitor, for storing energy recuperated by means of the recuperation unit 2 . The energy storage apparatus 4 is additionally connected to the recuperation unit 2 by means of a connecting element 27 .
[0058] The driver assistance system 12 has an output apparatus 3 that is designed to output driving information. In the embodiment shown, the output apparatus 3 is in the form of a visual output apparatus. To this end, the output apparatus 3 has a head-up display 13 .
[0059] Furthermore, the driver assistance system 12 has a computation unit 11 . The computation unit 11 has a computer-readable medium 10 and a processing unit 18 . By way of example, the processing unit 18 may be in the form of an electronic processor, particularly in the form of a microprocessor or microcontroller. By way of example, the computer-readable medium 10 may be in the form of an EEPROM, flash memory or flash EEPROM or NVRAM. The computer-readable medium 10 stores program code that, when executed on the computation unit 11 , instructs the computation unit 11 to carry out the aforementioned embodiments of the method for operating the vehicle 1 , particularly the embodiment shown in FIG. 1 . In this case, the computation unit 11 is designed particularly to ascertain a probable braking path for the vehicle 1 during ascertained imminent actuation of the recuperation unit 2 and also a probable profile of a speed and of an acceleration of the vehicle 1 on the ascertained braking path of the vehicle 1 on the basis of a prescribable level of a recuperation intensity of the recuperation unit 2 during the ascertained imminent actuation of the recuperation unit 2 .
[0060] To this end, the computation unit 11 is connected to at least one sensor 6 of the vehicle 1 via a signal line 28 . By way of example, the at least one sensor 6 is in the form of an optical camera. In addition, the computation unit 11 is connected to at least one communication unit 7 of the vehicle 1 via a signal line 29 . By way of example, the communication unit 7 is in the form of a radio reception unit, mobile radio reception unit, vehicle-to-vehicle communication unit and/or vehicle-to-infrastructure communication unit of the vehicle 1 . In addition, the computation unit 11 is connected to a navigation system 19 of the vehicle 1 via a signal line 30 . The navigation system 19 has a memory apparatus 8 with map data stored thereon and also a satellite-aided position finding apparatus 20 . As a result, it is possible to ascertain traffic regulations that apply in a region of instantaneous surroundings of the vehicle 1 on the basis of data ascertained by the at least one sensor 6 , on the basis of data received by the at least one communication unit 7 and/or on the basis of map data stored in the memory apparatus 8 , and to infer imminent actuation of the recuperation unit 2 therefrom. In addition, it is possible to infer imminent actuation of the recuperation unit 2 if braking of a further vehicle traveling ahead of the vehicle is ascertained on the basis of data ascertained by the at least one sensor 6 and/or on the basis of data received by the at least one communication unit 7 .
[0061] In addition, the computation unit 11 is connected, via a signal line 32 , to a sensor 17 that is designed to ascertain a degree of depression of a gas pedal 9 of the vehicle 1 . As a result, it is possible to infer imminent actuation of the recuperation unit 2 if the gas pedal 9 is released.
[0062] Furthermore, the computation unit 11 is connected, via a signal line 31 , to at least one sensor 16 that is designed to ascertain at least one operating parameter of the energy storage apparatus 4 . By way of example, the at least one sensor 16 is designed to ascertain an instantaneous temperature and/or an instantaneous state of charge of the energy storage apparatus 4 . As a result, the ascertainment of the probable braking path of the vehicle 1 and of the probable profile of the speed and also of the acceleration of the vehicle 1 during the ascertained imminent actuation of the recuperation unit 2 can additionally be effected on the basis of the at least one ascertained operating parameter of the energy storage apparatus 4 .
[0063] The computation unit 11 is additionally connected, via a signal line 35 , to a sensor 15 that is designed to ascertain an instantaneous speed of the vehicle 1 . Furthermore, the computation unit 11 is connected, via a signal line 36 , to at least one sensor 14 that is designed to ascertain an instantaneous tire pressure of tires of the vehicle 1 , which are not shown in more detail in FIG. 2 . As a result, the ascertainment of the probable braking path of the vehicle 1 and of the probable profile of the speed and also of the acceleration of the vehicle 1 during the ascertained imminent actuation of the recuperation unit 2 can additionally be effected on the basis of the ascertained instantaneous speed of the vehicle 1 and also the ascertained instantaneous tire pressure of the tires of the vehicle 1 .
[0064] The computation unit 11 is additionally designed to output at least one second parameter, denoting the ascertained probable profile of the speed of the vehicle 1 during the ascertained imminent actuation of the recuperation unit 2 , a third parameter, denoting the ascertained probable braking path of the vehicle 1 during the ascertained imminent actuation of the recuperation unit 2 , and a fifth parameter, denoting the ascertained probable profile of the acceleration of the vehicle 1 during the ascertained imminent actuation of the recuperation unit 2 , by means of the output apparatus 3 . To this end, the computation unit 11 is connected to the output apparatus 3 via a signal line 34 . In addition, the computation unit 11 is designed to transmit the ascertained probable profile of the speed and of the acceleration of the vehicle 1 and also of the ascertained probable braking path of the vehicle 1 to at least one driver assistance system 5 of the vehicle 1 . To this end, the computation unit 11 is connected to the at least one driver assistance system 5 via a signal line 33 . In addition, the ascertained probable profile of the speed and of the acceleration and also of the ascertained probable braking path of the vehicle 1 can be transmitted to at least one further vehicle if the communication unit 7 is in the form of a vehicle-to-vehicle communication unit, for example.
[0065] FIG. 3A shows driving information that is output by means of the output apparatus presented in FIG. 2 in a first representation.
[0066] In this case, the driving information that is output by means of the head-up display of the output apparatus, which is shown in FIG. 2 , contains a display 22 with a driving recommendation in the form of a turn recommendation and also a display 23 of an instantaneous speed of the vehicle.
[0067] In addition, the driving information that is output by means of the head-up display of the output apparatus contains a display 24 that denotes an ascertained probable profile of the speed of the vehicle during ascertained imminent actuation of the recuperation unit of the vehicle that is shown in FIG. 2 . In the representation shown, the display 24 contains a bar representation of the ascertained probable profile of the speed of the vehicle. In this case, the speed bars represent the predicted speed that the vehicle will probably have at different positions if recuperation is effected without interruption.
[0068] Furthermore, the output apparatus is used to output a display 25 that denotes an ascertained probable braking path of the vehicle during the ascertained imminent actuation of the recuperation unit. To this end, in the representation shown, the display 25 is used to output a plurality of distance values that indicate the respective distance from the instantaneous position of the vehicle. As presented in FIG. 3A , the speed decreases with distance covered, until the vehicle either comes to a standstill or achieves an “idling mode”.
[0069] The displays 24 and 25 can provide the driver of the vehicle with information by means of which the driver can initiate a braking process for the vehicle by virtue of actuation of the recuperation unit such that the vehicle essentially comes to a standstill in front of a light signal installation 21 , which is arranged in the region of surroundings lying ahead of the vehicle, if the light signal installation 21 currently outputs a stop order phase for the vehicle, as shown in FIG. 3A .
[0070] In this case, the displays 22 , 23 , 24 and 25 are output by means of the head-up display of the output apparatus such that they overlie a region of a road 37 , lying ahead of the vehicle, that is visible through a windshield of the vehicle, which is not shown in more detail.
[0071] FIG. 3B shows driving information that is output by means of the output apparatus presented in FIG. 2 in a second representation. Components having the same functions as in FIG. 3A are denoted by the same reference symbols and not explained again below.
[0072] The second representation shown in FIG. 3B differs from the first representation shown in FIG. 3A in that the head-up display of the output apparatus is used to output a display 26 by means of which, as explained above, a suitable time is presented for the driver of the vehicle, at which the recuperation needs to begin in order for the vehicle essentially to come to a standstill in front of the light signal installation 21 . The speed of the vehicle at the beginning of the recuperation process and also the distance of the position at which the recuperation process begins from the instantaneous position of the vehicle are denoted in FIG. 3B by means of a dot-dash line. In addition, the speed of the vehicle on termination of the recuperation process and also the distance of the position at which the recuperation process ends from the instantaneous position of the vehicle are denoted in FIG. 3B by means of a dotted line. In this case, the recuperation process ends, in the representation shown, when the speed of the vehicle falls below a threshold value of 6 km/h.
LIST OF REFERENCE SYMBOLS
[0000]
1 Vehicle
2 Recuperation unit
3 Output apparatus
4 Energy storage apparatus
5 Driver assistance system
6 Sensor
7 Communication unit
8 Memory apparatus
9 Gas pedal
10 Medium
11 Computation unit
12 Driver assistance system
13 Head-up display
14 - 17 Sensor
18 Processing unit
19 Navigation system
20 Position finding apparatus
21 Light signal installation
22 - 26 Display
27 Connecting element
28 - 35 Signal line
37 Road
40 - 80 Step
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A method for controlling operation of a vehicle with a recuperation unit may include determining at least one first parameter denoting possible imminent actuation of the recuperation unit, evaluating whether actuation of the recuperation unit is imminent, and if yes, calculating a probable profile for a speed of the vehicle during the actuation on the basis of a prescribable level of a recuperation intensity of the recuperation unit. The method may also include generating at least one second parameter denoting the ascertained probable profile of the speed of the vehicle during the ascertained imminent actuation of the recuperation unit and displaying the at least one second parameter with an output apparatus.
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FIELD OF THE INVENTION
This invention relates genrally to supports and particularly to supportive seat mechanisms for infants and toddlers.
BACKGROUND OF THE INVENTION
In the known art are various seats, many of them are usable in automobiles.
The following U.S. patents are noted:
U.S. Pat. No. 4,113,306 issued to H. F. Von Wimmersperg on 9-12-78 showed infant seat mechanism usable as both a vehicle safety restraint and as a stroller;
U.S. Pat. No. 3,858,936 issued to D. L. Gerken on 1-7-75 showed one of many types of infant seats or carriers with safety belts and angle adjustment;
U.S. Pat. No. 3,528,701 issued to C. A. Laughlin on 9-15-70 showed an infant carrier with provision for releasably anchoring it to a vehicle seat;
U.S. Pat. No. 3,351,380 issued to R. P. Sprague on 11-7-67 showed an infant carrier detachably affixable to a carriage (shopping cart);
U.S. Pat. No. 3,272,566 issued to E. Rocker on 9-13-66 showed another form of adjustable carrier;
U.S. Pat. No. 3,206,247 issued to L. W. Johnson on 9-14-84 showed a form of angle-adjustable infant seat adapted to hold on the back of a car seat.
However, no system is believed to be available that provides the advantages of the present invention according to the objects thereof.
SUMMARY OF THE INVENTION
A principal object of this invention is to provide a system that permits an infant by means of an infant carrier to be conveniently and quickly and securely and comfortably attached to either an infant/toddler car seat installed in an automobile or to an infant/toddler stroller, without need to reorient or reposition the infant in the infant carrier.
Further objects are to provide a system as described that is economical and has multi-uses in that any of the three co-acting elements, carrier, car seat or stroller can, in proper circumstances, be used alone.
And further objects are to provide the three co-acting elements for easy purchase and use until the child is old enough to be buckled safely in a regular seat belt (an exemplary State law requires that a child must be either four years old or weigh forty pounds before it can be buckled in a regular seat belt. Otherwise it must be in a car seat).
Still further objects are to provide a system as described that has a provision for quiet, simultaneous one-hand locking and unlocking of an infant/toddler car seat, that is light in weight and strong and safe but not unduly bulky.
For purposes of this disclosure, the infant carrier of this invention may be termed an insert, in that it inserts into either of the other two elements of the system. Further, wherever "car seat" or "infant car seat" is mentioned, it is to be understood that "infant or toddler" car seat is meant for the purposes of this disclosure, including the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects and advantages of this invention will become more readily apparent on examination of the following description, including the drawings in which like reference numerals refer to like parts.
FIG. 1 is a fragmentary exploded perspective view showing the relation between an infant carrier and a car-seat, according to this invention;
FIG. 2 is an exploded view showing the relation between the infant carrier of FIG. 1 and a stroller;
FIG. 3 is a rear perspective view of the infant carrier of FIG. 1; and
FIG. 4 is a partially sectional diagram of an exemplary old-art one-point release that may be used in this invention.
DETAILED DESCRIPTION
FIG. 1 shows an infant car seat 20 (usable by infant pre-toddler or toddler, as noted) of a type that has an opening 22 beneath, formed by looped legs 24 protruding from the bottom of the seat 25 for passage of an automobile seat belt (not shown) that detachably affixes the car seat 20 to a seat of an automobile.
This showing is diagrammatical and may differ in detail without affecting the spirit of the invention, various suitable car seats being usable.
The car seat preferably has a conventional seat belt 26 of its own, and may be used independently of the invention for infants or toddlers. However, in such case an infant would have to be disturbed to put it into and to remove it from the car seat 20.
The invention provides means, however, for preventing disturbance of an infant being secured to or removed from the car seat.
For this, the infant is secured by means of a conventional safety belt 28 in infant carrier 30 on the seat 31 thereof. The infant may be asleep or otherwise tranquil and is unlikely to be disturbed when the infant-carrier 30 is carried to and secured to the car seat 20 (arrow).
In this procedure, unnecessary and undesirable fumbling with fasteners is avoided by the invention. The infant carrier 30 simply snaps into place in the car seat 20, both sides of each one being secured to the other.
In accordance with a further provision of this invention, one-point finger pressure releases both sides of the infant carrier, when desired, from the car-seat, leaving one hand free to stabilize the infant and infant carrier. The provision is substantially symmetrical and can be operated from either side.
Details making the one-point release possible are conventional and will be described further later. The invention lies in use of a one-point release of a two-side securance of infant carrier to car seat, and in location of same, not in the details of the mechanism. Visible in this figure are portions of the provision. A respective hole 32, shown, is provided in the lower sidewall of the car seat at the junction of the preferably continuous back 34 with the preferably continuous arm 36.
The holes face each other. Each hole has on the outside of the car seat a plunger 38 shown, to pass from outside-in in the hole when pressed, and on the inside a concave conical or funnel-like entrance 40, shown.
The infant carrier 30 has, contained in a molded portion 42 across the lower rear, a pair of spring-extended, coaxial, linked latches 44, laterally protrusive part shown, that snap into the holes 32 when the infant carrier 30 is pressed back into the car seat 20, fixing it to the car seat.
To release the infant carrier 30 from the car seat 20, either plunger, 38 shown, is pressed.
Strength and stability of the intimate fit of the joined car seat 20 and infant carrier 30 will be evident.
For guiding and further stabilizing the infant carrier 30 a pair of laterally spaced rounded projections or protrusions 45, 46 may project rearwardly from the upper back portion of the infant carrier and fit into mating apertures 50, 52 in the car seat 20; the fit is preferably latch-free for free reception and release, in accordance with the one-point provision for attachment and release provision of this invention.
The infant carrier 30 can be used alone as indicated, and for this a rearward incline or tilt-adjustment mechanism 54 is provided on the back, a portion of which is visible here. This is described later.
FIG. 2 shows the analogous nesting relation of the infant carrier 30 fit into the stroller 56 of this invention, onto the seat 57 of which the infant carrier with infant safely buckled in it can be inserted, or if desired, the infant carrier may first be installed and then an infant buckled in place. The protrusions 46,45 on the back of the infant carrier 30 fit through respective apertures in grommets 58, 60 in the back of the stroller 56 when the infant carrier is installed in it. As with the car seat, preferably the protrusions have no latching provision. The safety belt 62 of the stroller 56 is then buckled around the infant carrier 30. A latch 44 or equivalent lateral protrusion on the infant carrier 30 may protrude freely through a corresponding aperture of laterally located grommet 64 on each of the sides of the stroller for better securance. The stroller is preferably of the conventional folding type so that when the stroller is used alone, the canvas seat 57 and frame 59 can compactly collapse. Eight wheels 61 are preferred, Loading forces on the stroller with the carrier in place are low and uniform.
FIG. 3 shows a folding incline mechanism 54 on the back of the infant carrier for tilt-adjustment when the infant carrier is used alone.
First and second laterally-spaced resilient upright rails 66, 68 have ends fixed top and bottom as at 70, 73 to the back of the infant carrier. Three cross grooves 72, 74, 76 are molded into the back of the infant carrier parallel with each other and transverse to the rails. The rails force into any desired groove a transverse member 78, which may be a roller, constrained to move up or down by a linkage. The linkage includes on each side an upper link 80, 82 connected to the ends of the transverse member, a lower link 84, 86 pivotally fixed as at 88 to a lower portion of a respective resilient upright rail, and a hinge joint 90, 92 connecting each lower link 84, 86 with an upper link 80, 82. A brace 94 laterally connects the hinge joints. In operation, the position, in a particular groove, of this transverse member 78 sets the angle of incline resting back on a floor or bed of the mechanism, providing tilt adjustment but folding flat for installation of the infant carrier 30 into the car seat 20 or the stroller 56, when desired.
FIG. 4 shows a conventional one-point (either side) release, latch mechanism 96 that may be used with the system of this invention.
The mechanism is shown partially compressed, for exposition.
The car seat has on each side, coaxially facing each other a socket assembly 98 with an inward-facing conical entrance 40, a cylindrical passage 32 with a shoulder 100 and a plunger 102 with a flanged end 104 in the passage resting against the shoulder and biased outward by a compression spring 106 under an end cap 108, on the outside.
A tube 110 with a plunger latch 44, 44' slidably protruding coaxially from each end is held in a molded portion in the back of the infant carrier, or otherwise clamped in place. An internal spring 112 compressed between portions of the plunger latches urges the plunger latches to protrude and engage the respective cylindrical passages 32. Pressing on either of the end caps 108 at the ends of the tube, retracts both plunger latches by means of a respective rack 114, 116 integral with each plunger latch and inwardly engaging a pinion 118 pivotally mounted in the tube between an overlap of the racks. A keyway 120, 122 and key portion 124, 126 of the tube at each end prevents rotation of the plunger latches as they snap-in-place or retract.
Other mechanisms that will do for the purpose include station wagon rear seat latching systems that release both sides of a seat by actuation at either end.
The carrier and car seat may be of any suitable thermoplastic or metal, furthering the economy of this three piece coacting set.
This invention is not to be construed as limited to the particular forms disclosed herein, since these are to be regarded as illustrative rather than restrictive. It is, therefore, to be understood that the invention may be practiced within the scope of the claims otherwise than as specifically described.
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A system for supporting an infant in different modes of use includes co-acting infant carrier by which an infant can be carried in arms or supported on a surface at a selected angle, an infant/toddler car seat into which the carrier with the infant can be snapped in place quickly for auto travel and as quickly removed, using only one hand, and a stroller into which the carrier can be inserted and attached for rolling transport.
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